CEH Marketing Reports - Pigments

May 2001 575.0000 A Pigments Page 1 CEH Marketing Research Report PIGMENTS By Raymond Will with Akihiro Kishi CEH Marketing Research Reports provide comprehensive analysis, historical data and forecasts pertaining to the international competitive market environment for chemical products. Detailed supply and demand data are developed for the United States, Western Europe and Japan with the cooperation of chemical producers and consumers worldwide. Updated information may be available from the following CEH Program services: q q CEH Online—The full text retrieval and update database. Updated monthly. CEH CD-ROM—The entire contents of the CEH on one CD-ROM and including CEH Online updates. Issued quarterly. Manual of Current Indicators (MCI)—Updates of statistical data derived from published sources. Issued semiannually. The Economic Environment of the Chemical Industry (EECI)—Economic indicators that impact the chemical industry; issued quarterly. CEH Inquiry Service— SRI Consulting researchers are available to answer your questions. U.S.A.—Telephone: Zürich—Telephone: Tokyo—Telephone: 650/859-3900 411/283-6333 813/5251-1741 Fax: Fax: Fax: 650/859-2182 411/283-6320 813/5251-1754 q q q © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0000 B PIGMENTS Pigments Page 2 TABLE OF CONTENTS Summary .................................................................................................................................................. World Market Size............................................................................................................................... World Supply/Demand ........................................................................................................................ Leading Producers ........................................................................................................................... Inorganic Pigments .......................................................................................................................... Organic Pigments............................................................................................................................. Production........................................................................................................................................ Consumption.................................................................................................................................... World Pigments Business Development ............................................................................................. Demand............................................................................................................................................ Supply .............................................................................................................................................. Market Participants .......................................................................................................................... Product Range.................................................................................................................................. Introduction.............................................................................................................................................. Environmental issues ............................................................................................................................... White Pigments........................................................................................................................................ Black Pigments ........................................................................................................................................ Inorganic Color Pigments ........................................................................................................................ Description........................................................................................................................................... Iron Oxide Pigments ........................................................................................................................ Natural Iron Oxide Pigments ....................................................................................................... Synthetic Iron Oxide Pigments.................................................................................................... Chrome Pigments............................................................................................................................. Complex Inorganic Pigments .......................................................................................................... Ultramarine Pigments ...................................................................................................................... Iron Blue Pigments .......................................................................................................................... Cadmium Pigments.......................................................................................................................... Bismuth Vanadate Pigments............................................................................................................ Rare Earth Sulfide Pigments............................................................................................................ Manganese Violet Pigments ............................................................................................................ Manufacturing Processes ..................................................................................................................... Iron Oxide Pigments ........................................................................................................................ Natural Iron Oxide Pigments ....................................................................................................... Synthetic Iron Oxide Pigments.................................................................................................... Chrome Pigments............................................................................................................................. Complex Inorganic Pigments .......................................................................................................... Cadmium Pigments.......................................................................................................................... Supply and Demand by Region ........................................................................................................... United States.................................................................................................................................... Iron Oxide Pigments .................................................................................................................... Producing companies............................................................................................................... Salient statistics........................................................................................................................ Consumption............................................................................................................................ © 2001 by the Chemical Economics Handbook—SRI International 7 7 11 11 11 12 13 14 16 16 17 17 18 19 30 32 33 33 33 33 34 35 35 37 38 38 38 39 39 40 40 40 40 40 43 44 44 45 45 45 45 48 54 May 2001 575.0000 C PIGMENTS Pigments Page 3 TABLE OF CONTENTS (continued) Price ......................................................................................................................................... Trade ........................................................................................................................................ Chrome Pigments......................................................................................................................... Producing companies............................................................................................................... Salient statistics........................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Complex Inorganic Pigments ...................................................................................................... Producing companies............................................................................................................... Production................................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Cadmium Pigments...................................................................................................................... Producing companies............................................................................................................... Salient statistics........................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Other Inorganic Pigments ............................................................................................................ Canada ............................................................................................................................................. Producing Companies .................................................................................................................. Consumption................................................................................................................................ Trade ............................................................................................................................................ Mexico ............................................................................................................................................. Producing Companies .................................................................................................................. Iron oxide pigments ................................................................................................................. Chrome pigments..................................................................................................................... Complex inorganic pigments ................................................................................................... Production.................................................................................................................................... Consumption................................................................................................................................ Trade ............................................................................................................................................ South America ................................................................................................................................. Iron Oxide Pigments .................................................................................................................... Chrome Pigments......................................................................................................................... Complex Inorganic Pigments ...................................................................................................... Cadmium Pigments...................................................................................................................... Consumption................................................................................................................................ Western Europe................................................................................................................................ Iron Oxide Pigments .................................................................................................................... Producing companies............................................................................................................... Salient statistics........................................................................................................................ Production................................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Chrome Pigments......................................................................................................................... Producing companies............................................................................................................... Salient statistics........................................................................................................................ © 2001 by the Chemical Economics Handbook—SRI International 62 63 66 66 67 69 74 74 76 76 77 78 80 81 81 81 81 85 86 86 86 86 86 86 87 87 87 87 88 88 88 89 90 90 90 91 91 92 92 92 92 98 98 102 107 108 109 109 113 May 2001 575.0000 D PIGMENTS Pigments Page 4 TABLE OF CONTENTS (continued) Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Complex Inorganic Pigments ...................................................................................................... Summary .................................................................................................................................. Producing companies............................................................................................................... Production................................................................................................................................ Consumption............................................................................................................................ Trade ........................................................................................................................................ Ultramarine Pigments .................................................................................................................. Summary .................................................................................................................................. Producing companies............................................................................................................... Production................................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Iron Blue Pigments ...................................................................................................................... Summary .................................................................................................................................. Producing companies............................................................................................................... Production................................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Cadmium Pigments...................................................................................................................... Producing companies............................................................................................................... Production................................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Trade ........................................................................................................................................ Bismuth Vanadate Pigments........................................................................................................ Producing companies............................................................................................................... Consumption............................................................................................................................ Rare Earth Sulfide Pigments........................................................................................................ Producing companies............................................................................................................... Production................................................................................................................................ Consumption............................................................................................................................ Price ......................................................................................................................................... Eastern Europe................................................................................................................................. Producing Companies .................................................................................................................. Production.................................................................................................................................... Consumption................................................................................................................................ Japan ................................................................................................................................................ Producing Companies .................................................................................................................. Iron oxide pigments ................................................................................................................. Chrome pigments..................................................................................................................... Other color inorganic pigments ............................................................................................... Production.................................................................................................................................... Consumption................................................................................................................................ © 2001 by the Chemical Economics Handbook—SRI International 113 115 116 117 117 117 119 119 121 121 121 121 122 122 123 123 125 125 126 127 127 128 128 129 130 132 132 134 134 136 136 137 137 138 138 138 138 138 138 144 145 146 146 149 149 149 150 151 ................................................................................................................................................................................................................ Taiwan ................................................................................................................................................ Quinacridone Pigments.................................................................................................................. Other Asian Countries ............................................................................................................................................................................................................................. Producing Companies ......... Trade .............................................................................................................. Quinacridone Pigments...................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................... Salient Statistics............................................................................ Trade ........................................... Other Organic Pigments ........................................................... Phthalocyanine Pigments...................................................................................................................................................................................................................................................................................................................... Producing Companies ...................... Imports.................. United States....................................... Manufacturing Processes ............................................................................................................... Paints and coatings ............................................................ Trade ........... pigmented fibers and rubber ................................................................................................................................................ Trade ............................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................................... Trade . Other ... Producing Companies .............................................. Perylene Pigments....... Printing inks..................................................................... Producing Companies .............................. Condensation Acid Pigments.................................................................................................................................................................................................................................................................................................................................................................... China...................................................................................................................................................................................................................... South America .... Producing Companies ........................................................................................................................................................................................... Supply and Demand by Region ................................................................ Azo Pigments. Mexico ....................................... Price ............................................... Basic Dye Pigments........... Trade ............................................................................................................................................................................. 154 155 157 157 160 160 161 162 162 162 163 163 163 163 163 164 166 167 168 168 168 169 169 170 172 173 173 173 173 180 184 187 191 194 198 199 200 201 201 202 202 202 203 203 204 205 © 2001 by the Chemical Economics Handbook—SRI International ........................May 2001 575............................ Organic Color Pigments ......................... Producing Companies ........................... Phthalocyanine Pigments........................................................................................................................................................... Plastics.................................................................................................. Producing Companies .......................................................... Azo Pigments.................................................................................................................. Description.................... Republic of Korea...................................................................................0000 E PIGMENTS Pigments Page 5 TABLE OF CONTENTS (continued) Price ......................................................................... Trade .................................................. Exports..................................................................................................................... Consumption......................................................................................................................................................................................................................................................................................................................................................................................................................................................................... Canada .................................... ............................................................... Textile printing .................................................................................................................................................................................................................................................................................................. China..................................................................................................... Price .......................................... Production...................................... Japan ..................................................................... Other Asian Countries ...................................... Consumption................................................................................... Other organic pigments................................................................0000 F PIGMENTS Pigments Page 6 TABLE OF CONTENTS (continued) Western Europe........................................................................................................................................................................................................................................................ Other ..................................................................................... Printing inks.................................................................................................................................................... Czech Republic....................................................................................................................... Production........................................................................................................................................................................................................ Republic of Korea........................................................................................................................................................................................ Producing Companies ................................................................... Phthalocyanine pigments............................................... Producing Companies ...................... India .............................................................................................. Imports....................................................May 2001 575................................................................................................................................................... Trade ...................................................................................... Eastern Europe........................................ Pigments for paper .................................................................................................................................................................................................................................................................................................................................................................................................................. Hungary.......................................................................................................................................................... Consumption............................................................................................................... China...................................................................................................... Taiwan ............................................................................................................................................................................................................. Producing Companies ...................................... Price ................................. Pigmented fibers .............................................................................................................................................................................. Exports........... Azo pigments ......................... 236 Bibliography ................................................................................................................................................................................................................................................... Production................................................................................................................................................................................................................................................................. Paints and coatings .......................................................................................................................................................................................................... 239 © 2001 by the Chemical Economics Handbook—SRI International ......................................... 205 206 206 208 211 212 214 215 217 217 217 219 219 219 220 220 221 222 222 223 223 223 223 224 224 226 228 231 231 233 234 235 236 236 236 Appendix—Special Effect Pigments ............................ Plastics and rubber ....... Commonwealth of Independent States ...................................................................................................................................................................................................................................................................................... 6 billion for inorganic color pigments and $4. the global pigment market appreciated by 25% between 1996 and 1999. while in dollar terms it grew by only 7%.9 billion for organic pigments. dollar increased in value by 17% relative to the Euro.5 billion) Organic Pigments High-Performance 15% Iron Oxide 13% Inorganic Pigments Complex Inorganic 12% Phthalocyanine 23% Other Inorganic 8% Chrome Pigments 6% Azo/Other 23% World Pigment Production by Region Eastern Europe 3% Central/South America 5% Japan 11% Middle East. © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575.5 billion—$2. Africa and Other 3% Western Europe 37% Other Asia 14% North America 28% * Between 1996 and 1999 the average unit weight value for color pigments declined about 13% in dollar terms. stated in Euro terms. of which high-performance organic pigments accounted for $1. over the same period the U. Therefore. Between 1996 and 1999 the global color pigments market has been impacted by declines for prices for most pigments classes. however.1 billion.0000 G PIGMENTS Pigments Page 7 SUMMARY WORLD MARKET SIZE In 1999.S. The following pie charts provide an overview of the total world market value for colored pigments by chemical class and by region:* World Market Value of Colored Pigments by Chemical Class—1999 (total market value = $7. the world market value for colored pigments (inorganic and organic) reached $7. . Includes all organic pigments. Western Europe is the largest colored pigments–producing region. © 2001 by the Chemical Economics Handbook—SRI International . North America and Europe (i. followed by North America with 28%.400 1. for the three main organic pigment classes—classical azo pigments. Together with Japan. Shown below is the world market value by type of organic pigment.600 1.000 800 600 400 200 0 Central/ South America Eastern Europe Middle East and Africa and Othera Millions of Dollars High-Performance Pigments Phthalocyanines Azo/Other North America Western Europe Asia. while Asia accounted for 25% of the total market.May 2001 575. Other Japan a. these regions also account for the dominant share of the most profitable pigments market—high-performance pigments.e.0000 H PIGMENTS Pigments Page 8 With a 37% market share. Western and Eastern Europe) are clearly the largest markets for organic pigments. The following graph shows the world market value in 1999 by region.200 1. phthalocyanine pigments and organic high-performance pigments: World Market Value of Organic Pigments by Region and Chemical Class—1999 1. 0000 I PIGMENTS Pigments Page 9 World Market Value of Organic Pigments by Chemical Class—1999 High-Performance Pigments 12% Phthalocyanine Pigments 29% Azo/Other 59% Total Market Value = $4. but exclude consumption of special effect (pearlescent/ luster and metallic pigments) and anticorrosion pigments. printing inks. The following table summarizes the world pigments consumption in value terms in 1999. while the high-performance pigments group typically retains higher margins. paper and leather. followed by phthalocyanines (blue and green). The data include all major pigment applications. © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. High-performance pigments accounted for the remaining 12%. The classical azo and phthalocyanine pigments groups are characterized by lower profit margins resulting from rising competition from lower-priced imports. Ciba Specialty and BASF. as well as textile printing. with a share of 29%.9 billion With a 59% world market value share in 1999. azo pigments are the largest group of organic pigments. paints and coatings and plastics. This latter group is dominated by the leading organic pigment producers: Clariant. May 2001 575.260 84 74 31 189 350 557 446 269 1.Pigments Page 10 World Market Value of Color Pigments by Region—1999 (millions of dollars) North America Iron Oxides Chromes Chromates Chromium Oxide Complex Inorganic Ultramarines Iron Blues Cadmiums Bismuth Vanadate Rare Earth Sulfides Total 310 56 39 299 26 8 4 6 0 747 South America 52 11 11 71 9 2 3 0 0 159 Western Europe 385 37 121 267 25 16 6 10 0 866 Eastern Europe 33 7 5 13 6 2 5 0 0 71 Africa and Middle East 71 9 8 28 11 3 4 0 0 134 Japan 54 13 25 142 7 2 1 2 0 246 Rest of Asia 105 47 22 116 5 8 4 1 0 307 Other 10 3 3 4 2 0 0 0 0 21 Total 968 182 233 939 91 40 28 19 1 2.099 4.458 CEH estimates.907 7.138 36 67 11 114 185 406 0 0 406 540 173 183 244 600 846 208 381 141 731 1.038 8 15 7 31 52 2.272 2.695 1.0000 J © 2001 by the Chemical Economics Handbook—SRI International .551 PIGMENTS .565 2.114 1.551 Azo/Other Phthalocyanine High-Performance Total Total Colored SOURCE: 641 529 395 1. Headquarters Bayer. Bayer. however. while organic pigments typically have higher prices and higher premiums. the inorganic pigment business is significantly smaller. Only a few companies manufacture both pigment groups. Laporte (acquired by Kohlberg. Their headquarters and manufacturing locations are shown in the following table: World’s Largest Synthetic Iron Oxide Pigment Manufacturers Company. United States Toda Kogyo. for BASF and Ciba.0000 K PIGMENTS Pigments Page 11 WORLD SUPPLY/DEMAND LEADING PRODUCERS In general. © 2001 by the Chemical Economics Handbook—SRI International . q q q INORGANIC PIGMENTS The largest inorganic pigment is synthetic iron oxide. Japan SOURCE: CEH estimates. Worldwide. United Kingdom Rockwood Pigments. which holds roughly half of the world’s market. the top four producers of synthetic iron oxide pigments in 2000 are ranked as follows: Bayer. Elementis. This tendency to specialize is attributable to the differences between inorganic and organic pigments in: q manufacturing processes—having no chemistry in common volumes—organic pigment market segments typically are smaller market segments—few applications in common prices and premiums—inorganic pigments tend to be less expensive. BASF and Ciba manufacture both. and Toda Kogyo.May 2001 575. Germany Manufacturing Locations Brazil China (finishing plant) Germany China United Kingdom United States China Germany Italy United Kingdom United States Japan Elementis. Kravis Roberts). pigment producers specialize either on the manufacture of inorganic pigments or organic pigments. Ltd. followed closely by Ciba Specialty.. Switzerland Clariant... Japan SOURCE: CEH estimates. Germany Ciba.0000 L PIGMENTS Pigments Page 12 O RGANIC PIGMENTS The world’s largest organic pigment manufacturers include four Western European firms.) Japan Denmark (KBK) India (Shudishan) United States (Sun Chemical) Japan France (Francolor) Mexico Bayer. are the market leaders of organic pigments. Germany Manufacturing Locations Brazil China Germany United States Germany Mexico United States China Germany Switzerland United Kingdom China France Germany India Japan Mexico Spain United States Japan United States (Diacolor-Pope) Dainippon Ink and Chemicals. Clariant.. followed by three Japanese companies.May 2001 575. Germany Dainichiseika Color and Chemicals Mfg. At some distance follow BASF and other listed companies. © 2001 by the Chemical Economics Handbook—SRI International . Japan Toyo Ink Mfg. Co. Co. Japan China (Suzhou Lintong Dyestuff Chemical Co Ltd.. Within the large-volume group of phthalocyanine pigments BASF is the world’s leading producer. Ltd. headquarters and manufacturing locations are shown in the following table: World’s Largest Organic Pigment Manufacturers Company. Headquarters BASF. Inc. Western Europe leads in production of chrome (or chromium) pigments and organic pigments and in the total production of all colored pigments. The figures below illustrate world production of organic pigments by region and chemical class in 1999. China. Five countries. Asia has become an important organic pigments– producing region in volume terms. India. The following graphs show the estimated world production by major pigment group in 1999: World Production of Pigments—1999 Other 20% Complex Inorganic 6% HighPerformance 7% Chromes 15% Azo 35% Phthalocyanine 17% Other Pigments 8% Carbon Black 8% Iron Oxides 16% Titanium Dioxide 68% Total Production = 5. black and colored pigments reached 5.7 million metric tons in 1999.7 Million Metric Tons Synthetic iron oxides represent the largest share of the worldwide colored pigments market and production is dominated by Western Europe. Likewise. © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. including organic pigments. about 8% pigment-grade carbon black and only 8% for other colored pigments. as a percent of the total on a dry weight basis. accounting for about 25% of total world production. including Japan.0000 M PIGMENTS Pigments Page 13 PRODUCTION Total world production of white. of the three major regions covered in this report. The United States is a significant producer of organic pigments. Of this volume approximately 68% was titanium dioxide. account for most Asian production. 16% iron oxide pigments. During the last decade production of and demand for organic pigments in Eastern Europe has declined sharply and is only now gradually stabilizing. the Republic of Korea and Taiwan. accounted for nearly 26% of total organic pigments production in 1999. however. anthraquinone and perylene. Among the most expensive pigment groups are pigments such as diketo-pyrrolo-pyrrole quinacridone. The following table gives an estimate of the world pigments consumption by region and main pigment class: © 2001 by the Chemical Economics Handbook—SRI International . Most of the phthalocyanine.7 million metric tons in 1999.to medium-value group of products. About 60% of organic pigments have an azo structure in their molecule.and azo-based pigments are considered to be in the lower. in the hands of only a few international companies. phthalocyanine blue and green. CONSUMPTION The world consumption of white.May 2001 575. The high-performance products are found primarily in the polycyclic pigments. black and colored pigments reached approximately 5.0000 N PIGMENTS Pigments Page 14 World Production of Organic Pigments—1999 (total production = 249 thousand metric tons) Polycyclic and Other 8% Other 12% Other Azo Pigments 8% United States 29% Naphthol AS 8% Japan 14% Phthalocyanine Blue and Green 29% Diazo 12% Other Asia 19% Western Europe 26% Monoazo 13% Red Lakes 22% By Region By Chemical Class Two pigments. The business of these pigments is. 200 93.000 2.866 1 64.200 2.100 PIGMENTS . dry pigment basis) North America White Titanium Dioxide Zinc Oxide Black Carbon Black Color Inorganic Iron Oxides Chromes Chromates Chromium Oxide Complex Inorganic Ultramarines Iron Blues Cadmiums Bismuth Vanadate Rare Earth Sulfides Total Color Organic Azo/Other Phthalocyanine High-Performance Total Total Color Total South America Western Europe Eastern Europe Africa and Middle East Japan Rest of Asia Other Total 172.640 4.034 880.Pigments Page 15 World Consumption of Pigments by Region—1999 (metric tons.0000 O SOURCE: CEH estimates.671 350.895 13 1.382 538 300 12 94.496 8.380 6.914 10.882 1.181 64.631 85.385 872.350 10.000 2.200 0 73.886 46.000 3.000 4.000 2.304 282.395 61.769 36.230 15.000 22.496 237.118 30.682 0 36.478 22.677 4.049 1.099.600 48.600 1.389 569 4 327.400 3.595 95.719 69.000 4.607 30.900 365.000 2.851.709 43.986 0 10.000 500 108 440 50 0 5 471.000 120.200 71.520 28.746 309.600 2.700 4.553 3.308 1.000 42.800 4.000 137.348 6.077 6.242 2.318 6.000 42.000 3.491 147.500 8.144 1 59.719.000 7.250 28.793 1.000 13.694.500 1.400 862 2.177 14.500 261.348.708 5.000 12.200 754 11.525 1.059 410.127 249.280 16.189 17.200 475.044 1.000 500 300 17.581 3.000 400 1.000 350 30 5.000 12.200 1.692 754 377 0 52.094 64.815 72.980 700 600 200 1.659 53.000 362 172 47.000 19.500 12.154 2.600 4.978 834 10.000 18.640 47.441 May 2001 575. © 2001 by the Chemical Economics Handbook—SRI International 1.027 5 404.399 159.500 1.100 652.500 400 400 0 28.200 200.800 500 100 50 53.709 7.046 6.000 3.000 8.250 9.000 189.338.550 84.859 1 122.908 2.700 300 6.300 7.000 3.000 21.112.030 48.887.600 4.300 4. 0000 P PIGMENTS Pigments Page 16 Titanium dioxide. Western Europe is. The following pie chart gives the world consumption in volume by main application for 1999: World Consumption of Organic Pigments by Market Value—1999 Pigmented Fibers 3% Textile Printing 4% Plastics 12% Paper Other 3% 2% Printing Inks 54% Paints and Coatings 22% WORLD PIGMENTS BUSINESS DEVELOPMENT The world pigment business situation and particularly that of organic pigments. In Japan. titanium dioxide and carbon black are each described in detail in separate marketing research reports. paints and coatings and plastics—accounted for about 88% of total organic pigments consumption in 1999. Three main applications—printing inks. Within color pigments. In Asian countries © 2001 by the Chemical Economics Handbook—SRI International . The United States is the largest color pigment–consuming country. Iron oxide pigments accounted for about 65% of the total color pigments consumption in 1999. with a slightly stronger growth for Western Europe and stronger growth for the United States. Worldwide markets for pigments are expected to grow more or less in line with GDP during the next five years.May 2001 575. the demand for pigments is expected to grow only slightly. accounting for about 22% of the total consumption. accounting for about 37% of total consumption. From this perspective it is understandable that much of the market attention is focused on this single pigment. accounted for about 24% of the total pigment consumption in 1999. paints and coatings. the most important white pigment. accounted for 68% of total world pigment consumption by weight. the maturing markets in some applications and regions. DEMAND The consumption of pigments is driven primarily by growth in the printing inks. is expected to change steadily during the next decade. the largest consuming region. Because of this. however. the continued oversupply of classical pigments (keeping prices depressed) and the ever increasing environmental pressures. and plastics industries. The color pigments. iron oxide pigments are the largest in volume terms. which are described in this report. The major business trends are described below. Some of the most important challenges for pigment producers will be to cope with the rapid globalization of the business. Total consumption of iron oxide pigments by volume will grow moderately over 1999-2005. will experience moderate growth. which is the largest market for iron oxides.May 2001 575. competitive factors and the impacts of environmental regulations. commodity-type azo pigments and phthalocyanine pigments) and. in a few regions such as Asia and Oceania. Overall it can be expected that during 1999-2004. the market value in Asia (excluding Japan) will grow by 5-6% per year. particularly in surface coating applications but also for printing inks. China will require more sophisticated pigments for colored plastic goods. However. possibly above the growth rate in North America.to medium-tier products is expected to continue to migrate from Western Europe and the United States to the lower-cost countries. as will consumption of cadmium pigments. followed by paints and coatings and plastics.0% per year by volume. as well as for pigment-printed textiles. For the export market. In South America. One of the two major classes of chrome pigments. averaging 4-8% per year during 1999-2004. chrome orange and molybdate orange).0000 Q PIGMENTS Pigments Page 17 other than Japan. where the development and use of specialty high-performance organic products continues to increase. however. SUPPLY The production of low. paints and coatings. demand for pigments will grow significantly. closed their plants or were acquired by larger. is expected to continue to decline. MARKET PARTICIPANTS During the last decade.g. A number of smaller producers. The largest end-use markets for color inorganic pigments are construction. will not be spectacular. Actual value increases. aided by their partial absorption of the markets lost by cadmium and chrome pigments. During 1999-2004. the domestic demand for pigments is expected to grow modestly. South America (primarily Argentina and Brazil). iron oxide pigments. the color pigments industry has passed through a period of significant restructuring. color organic pigment consumption in the three major regions combined will grow 2. lead chromates (primarily chrome yellow. Consumption of the other major class. to a lesser degree. Health and environmental concerns about heavy metal–containing pigments and increased competition from organic replacements are adversely affecting overall consumption of lead chromate and cadmium pigments. In early 2001. Western Europe and Japan were distributed as follows: © 2001 by the Chemical Economics Handbook—SRI International . such as China and India (e.. primarily China and India. plastics and ceramics. while smaller than in the United States or Western Europe. The highest growth rate will be in plastics applications.5 to 3. Other Asian nations will develop a demand pattern similar to China and it can be expected that the demand in most Southeast Asian countries will grow substantially. remaining well below the increase in any of the three major countries/regions. is still increasing gradually. consumption of cadmium pigments. color pigment producers in the United States. responding to the globalization of pigment markets. Color organic pigments are consumed mostly for printing inks. mainly Western European or Japanese firms. Product lines were realigned toward the more profitable. with continued demand from the construction industry. Worldwide consumption of complex inorganic pigments will experience some growth in volume. higher-value pigments. green chromium oxide. unable to compete with larger international firms. Japan and Western Europe within a few years. In Asia and particularly in China and India. Because some companies produce both inorganic and organic pigments. 20 40 14 74 Organic 18 11 16 45 Total 38 51 30 119 Excludes white pigments and carbon black. On the supply side. SOURCE: As a result of the anticipated market changes discussed above. Toll manufacturing and swap deals will become even more important. particularly for pigments used in end products © 2001 by the Chemical Economics Handbook—SRI International . plastics and spin-dyeing markets. complex inorganic color pigments. A strong local market presence is required in order to capture a sizeable volume of this growing business.g. Large producers are finding their competitive strengths by streamlining their product ranges and shifting production to lower cost countries. such as the printing inks. some of the most important challenges to producers will include: q A continued phase-out of heavy metal–containing pigments. q q q PRODUCT RANGE From a product portfolio perspective. will continue as pigment producers secure their shares in the increasingly competitive market. The downstream integration of pigment producers to end-use markets. Global price competition and market efficiencies are in turn facilitated by electronic commerce as well as advances in automated inventory control and logistics management for both producers and consumers of pigments. CEH estimates. coating. many of the Asian countries have clearly emerged as the most rapidly growing markets for pigments. On the demand side. including high-performance pigments. These pigments will be replaced by organic.. the producers of pigments are faced with significant challenges as well as opportunities: q Prices are becoming uniform between regions as markets become increasingly efficient and global. For this reason. etc. the sourcing of unfinished (requiring grinding. It can be expected that heavy metal pigment substitution will be completed in the United States.) large-volume pigments from lower-cost production sites in these countries helps sustain corporate profit margins. bismuth vanadate and rare earth sulfide pigments). each number represents the net number of corporate entities involved in that particular region(s) or pigment category. new opportunities are further developing for international companies. as well as novel inorganic pigments (e.0000 R PIGMENTS Pigments Page 18 Number of Color Pigment Producers by Major Region—2001a Inorganic United States Western Europe Japan Total a.May 2001 575. the totals do not equal the sums of the categories. The other countries will soon have to follow suit. Other markets include paper. elastomers.0000 S PIGMENTS Pigments Page 19 that are destined for Western markets. powder coatings and radiation-curable inks and coatings). This report focuses on pigments classified as colorants—those that possess opacity and contribute to the color or color-related properties of the vehicles into which they are incorporated.. Western Europe and Japan. Extender pigments (used for cost reduction and to control such other noncolor characteristics as viscosity and gloss of the end product and anticorrosiveness) and functional pigments are briefly treated only qualitatively. Pigments can be defined as follows: Color. The data are segmented first by inorganic color pigments and organic color pigments and then geographically by North America. © 2001 by the Chemical Economics Handbook—SRI International . other inorganics and organics—are treated separately.g. * An extender pigment is a pigment used to reduce cost per unit volume by increasing bulk. primarily titanium dioxide and black pigments. white or fluorescent particulate organic or inorganic solids which usually are insoluble in and essentially physically and chemically unaffected by. Pigments are usually dispersed in vehicles or substrates for application. Small.g.to medium-sized producers of pigments. complex inorganics. They alter appearance by selective absorption and/or by scattering of light. information is presented for South America.May 2001 575. in particular. primarily carbon black. pigments with increased fastness and heat stability). q INTRODUCTION The worldwide pigments industry produces hundreds of colorant. Pigments retain a crystal or particulate structure throughout the coloration process. the supply of and demand for each major colorant group—iron oxides. customized pigment dispersions. Further. plastics (including spin-dyed fibers) and construction materials. Further information on these pigments (including metal flakes) may be found elsewhere in the Chemical Economics Handbook. cadmiums.. producers will have to continue to modify their pigment lines to ensure acceptance in more environmentally acceptable technologies (e. at least temporarily. the vehicle or substrate in which they are incorporated. the Republic of Korea and Taiwan. China. within each geographic segment. producers of heavy metal–based color inorganic pigments will be facing critical decisions regarding their viability to remain in the pigments business at all. In many cases.* The major markets are paints and coatings. destroys any crystal structure of the color substances.” according to the Ecological and Toxicological Association of the Dyestuff Manufacturing Industry (ETAD). food and cosmetics. In addition. which together produce and consume the majority of the world’s pigments. White pigments. waterborne coatings. Eastern Europe. glass. will have to invest in R&D to be in a position to offer new products and customized service (e. ceramics. “dyes are soluble and/or go through an application process which. extender and functional pigments for a wide spectrum of industrial and consumer markets. chromes. In contrast. textiles. inks. are only mentioned briefly since titanium dioxide and carbon black are extensively treated in the CEH marketing research reports on those subjects. q In the surface coating and printing ink markets. black. the two primary ones are as colorants and extenders. antifouling capability. white or color. rubber acceleration activation and reinforcement. The following list is a key to the color groups and chemical compositions: Representative Pigments by Chemical Class and Color Inorganic Pigments White Pigments Antimony Trioxide PW-11 Calcium Carbonate Lithopone PW-5 Titanium Dioxide White Lead or Basic Lead Carbonate PW-1 Zinc Oxide (zinc white) Zinc Sulfide Black Pigments Acetylene Black Bone Black Carbon Black Furnace Black Thermal Black Complex Inorganics Graphite or Crystallized Carbon Lampblack Magnetite or Naturally Occurring Iron Oxide Manganese Black Mineral Black Synthetic Black Iron Oxide Color Pigments Cadmium Pigments (all :1 are Lithopone form) Orange Cadmium Sulfoselenide Orange PO-20 PO-20:1 Cadmium Mercury Sulfide PO-23 Red Cadmium Sulfoselenide Red PR-108 PR-108:1 © 2001 by the Chemical Economics Handbook—SRI International . Pigments may be segregated in any one of several different ways.May 2001 575.0000 T PIGMENTS Pigments Page 20 Pigments serve several functions. (2) chemical type— organic or inorganic. Other functional applications include providing corrosion or heat resistance. In this report the criteria on which the classification system is based are as follows: (1) colorant—black. (3) origin—natural or synthetic and (4) chemical structure. 0000 U PIGMENTS Pigments Page 21 Representative Pigments by Chemical Class and Color (continued) Inorganic Pigments (continued) Color Pigments (continued) Cadmium Mercury Sulfide PR-113 Yellow Cadmium/Zinc Sulfide Yellow (lemon) PY-35 PY-35:1 Cadmium Sulfide Yellow (primrose) PY-37 PY-37:1 Chrome Pigments Barium Chromate PY-31 Chromium Oxides or Chromium Oxide Greens or Chrome Oxide Greens Chromium Oxide Green or Anhydrous Oxide PG-17 Hydrated Chromium Oxide Green or Hydrated Oxide or Guignet’s Green PG-18 Chromium Phosphate or Arnavdon’s Green PG-17:1 Lead Chromates Basic Lead Silicochromate PO-21:1 Chrome Green PG-15 Chrome Orange PO-21 Chrome Yellow PY-34 Molybdate Orange PR-104 Normal Lead Silicochromate (yellow) Strontium Chromate PY-32 Zinc Chromate or Zinc Yellow PY-36 Complex Inorganic Pigments Cobalt Blue or Cobalt Aluminate Blue Spinel PB-28 Cobalt Chromite Blue-Green Spinel PB-36 Cobalt Chromite Green Spinel PG-26 Cobalt Titanate Green Spinel PG-50 Cobalt Violet Phosphate PV-14 Copper Chromite Black PBk-28 © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. 0000 V PIGMENTS Pigments Page 22 Representative Pigments by Chemical Class and Color (continued) Inorganic Pigments (continued) Complex Inorganic Pigments (continued) Chrome Titanate or Chrome Antimony Titanium Buff Rutile PBn-24 PBn-29 PBn-31 Iron Cobalt Chromite Black PBk-27 Manganese Titanate or Manganese Antimony Titanium Buff Rutile PY-164 Nickel Ferrite Brown Spinel PBn-34 Nickel Titanate or Antimony Titanium Yellow Rutile PY-53 PY-119 PY-157 PY-161 Iron Oxide Pigments Natural Iron Oxide Pigments Black PBk-11 Brown Metallic Brown Natural Van Dyke Brown Umbers Burnt (deep reddish brown) Raw PBn-7 Micaceous Iron Oxide Black Natural Red PR-102 Yellow to Red Ochers (yellow) PY-43 Siennas (yellow-orange-red) Raw Sienna (yellow) Burnt Sienna (red) Synthetic Iron Oxide Pigments Black PBk-11 Brown PBn-6 Red Oxide Synthetic Ferric Oxide PR-101 Tan PBn-11 (ferrite containing zinc oxide or magnesium oxide) Yellow PY-42 © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. Milori or Prussian Blues PB-27 Manganese Violets PV-16 Rare Earth Sulfides PO-78 PR-265 (two types) PR-275 (two types) Yellow Pigment Ultramarine Blue PB-29 Ultramarine Violet PV-15 Organic Color Pigments Azo Pigments Arylide (Hansa) Yellows and Oranges PY-1 PY-3 PY-65 PY-73 PY-74 Benzimidazolones Pbn-25 PO-36 PO-60 PO-62 PR-171 PR-175 PR-176 PR-185 PR-208 PV-32 PY-120 PY-151 PY-154 PY-156 PY-175 Diarylide Oranges and Yellows Dianisidine Orange PO-16 Diarylide Yellow AAA PY-12 PY-13 Diarylide Yellow AAOT PY-14 PY-17 PY-83 © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575.0000 W PIGMENTS Pigments Page 23 Representative Pigments by Chemical Class and Color (continued) Inorganic Pigments (continued) Other Inorganic Pigments Bismuth Vanadate PY-184 Iron Blues or Ferriferrocyanides or Chinese. May 2001 575.0000 X PIGMENTS Pigments Page 24 Representative Pigments by Chemical Class and Color (continued) Organic Color Pigments (continued) Azo Pigments (continued) Dinitraniline Orange PO-5 Disazo Condensation Pigments PBn-23 PO-31 PR-144 PR-166 PY-93 PY-95 PY-128 Lithol® Red Sodium Salt PR-49 Barium Salt PR-49:1 Calcium Salt PR-49:2 Strontium Salt PR-49:3 Lithol® Rubine PR-57 Calcium Salt PR-57:1 Naphthalene Sulfonic Acid Pigment Lakes PO-19 PR-60:1 PR-66 PR-67 PY-104 Naphthol Reds and Browns PR-2 PR-5 PR-7 PR-9 PR-17 PR-22 PR-23 PR-31 PR-112 Naphthol Red PR-170 PBn-1 Permanent Red 2B PR-48 Barium Salt PR-48:1 Calcium Salt PR-48:2 Strontium Salt PR-48:3 Manganese Salt PR-48:4 © 2001 by the Chemical Economics Handbook—SRI International . 0000 Y PIGMENTS Pigments Page 25 Representative Pigments by Chemical Class and Color (continued) Organic Color Pigments (continued) Azo Pigments (continued) Pyrazolones Bright Orange Red PO-13 PO-34 Red PR-38 Red Lake C Sodium Salt PR-53 Barium Salt PR-53:1 Red 2G PR-52 Calcium Salt PR-52:1 Manganese Salt PR-52:2 Scarlet 3B Lake PR-60 Toluidine Red PR-3 Condensation Acid Pigments Alkali Blue PB-19 PB-61 Perylene Pigments PR-123 PR-149 PR-178 PR-179 PR-190 PR-224 Phthalocyanine Pigments Copper Phthalocyanine Blue PB-15 Alpha 15:1 NC (noncrystallizing) Alpha 15:2 NCNF (noncrystallizing/nonflocculating) Beta 15:3 NC Beta 15:4 NCNF Copper Phthalocyanine Green PG-7 PG-36 Phthalocyanine Blue.May 2001 575. Metal-Free PB-16 © 2001 by the Chemical Economics Handbook—SRI International . © 2001 by the Chemical Economics Handbook—SRI International . The following table presents the commercially most important organic pigments. The largest-volume products are boldfaced.4-Diketo-pyrrolo-pyrroles (DPPs) PR-254 PR-255 Flavanthrone Yellow Fluorescent Organic Pigments Indanthrone Blue Isoindolines.May 2001 575.0000 Z PIGMENTS Pigments Page 26 Representative Pigments by Chemical Class and Color (continued) Organic Color Pigments (continued) Quinacridone Pigments PO-48 PO-49 PR-122 PR-202 PR-206 PR-207 PR-209 PV-19 PV-42 Other Pigments Alizarine Maroon PV-5:1 Alizarine Red PR-83 Aniline Black PBk-1 Anthanthrone Orange Basic Dye Pigments Ethyl Violet PB-14 Methyl Violet PV-3 Fugitive Methyl Violet PV-3:3 Rhodamine Red or Alizarine (Madder) Lake PR-81 Rhodamine Violet PV-1 Carbazole Dioxazine Violet PV-23 1. Yellow and Orange PY-139 Quinophthalones PY-75 PY-138 Tetrachloroisoindolinones PO-42 PO-61 PR-180 PY-109 PY-110 Victoria Blue BO PB-1 PB-1:X SOURCE: Compiled from various sections of this report. arranged by color as well as by chemical constitution. 154. 119. 41. 94. 53:1. 128 13. 5. 3. 5 22. 48:4.0001 A Naphthol Naphthol AS Isoindoline/one 38 © 2001 by the Chemical Economics Handbook—SRI International Laked PIGMENTS . 48:3. 242. 97. 168. 187. 151. 65. 155 12. 81. 13. 262 257 1. 185. 87. 200 17. 4. 190. 9. 180 . 58:4. 69 260 5 May 2001 575. 14. 12. 221. 6. 18. 214. 74. 68 2. 181. 238. 60. 10 23. 170. 147. 5. 152. 136. 126. 41 Metal Complex Naphthol Naphthol AS 117. 73. 170. 166. 239. 153. 83. 208 32 25 116. 66. 98. 176. 210. 121. 256 25 25 1 8. 114. 185 61. 15. 116 113. 10. 252. 55. 175. 7. 38. 111. 176 15. 171. 194 1 Benzimidazolone Disazo Bisacetoacetarylide Diarylide 36. 22. 8. 220. 16 Pyrazolones Disazo Condensation 93. 14. 13. 53. 17. 240 110. 3. 21. 52:1. 49:2. 17:1. 48:2. 150. 63. 191 120. 169. 62 171. 38 Red Lakes BONA 48:1. 31. 183. 6 2. 139. 177. 68 151. 248. 237. 136. 63:1. 52:2. 184. 127. 188. 111 144. 173. 23. 129. 174.Pigments Page 27 Commercial Organic Pigments by Color Index and Chemical Classa Yellow Azo Pigments Monoazo Nonlaked Orange Red Violet Blue Green Brown Black 1 . 60. 75. 46 49:1. 34 31 37. 95. 146. 112. 179 59. 57:1. 17. 65. May 2001 575. 15:6. 192. CEH estimates. 3 . 10. 62 1. but with world output of less than one thousand metric tons. 177 5:1 60 31 51 216. 255 23. 30. 27 1. 4 122 . 61. Colour Index. 178. 2. 67 90. All other numbers indicate pigments of commercial importance. with world production of more than 10 thousand metric tons. 2. 169 1. 224 29 15. 209 19. 68 48. but with world output of less than 10 thousand metric tons. 14. Italic numbers denote pigments with significant commercial importance. 36 26 61 20 Quinacridones Quinophthalone Thioindigo Triarylcarbonium Other Aniline Black Other a. 1 101. 19. 206. 16. 15:2. 149. 226 254. 9. 202. 207. Vat Red 74 123. 15:1. 37 43 194. 181 81:1. 42 7 .0001 B SOURCES: © 2001 by the Chemical Economics Handbook—SRI International 108 147 24 PIGMENTS . 192 64. 2. 179 . 59. 190. 15:3.Pigments Page 28 Commercial Organic Pigments by Color Index and Chemical Classa (continued) Yellow Polycyclic Pigments AnthraquinoneStructured Pigments Anthanthrone Anthrapyrimidine Anthraquinone Flavanthrone Indanthrone Isoviolanthrone Pyranthrone Diketo-Pyrrolo-Pyrrole Dioxazine Perinone Perylene Phthalocyanines Orange Red Violet Blue Green Brown Black 168 83. 15:4. 89. 251 Boldface numbers indicate the largest-volume pigments. 49 138 88. also granules) Presscakes (water-wet pastes or granules) Flushed colors (thick. Other properties considered by the end user are gloss. Basic properties include hue. for example. For example. chemical purity. rheology (fluidity). ink.0001 C PIGMENTS Pigments Page 29 The standard designation of individual pigments is by their generic name and chemical constitution as assigned by the Colour Index (CI). PR-1 is Pigment Red 1. PO1 is Pigment Orange 1. dispersibility and fastness to light and heat (which tend to be the most noticeable properties affected by the media). including the following: q Dry colors (usually powders. oily pastes) Fluid dispersions or slurries (pourable pastes) Color paste concentrates (pastes) Resin-bonds or predispersions (powders) Plastic color concentrates or masterbatches (pigment contained in plastic pellets) Surface-treated colors (powders or pastes) q q q q q q q Pigment quality is determined by its properties in the end-use application. Pigments are available in a variety of commercial forms. published by The Society of Dyers and Colourists (of the United Kingdom) and The American Association of Textile Chemists and Colorists. hiding power or opacity. Throughout this report. crystal and solvent stability. tinctorial strength. whether the finished product is. © 2001 by the Chemical Economics Handbook—SRI International . According to the Colour Index.May 2001 575. adhesiveness and abrasiveness. durability. transparency. bleeding. flocculation and migration. the generic name Pigment Red 101 with Constitution Number 77491 has been assigned to synthetic red iron oxide pigment. a surface coating. CI names for pigments are abbreviated as shown in the following examples: PBk1 is Pigment Black 1. PG-1 is Pigment Green 1. PBn-1 is Pigment Brown 1. cement or plastic. PB-1 is Pigment Blue 1. the technical value of a pigment is its fastness under the combined effects of the media of incorporation and the external environment. resistance to chemical attack. PV-1 is Pigment Violet 1 and PY-1 is Pigment Yellow 1. National Library of Medicine. Registry of Toxic Effects of Chemical Substances (RTECS).1c Positive carcinogenicity in rats. OSHA. b. the pigments with significant markets are practically nontoxic.000 (mouse) >7. however. followed by concerns over the neurological damage that may be caused to children by lead-containing pigments. National Institute for Occupational Safety and Health (NIOSH).080 (rat) na 0. anticipated to be a human carcinogen No evidence of carcinogenicity 0. Toxicology Data Network (TOXNET). Total dust. the pigments that receive the most regulatory attention contain lead. The following table shows some relative acute toxicity ratings.S. The following table summarizes the major regional and national environmental and health regulations affecting inorganic and organic pigments and their markets: © 2001 by the Chemical Economics Handbook—SRI International . Oral Dosage (milligrams per kilogram) Iron (III) Oxide (Pigment Red 101) Lead Chromate (Pigment Yellow 34) Cadmium Sulfide (Pigment Orange 20) Lithol Red Sodium Salt (Pigment Red 49) Red Lake C Toner (Pigment Red 53:1) Lithol Rubine (Pigment Red 57) Quinacridone (Pigment Violet 19) Dairylide Yellow AAA (Pigment Yellow 12) Dairylide Yellow AAOT (Pigment Yellow 14) a. c. As measured by chromium trioxide equivalent. d.0001 D PIGMENTS Pigments Page 30 ENVIRONMENTAL ISSUES In general. chromium or cadmium. Carcinogenicity is a concern.800 (rat) >5.05d na na No adequate evidence of carcinogenicity in humans na na >10.000 (rat) na No evidence of carcinogenicity na No evidence of carcinogenicity in rats na na na SOURCE: The main issue driving the regulation of pigments is concerns over carcinogenicity. na Permissible Air Exposure Limitsa (mg/m3 ) 15b Carcinogenicity No adequate evidence of carcinogenicity in humans Suspected human carcinogen >12. Cadmium basis.800 (rat) >10.000 (rat) >10.May 2001 575. U. As a result. as well as carcinogenicity and exposure limits for some of the major commercial pigments: Toxicity Characteristics and Exposure Limits for Selected Major Commercial Pigments LD50. for some of the inorganic pigments such as lead chromate and cadmium sulfate. Washington and Wisconsin. Environmental Protection Agency (EPA) Resource Conservation and Recovery Act (RCRA) Restrictions on metal concentrations in waste for disposal U. Pigments Affected Lead chromate Markets Affected Highway paint Lead chromate Cadmium Strontium chromate Zinc chromate All packaging and packaging components (coatings. consumer paints. highway miles Coalition of Northeastern Governors (CONEG)a State regulations to limit toxic metals in solid waste U. New Hampshire. New York. paper. SOURCE: © 2001 by the Chemical Economics Handbook—SRI International .S.S. Iowa. Maine. Virginia. consumer paints and paint applied to manufactured goods for consumer use U. children’s toys.S.0001 E PIGMENTS Pigments Page 31 U. Occupational Health and Safety Administration (OSHA) Proposed more stringent permissible exposure level for cadmium in the workplace a. Minnesota. CEH estimates. Food and Drug Administration Approvals for pigment use as an additive to foods and pet foods and to food and pet food packaging Approvals for pigment use in cosmetics Consumer Product Safety Act Lead content in children’s toys. inks and labels) All Foods and pet foods.May 2001 575. plastic and other food and pet food–packaging materials All Lead chromate Cosmetics Artist materials.S. painted consumer products Cadmium Lead chromate Strontium chromate Zinc chromate All markets Cadmium All markets Includes the following states: Connecticut.S. Rhode Island. Environmental and Health Regulations Affecting Pigments Regulatory Agency/Regulation State Lead Paint Bans Affects over 25 states and more than 75% of U. Western Europe and Japan combined consumed approximately 2. Lithopone (PW-5) is a calcined coprecipitate of zinc sulfide and barium sulfate. plastics/elastomers. accounting for as much as 69% of the total world white pigment consumption by volume (excluding use for nonpigmentary applications). White lead (PW-1) pigment use still persists to a very minor extent in the surface coatings industry. paints. Opaque white pigments are important not only because of the predominant use of white itself but also because of the requirement for white to produce tints or lighter hues of other colors. In China and Eastern Europe. about 9% of the total U. The refractive index or hiding power of TiO2 pigments is higher than that of any other commercial white pigment. mostly of the lead-free type. Because of its outstanding optical properties and good environmental and health attributes. zinc oxide. zinc oxide consumption is accounted for by paints and ceramics. (See the CEH Titanium Dioxide Pigments marketing research report for more in-depth information. It is a white opacifying pigment with hiding power about one-fifth that of titanium dioxide. less than 5% of total consumption goes into corrosion-resistant paints and coatings.May 2001 575. In these three regions. viscosity modifier or reinforcing agent and it is thus outside the scope of this report (see the CEH Fine-Ground and Precipitated Calcium Carbonate product review for more information). plastics and other uses. the surface coatings market accounts for 50% or more of the total TiO2 consumption. where its value is primarily as a corrosion inhibitor. Antimony trioxide (PW-11) is used primarily for its flame-retardant properties and. Other major pigment uses include paper and paperboard (where it is also a filler). because of its low cost per unit of hiding power. zinc sulfide and antimony trioxide.5% of total Japanese zinc oxide consumption is for paints and ceramics. resulting in scattering of light and high opacity. thus. printing inks. white lead (basic lead carbonate). but they are less than one-seventh as efficient as TiO2 in this capability. zinc sulfide and antimony trioxide. white lead. Zinc oxides also provide hiding power in paints. However. zinc oxide pigments are still widely used. © 2001 by the Chemical Economics Handbook—SRI International . bulking agent. The market for all lead-based pigments declined dramatically in the 1980s due to legislation limiting the level of lead in paints for household consumption and in products for children’s use.5 million metric tons of TiO2 in 1997. is outside the scope of this report. its main functions are as an extender. all of which are inorganic. The most important property that zinc oxides impart to paints is mildew resistance.0001 F PIGMENTS Pigments Page 32 WHITE PIGMENTS White pigments. are characterized by high indexes of refraction. as the gradual substitution by TiO2 pigments has only recently gained momentum. Other whites that are of minor commercial importance include lithopone. ceramics and building materials. The white leads consumed in the United States are used almost entirely as heat stabilizers for polyvinyl chloride wire and cable products. as a chemical intermediate and as a coating ingredient in photocopying paper). ceramic and ink industries. titanium dioxide has totally displaced the older white pigments such as white lead and zinc oxide in most markets.) Although ground calcium carbonate “pigment” is consumed in significant quantities worldwide for paper. lithopone. About 6. continues to find some limited worldwide application as a white pigment in the paint. Although the primary uses for zinc oxide are nonpigmentary (as a filler and activator in elastomer vulcanization. Other white pigments of less commercial importance than TiO 2 for pigmentary applications include zinc oxide (see the CEH Inorganic Zinc Chemicals product review). The United States. filler.S. titanium dioxide (TiO2) is consumed in the largest volume. Of the opaque white pigments. continue to make them the pigment of choice in certain markets. In recent years. is as a reinforcing agent for rubber products. low-grade coal). Western Europe and Japan combined totaled roughly 222 thousand metric tons in 1997.May 2001 575. synthetic black iron oxide. Consumption of carbon black for pigment uses in the United States. either naturally or synthetically produced) and an organic black pigment aniline black. The major pigment use for carbon black is in printing inks. Furnace black. graphite (crystallized carbon. Black iron oxides and complex inorganic color pigments (formerly known as mixed-metal oxide pigments) are discussed in the INORGANIC COLOR PIGMENTS section of this report. manganese black (naturally occurring manganese dioxide). which includes a variety of carbonaceous pigments produced by combustion or cracking of hydrocarbon raw materials. combined with their relatively low price. include magnetite (naturally occurring iron oxide). Viaton Industries with Rana Gruber) have started to manufacture micronized natural iron oxide red pigment. Iron oxides are available in both natural and synthetic forms in a wide range of yellow. account for more than 95% of the carbon black produced. synthetic iron oxides. good lightfastness. Their primary disadvantage is lack of brightness compared with other inorganic pigments. However. acetylene black and bone black are available. have replaced natural oxides in many applications. iron oxides are the largest-volume inorganic pigments. most of which are produced in small quantities with limited commercial significance. mineral black (powdered. because of their greater color strength. good chemical resistance and heat stability under normal ambient conditions.e. such other types as lampblack.S. Pigment applications account for most of the balance of carbon black consumption. Because of their low cost combined with such properties as high opacity. However. they are attractive for a variety of commercial applications. Recently. iron oxides have a larger-volume market share than all other color pigments together. from highly aromatic oil feedstock and thermal black. followed by plastics and then paints and coatings. some grades of the natural oxides have special properties (for example. consumption. roughly 90% of annual U. manufacturers of natural iron oxide pigments (i. The major use of carbon black. siennas have a certain translucency) that. Other black pigments. On a worldwide basis. red and brown colors as well as black shades.0001 G PIGMENTS Pigments Page 33 BLACK PIGMENTS By far the largest-volume black pigment worldwide is carbon black. Unlike most pigments. carbon black is often used for functional purposes other than for coloring or opacifying. INORGANIC COLOR PIGMENTS DESCRIPTION IRON O XIDE PIGMENTS Excluding titanium dioxide and extender pigments. strong absorption of ultraviolet light. from natural gas. complex inorganic pigments. Detailed information on production and consumption of carbon black is contained in the CEH Carbon Black marketing research report. © 2001 by the Chemical Economics Handbook—SRI International . including carbon paper. better color uniformity and higher product purity. Most of these ores contain considerably less than 100% iron oxide. natural iron oxides are processed from various ores. In weight terms. These mixed inorganic compounds (iron silicates and aluminates) are responsible for the unique translucency of sienna pigments. but can be calcined to form a brown ferric oxide (metallic brown). is mined as a limonite ore normally containing roughly 50% Fe 2O3 plus other inorganics. the principal ones of which are hematite. Today. Hematite (Fe2 O3 ) is generally associated with red coloration although it does exist as a gray substance of flaky structure commonly called micaceous iron oxide. Black natural iron oxide pigment is derived from magnetite (Fe3 O4 ). If sufficiently pure. Umbers are yellow-brown in the raw state because of the higher manganese dioxide content compared with other natural iron oxide pigments.May 2001 575. in terms of volume. umbers may be calcined to a deep reddish-brown color (burnt umber). the company claims that these pigments have further advantages. siderites may calcine to red. Natural red iron oxides are a deep red color because of their high hematite content (typically around 75%). The brown umber shades are also derived from limonite. Sienna can be converted by calcination to burnt sienna. The yellow pigment. such as an environmental friendly production process. but information on these applications is not included in this report. The balance of the ore components consists of inert substances with little color value. limonite. such as silica and alumina. usually contain less Fe2 O3 than siennas. Like siennas. Silica and alumina are normally associated with hematite. Natural Iron Oxide Pigments Natural iron oxide pigments may well have been the first coloring substances known. Some iron oxides are used for nonpigmentary purposes such as foundry sands or industrial chemicals. They are not used as such for pigmentation. only a few deposits are sufficiently pure and possess the required brightness and color to justify processing into pigment form. lower oil absorption and so forth. although they may contain as much as 50% Fe2 O3 . more than four times more red iron oxide pigments were sold than all red organic pigments in 1995. the information in this report necessarily includes some nonpigmentary iron oxides. which is the product favored over raw umber in the commercial market. the lighter yellow colors. Iron oxides are also used in magnetic media such as audio. Only a minute quantity of the magnetite mined is consumed in pigment applications.0001 H PIGMENTS Pigments Page 34 which apparently has a 15% higher color strength than standard synthetic iron oxide pigments. geothite. Since data for some of these applications are incorporated with data for pigment use. sienna. © 2001 by the Chemical Economics Handbook—SRI International .and videotapes and computer disks. which is dark brown. They have been used for centuries for their colorant properties and have proven their stability under the stress of time and a variety of climatic conditions. Also. Ochers are essentially clay-containing limonite. siderite and magnetite. diskettes and tapes. partly combined with the iron oxide. is red. Ochers. a magnetic substance used primarily for coal washing. The most important iron oxide pigment. The following sections briefly describe the two types of iron oxide pigments—natural and synthetic. Siderites are basically ferrous carbonate. although magnetite is often 95% Fe3 O4 and calcined siderite is 93-98% Fe2 O3 as used by pigment producers. Although these ores are widely distributed. Geothites and limonites are ferric oxides in hydrated form (Fe2 O3 ·xH2O) and are opaque yellow shades. In addition. chrome orange and molybdate orange). yellow. even with these disadvantages the natural iron oxide pigments continue to have commercial importance because of their low price. lead molybdate and lead sulfate. Synthetic Iron Oxide Pigments Synthetic iron oxides. Synthetics are red. However. good hiding power and satisfactory lightfastness. All of the colors are available in a variety of shades. Pigment Yellow 42 (Fe2 O3 ·xH2O) is related to the natural limonite counterpart and synthetic Pigment Black 11 is the manufactured variant of natural magnetite pigment (Fe3 O4 ). modern methods of quality control and improved beneficiation methods for natural iron oxides yield constantly improving products of good color value per unit price. is a solid solution of lead chromate. to produce the required colorant shades. depending on the exact method of manufacture. The chemical formulas of the synthetic products are directly comparable with the natural pigments. to light yellow. CHROME PIGMENTS The chrome pigments discussed in this report include the lead chromate salts (chrome yellow. is the manufactured version of natural red hematite. red and/or yellow oxides. which has a definite green hue and is composed of lead chromate. for example. lack of stability at high temperatures and possible discoloration upon long exposure to the © 2001 by the Chemical Economics Handbook—SRI International . Commercial molybdates generally contain 75-85% lead chromate. the brown products are generally produced by blending black. depending upon the chemical composition. chromium oxides (including hydrated chromium oxide) and normal lead silicochromate. because they are chemically manufactured under controlled conditions. the natural iron oxides are categorized not in terms of the ores from which they originate but as ochers (yellow).0001 I PIGMENTS Pigments Page 35 Commercially. Medium and light red shades are produced by increasing the concentration of lead carbonate. In the United States. siennas (red-orange-yellow) and umbers (brown). Pigment Red 101. To meet particular customer specifications. The lead chromate salts vary in hue from greenish yellow through orange to pale red. Molybdate orange (PR-104). Greater temperature stability and lightfastness are achieved through lower concentrations of lead sulfate. several natural oxides may be physically blended or synthetic oxides added. lead carbonate and lead sulfate in solid solution. The light yellow does not have lead carbonate and has a different crystalline structure and therefore a different hue. Chrome yellow also includes a medium yellow. An extensive number of grades of each of these products is available. because of their poor alkali and acid resistance. The naturals generally have less color strength and uniformity than synthetic iron oxide pigments. Thus. which varies in hue from light orange to red. at a relatively low cost. particle size and particle size distribution of the pigment. synthetic ferric oxide (Fe2O3 ). Chrome yellow (PY-34). However. which is theoretically pure lead chromate. Chrome orange (PO21) is structurally basic lead chromate (PbCrO 4 ·PbO). black and brown. crystalline structure. Chrome yellows and oranges offer more intense colors than iron oxides.May 2001 575. Its variation in color from light orange to redder and deeper shades is associated with particle size differentials. ranges from primrose yellow. possess a higher degree of consistency from batch to batch than do the natural iron oxides. they are inappropriate for certain applications. lead chromates may be chemically treated to improve resistance to light. market in 1963 as one in a series of coated silica-cored pigments. provide good hiding power and tinting strength and have acceptable heat resistance. Chrome greens (PG-15) are normally blends of chrome yellows with iron blues. marketplace.0001 J PIGMENTS Pigments Page 36 atmosphere (because of their reaction with sulfide to produce lead sulfide). with low iron blue content. Final properties of the pigment are dependent on the choice of metal oxides and the order in which they are applied. it is. Typically these coatings may add 3-5% to the weight of the pigment particle. thereby extending the areas of possible application to high-temperature plastics and corrosive environments. Manufacturers continue to improve the heat stability and chemical resistance of molybdate orange. © 2001 by the Chemical Economics Handbook—SRI International . however. The chrome greens are commercially available in pure forms and also in forms reduced with extender pigments. because of its performance characteristics. A specialty chrome green product. To combat these deficiencies. It possesses brilliant hue and fine particle size. it is often blended with other products to produce desired hues in the commercial marketplace. Chromium oxide is the most stable green of the commercially available green pigments. titanium dioxide. Pigment particles may be encapsulated with thin layers of metal oxides (e. by the organic pigment. However. silica. They vary in color from light green. Of the lead chromate salts. However. molybdate orange has the best hiding power. Lead chromates may also be treated by organic agents to improve ease of dispersion. often called Guignet’s green. is appropriate in hightemperature applications such as ceramics. heat.g. antimony oxide or tin oxide) to improve resistance. to some extent. chrome green has been replaced.May 2001 575. thus. Although this high-performance product is relatively expensive. Like the lead chromate salts. The hydrated version has a brilliant green hue as opposed to the drab green of the anhydrous oxide. chrome greens are relatively inexpensive. The low density of this silicochromate produces a high-bulk paint formulation ideal for thick coatings and economical to use on various types of road surfaces. can withstand high temperatures and. to very dark greens. It was introduced to the U. chemicals and other harsh conditions. which is almost pure chromium sesquioxide and the hydrated oxide (PG-18). which contain 60-65% iron blue. the hydrated oxide is less acid resistant and heat resistant than chromium oxide and loses its water of hydration at high temperatures.. Since molybdate orange is compatible with many inorganic as well as organic pigments. which are generally applied as thick films. regardless of end-use application. Normal lead silicochromate is a pigment with a silica core coated with medium yellow lead chromate.S. they are subject to darkening in the presence of sulfur and susceptible to fading in an alkaline environment. Chromium oxide itself. being substituted to some extent for phthalo green. Since that time it has found use in traffic paints.S. resulting in easy dispersibility for an application such as printing inks. phthalocyanine green. which is a mixture of high-performance chrome yellow and phthalocyanine blue. The chromium oxide greens comprise both the anhydrous oxide (PG-17). is available in the U. Because of these deficiencies and concern about the toxicity of the lead component of this pigment. Both chromium oxide greens possess outstanding lightfastness and resistance to attack by acids and alkalies. Small quantities of other metals or compounds (modifiers) may also be introduced into the crystal to alter the pigment properties without changing the crystal structure. are appropriate for a variety of commercial applications. Similarly. blue. The two most important crystal structures are rutile and spinel. these pigments. especially when combined with some organic pigments. weather resistance and lightfastness. green. chemical inertness. When used with organics. Synthetic complex inorganic color pigments are available in a wide range of colors. although usually color. as well as varying shades of these colors. which are based on the oxides of two or more metals. in combination with other inorganics or combined with stable organics. red. Both function as colorants.0001 K PIGMENTS Pigments Page 37 COMPLEX INORGANIC PIGMENTS The complex inorganic color pigments (formerly known as mixed-metal oxides) are a small but important group of inorganic pigments. Another disadvantage of this group of pigments is their high price. which tends to limit their use to applications in which their excellent thermal stability makes them indispensable. Among the most important in the commercial marketplace are the nickel titanates (PY-53). including violet. Because of their outstanding heat resistance. when bans or proposed bans due to the uncertainty of the safety of cadmium use caused these countries to seek substitute products. As a group.May 2001 575. Complex inorganic color pigments include all color pigments formed by the incorporation of colorprocessing metal ions into the crystal lattice of an oxidic compound that is uncolored in its pure form. The complex inorganic color pigment oxides may be used alone. chemical structure or crystal structure is the criterion used in the industry. brown and black. a higher-valence metal ion. chrome titanates (PBn24). although twelve other crystal classes of the complex inorganic color pigments have been identified. Since both nickel and chromium have a lower valence in these compounds than titanium. sometimes called camouflage green). the pigment grade is generally of a © 2001 by the Chemical Economics Handbook—SRI International . usually antimony. must be added to balance the resultant loss of charge. Although the actual chemical composition of most complex inorganic color pigments is variable. Thus. manganese titanates (PY-164) and cobalt chromites (PG-26. complex inorganics possess low tinting strength. the two used most often are ceramic and pigment grades. yellow. The two yellow pigments just described are members of the nickel-titanate and chrome-titanate series of complex inorganic color pigments. For example. In each of these series the range of color hues is dependent upon the actual amount of each of the metals in the pigment composition. While several grades of complex inorganic color pigments are available. the introduction of nickel ions to replace some of the titanium atoms in the titanium dioxide rutile lattices results in a nickel rutile yellow colorant. Nickel and chrome titanates together account for approximately 50% of the total complex inorganic color pigments used. higher-than-average pigment loadings are often necessary to produce desired colors. They can be classified in several ways. At least fifty different complex inorganic color pigments are available in the United States. These combinations were traditionally more prevalent in European countries such as Sweden. each identifiable oxide does have a basic chemical formula differentiating it from all other oxides. the complex inorganic color pigments provide the opacity and base color while the organic colorant adds color intensity and brightness. Switzerland and Denmark. However. a reddish chrome rutile yellow is formed when chromium is substituted for titanium in the crystal structure. A combination of complex inorganic color pigments with organics can be substituted for cadmium pigments in some applications. rubber. in the commercial marketplace. All the U. Ultramarine blue is a brilliantly colored pigment with good heat stability but poor ultraviolet stability. This market has been static and is expected to decline as iron blue is replaced by phthalocyanine blue to make phthalocyanine green. textiles. PY-35 and 37. The violets contain less sodium than the blues.and zinc-based oxides are used for plastics. To produce redder colors.May 2001 575. for example. Demand for iron blues has been declining. supply of iron blue is now imported. and the cobalt-. selenium is substituted for part of the sulfur in the cadmium sulfide crystal lattice. Ultramarine violet is believed to have fewer applications than blue. the titanium-based variety are used primarily for plastics and paints. iron blues can be used for black ink toning.g. Ultramarine pigments are no longer manufactured in the United States. Milori or Prussian blues.S. To modify the basic golden yellow color of cadmium sulfide. ULTRAMARINE PIGMENTS The ultramarine blues (PB-29) and violets (PV-15) are complex sodium aluminum sulfosilicates. a chrome green replacement. [(Cd/Zn)S]). Currently. although they have been replaced somewhat by the organic pigment alkali blue (PB19 and PB-61) in this end use. cadmium pigments are supplied and used mainly in the lithopone form although the tinting strength of the lithopones is much weaker than that of the pure pigment forms.. lithopone-type pigments. CADMIUM PIGMENTS All cadmium pigments are based on the compound cadmium sulfide. Small quantities of iron blues are consumed in paints and coatings. © 2001 by the Chemical Economics Handbook—SRI International . Pigment Orange 20 (Cd[S/Se]) and Pigment Red 108 (Cd[Se/S]) are examples of colorants that result from this reaction.0001 L PIGMENTS Pigments Page 38 finer and more uniform particle size with a softer texture than the ceramic grade. zinc may be introduced to replace some percentage of the cadmium and to produce greener shades of yellow (lemon and primrose. plastics. Thus. IRON BLUE PIGMENTS Iron blues (PB-27) are also known as Chinese. Applications for ultramarine blue include printing inks. food colorants and paper manufacture. artist’s colors. certain plastics (e. the cadmium pigment class also includes blends of cadmium sulfide with zinc or mercury sulfides and with cadmium selenide to produce colors ranging from lemon yellow to maroon. In fact. yet equally stable. dried and calcined. Within the ink category. only Société Languedocienne de Micron-Couleurs SA (SLMC) in France is still producing mercadium pigments. Other applications for iron blues include carbon paper. due in part to environmental concerns. which itself produces a golden yellow pigment (PY-37) when precipitated. and the past few years have shown an increasing replacement of iron blues by other pigments. it is inappropriate for exterior applications. low-density polyethylene). Iron blues can also be used in combination with chrome yellow to make chrome green (PG-15). iron. However. paints and ceramics. However. cosmetics and roofing granules. primarily by phthalocyanine. chrome-. In general. but it possesses great permanence. iron blues are also being replaced in these applications. Some pigment grades are surface-treated to improve their wettability and dispersibility. the zirconium-based complex inorganic color pigments are used for high-temperature ceramic applications. Violet is much weaker in color. Furthermore. the inert extender barium sulfate is frequently added to the cadmiums to yield lower-cost. light degradation and color particle migration. The currently available pigments are all based on the main constituent.May 2001 575. As a class. which are water-soluble. and insolubility in organic solvents. located primarily in Western Europe. burgundy and yellow. The pigments are brilliant yellow pigments with a green tint. Rare earth sulfide pigments can be regarded as high-performance pigments as they possess the following characteristics: q Excellent heat stability (up to 350°C) Very good weather/light stability Acceptable tint strength (70-100% of heavy metal pigments) Excellent opacity q q q © 2001 by the Chemical Economics Handbook—SRI International . cerium sulfide. Thus. Their poor weatherability is due to the oxidation of sulfides to sulfates. the selenide-containing cadmium pigments (reds) withstand poor weather better than the sulfides (yellows).Se) (cadmium sulfoselenide) Red Maroon SOURCE: CEH estimates. a growing market. Variations in color are achieved by the addition of other rare earth sulfides and by modification of the physical form. rare earth sulfide pigments are a novel group of pigments introduced by Rhône-Poulenc in France. RARE EARTH SULFIDE PIGMENTS Although rare earths have been used for color since their discovery. the remaining 10% is in plastics. good dispersion characteristics.0001 M PIGMENTS Pigments Page 39 The chemical basis for the range of colors possible with cadmium sulfides and sulfoselenides is as follows: Color Range with Cadmium Pigments (Cd. with 90% of total consumption. Currently there are six specific pigments with varying color shades—orange. is in paints and coatings. In addition. Limitations of the cadmium pigments include poor acid resistance and poor weatherability.Zn)S (cadmium/zinc sulfides) Primrose Lemon CdS (cadmium sulfide) Golden Yellow Orange Cd(S. red. excellent hiding power. Their main application. cadmium pigments have two attributes that are primarily responsible for their strong market acceptance—excellent high-temperature stability and high color saturation for a broad range of colors from primrose yellow to maroon. Worldwide there are already a number of producers. these versatile colorants have such other advantageous properties as high resistance to alkali attack. BISMUTH VANADATE PIGMENTS Bismuth vanadate pigments are a relatively new group of high-performance pigments introduced primarily as an alternative to lead chromate pigments. chlorides and sulfates Further grinding or micronizing to produce the finished pigment q q q Synthetic Iron Oxide Pigments Three principal methods are employed in the manufacture of synthetic iron oxides—precipitation reactions. Generally.0001 N q PIGMENTS Pigments Page 40 Good migration resistance (in compliance with European and U. the following four steps are taken to produce a pigment-quality natural iron oxide: q Grinding and classification to reduce particle size and liberate undesirable impurities Drying Calcination to dehydrated oxides or to promote reactions leading to desired color shades or to eliminate carbonates. the ultimate commercial application of the pigment determines the degree to which the ore must be treated. MANGANESE VIOLET PIGMENTS Manganese violet (PV-16) is actually a member of the complex inorganic color pigments. Furthermore.S. Ohio is the only U. These processes often utilize spent pickling acid generated by the steel industry as raw materials. the methods of processing the ore to produce iron oxide pigments vary considerably. it is translucent rather than opaque and it is not particularly alkali-resistant. manufacturer of this pigment.) of hot steel.May 2001 575. This prerequisite is the main driver. polyamides and polycarbonate) and coatings. as rare earth sulfide pigments are aimed directly at replacing heavy metal pigments in plastics (particularly technical plastics such as ABS. the properties of manganese violet are different from those of other inorganic complexes. Ferrous © 2001 by the Chemical Economics Handbook—SRI International . etc. which passes all current regulations. The primary application for manganese violet is in cosmetics. Pickling acid removes the oxides of the mill scale during the forming (rolling.S. However. The Shepherd Color Company in Cincinnati. by conversion to soluble iron compounds in a hydrochloric or sulfuric acid bath. thermal decomposition of iron compounds and organic reduction processes utilizing iron as the reducing agent. For example. MANUFACTURING PROCESSES IRON O XIDE PIGMENTS Natural Iron Oxide Pigments Because of the marked variation in the chemical composition and physical properties of iron ore deposits. drawing. regulations regarding food contact) Dimensional stability when incorporated with crystalline polymers Very good ease of dispersion q q An important characteristic of these pigments is their overall favorable toxicity status. since it is a precipitated rather than a calcined pigment. In the second. scrap metallic iron may be used as the reducing agent in the organic reduction process of iron oxide production. The chemical reactions of the Penniman-Zoph process are as follows: FeSO4 4 Fe(OH)2 + + 2 NaOH O2 Fe(OH) 2 + Na2SO4 + 2 H2O FeSO4 2 Fe2O 3 • 2 H2O seed 4 FeSO 4 + O2 + 6 H2O + H 2SO4 2 Fe2O3 • 2 H2O FeSO4 + + H2 4 H2SO4 Fe (scrap iron) The reaction is stopped when the desired color is obtained and the final precipitate is washed. Synthetic yellow iron oxides are commonly produced by one of two precipitation processes. ground and bagged for sale. various chemical environments and ultraviolet light. Both color and chemical stability are of major concern since. In this case. a ferrous sulfate solution is treated with heat and compressed air. which employs both organic and inorganic raw materials. leaving iron oxides behind. Further. Four different methods are available for the manufacture of red oxide pigments: q Two-stage calcination of ferrous sulfate to copperas red ferric oxide Thermal dehydration of yellow iron oxide to yield ferrite red Precipitation from ferrous sulfate solution. The aniline is subsequently removed from the paste. The difference between the two processes is that in one. Particle size in particular must be monitored closely since it is particle size and size distribution that determine the color of the final pigment product. ground and bagged. In all of these production processes. It not only acts as a neutralizer for the sulfuric acid formed in the process. the Penniman-Zoph process. which is then purified. Ferrous sulfate heptahydrate (copperas) by-products from the sulfate process of producing titanium dioxide may also be used. hydrochloric or sulfuric acid can be regenerated and reused in the steel plants. dried. Another process used to produce synthetic yellow is the aniline process. The initial steps of this process involve the preparation of a “seed. Thus. In both. pigments of high and consistent quality are the goal of the manufacturers. Nitrobenzene and scrap iron raw materials undergo an oxidation-reduction reaction in which the nitrobenzene is reduced to aniline while the metallic iron is oxidized to iron oxide paste. ferrous sulfate is the sole source of ferrous ions. filtered.May 2001 575. test measurements are conducted at each step of the pigment processing to insure that quality standards are met. but also serves as a continuous additional source of ferrous ions. metallic scrap iron is used as an additional component. In the processing. The oxides contain 2-10% ferrous chloride. which must be washed prior to pigment use. resulting in the conversion of ferrous ions to trivalent insoluble oxides. usually in the presence of oxygen and metallic iron © 2001 by the Chemical Economics Handbook—SRI International q q . The seed is circulated over the scrap iron in the presence of compressed air and iron oxide grows onto the seed. pigments are frequently subjected to extremes of temperature.0001 O PIGMENTS Pigments Page 41 chloride or ferrous sulfate obtained from spent pickling acid is roasted to drive off water and sulfur oxides.” which is subsequently placed in a tank containing scrap iron and ferrous sulfate solution. the scrap iron is oxidized to iron oxide. dried. in subsequent applications. in which a black intermediate is precipitated from an alkaline aqueous ferrous salt solution.) Black iron oxide. magnetic ink). (Under normal conditions yellow. rather than spheroidal like copperas red particles. is produced in the cubical form using methods similar to those used to make yellow oxides. it is used primarily in applications that make use of its high magnetic strength (e.. rather than red. involves dehydration followed by hightemperature calcination: FeSO4 • 7 H2O 6 FeSO 4 • H2O ∆ -H2O ∆ FeSO4 • H2O 2 Fe2O 3 + + 6 H2O + 3 SO2 Fe2(SO4)3 The second stage may occur in the absence of air: Fe2 (SO4)3 ∆ Fe2O3 + 3 SO3 or in the presence of air: 6 FeSO 4 • 6 H2O + 11/2 O2 ∆ Fe2 O3 ∆ + 2 Fe2(SO 4)3 + 6 H2O 2 Fe2(SO4)3 2 Fe2O3 + 6 SO3 The second route to red oxide pigments.May 2001 575. Fe2 O3 . may be calcined at high temperature to oxidize the FeO and change the color from black to red. Fe3 O4 or FeO. The ferrous hydroxide formed is aerated and heated to oxidize the iron precipitate and yield black iron oxide. a by-product in the sulfate process of manufacture of titanium dioxide pigment. such as the precipitation method. as shown in the following reaction: 6 Fe(OH)2 + O2 2 Fe3 O4 + 6 H2O The majority of the synthetic black iron oxide is produced in the cubical form. which is manufactured in both cubical and acicular forms. yields red oxide particles that are acicular (needle-shaped). Red oxides manufactured by precipitation from ferrous sulfate solution require growth of iron oxide particles on nucleating crystals or seeds under stringently controlled precipitation conditions.g. the thermal dehydration of synthetic yellow to ferrite red. FeSO4 ·7H2O). This difference in particle shape results in a yellowish red color. oxides are produced. The original cubical shape of the black iron oxide particles is maintained during the calcination and an extremely pure red iron oxide results. Because the acicular form is more expensive to produce. © 2001 by the Chemical Economics Handbook—SRI International .0001 P q PIGMENTS Pigments Page 42 Oxidation of synthetic black iron oxide The two-stage calcination to copperas (ferrous sulfate heptahydrate. Synthetic black iron oxide. production of nitric acid and the resultant acidification of the pigment slurry increases the solubility of lead chromate. are manufactured by precipitation. The resulting solid solution is a coprecipitate of lead chromate. Proper control of particle size enhances uniformity in hiding power. The light yellow is precipitated at high temperatures while primrose is processed at lower heats. is the major process used worldwide to produce synthetic black iron oxide. such as application of a silica coating or addition of aluminum. only the cosmetics industry evaluates quality on the basis of shade.0001 Q PIGMENTS Pigments Page 43 The acicular form of black iron oxide pigment is manufactured by chemical reduction of synthetic ferrite red. Aftertreatments. the temperature during precipitation. However. essentially pure chromate. Chrome oranges are precipitated under alkaline conditions. The degree of alkalinity determines the particle size and. however. the precipitation step is followed by use of selected chemical additives to improve properties of the final product and to permit production of many different grades of yellow and orange colorants. the concentration and addition sequence of the reactants. the presence of particle-size control agents and the time of reaction. lead molybdate and a small amount of lead sulfate. Molybdate orange is manufactured by the addition of a solution of sodium chromate. the hue. For some lead chromates. redissolving is not practiced by the largest producer in the United States. like many other inorganic pigments. are prepared by coprecipitation of lead chromate with lead sulfate and/or with lead carbonate. This aniline process. Chromium oxide greens are calcined pigments prepared by the reduction of sodium bichromate with sulfurous and/or carbonaceous materials.May 2001 575. is produced directly in the reactions above. All other industries are more concerned with pigment strength. are used to augment stability. Medium yellow. similar to the treatments used in the production of chrome yellow and orange. antimony and/or titanium hydroxides. Primrose and light yellow. the flow rate of the reactants. This pigment particle growth is limited by the addition of lead carbonates or phosphates. the rate of slurry agitation. Key factors involved in the precipitation process include the purity of raw materials. Precipitation is followed by drying and grinding without a calcination step. CHROME PIGMENTS Lead chromate pigments. A variety of black shades may be obtained using any of these production methods. The particle size determines the resultant shade. Chrome yellow is precipitated with either alkaline chromate or acidic dichromate as follows: Pb(NO3)2 + Na2 CrO4 PbCrO4 + 2 NaNO3 2 Pb(NO3)2 + H2O + Na 2Cr2O7 2 PbCrO4 + 2 NaNO3 + 2 HNO 3 In the second equation. described in the section on yellow iron oxide. of the final product. Redissolving the chromate allows growth of larger pigment particles. The chemical reactions are as follows: © 2001 by the Chemical Economics Handbook—SRI International . sodium molybdate and sodium sulfate to a solution of lead nitrate under carefully controlled conditions. thus. color intensity and tint of a pigment. However. The starting materials used to produce lead chromates include a soluble lead salt (usually a nitrate) plus sodium chromate or dichromate as well as acids and alkalies. barium sulfate is mechanically blended with the cadmium pigment after it has been calcined. the two substances tend to mix well. in the form of barium sulfide. The mixture is then calcined at high temperature (660-1. Cadmium sulfoselenides are produced by mixing cadmium sulfide with an alkaline sulfide-selenide. COMPLEX INORGANIC PIGMENTS The first step in the production of complex inorganic color pigments (formerly known as mixed-metal oxides) is the selection and mixing (may be dry or wet) of the appropriate raw materials.400°C). Coprecipitation of cadmium sulfide and barium sulfate occurs. dried and pulverized. The final filter cake is disaggregated for the marketplace or for further processing. making it useful for high-temperature applications. The method of manufacture for hydrated chromium oxide greens is hydrolyzation of a complex chromium borate formed by heating sodium bichromate with boric acid at high temperatures. Cadmium lithopones are usually produced by one of two methods. The brilliant colors of the cadmium pigments develop during the following calcination step at 500-700°C when the pigment material is converted from the cubic to the more stable hexagonal structure and the particles grow larger. After calcination. blends of chrome yellows and iron blues. Normal lead silicochromates are prepared by coating a core of silica with medium yellow lead chromate. The high temperature not only provides the required energy for the reaction. by slurrying together wet yellows and blues or by precipitating lead chromate in the presence of an iron blue suspension. Either cadmium sulfate or cadmium nitrate (bought in bulk or made by the pigment manufacturer from cadmium metal or cadmium oxide and the appropriate acid) is the usual starting material in the production of cadmium pigments. In the alternative method. Chrome greens. At this stage of manufacture the particles are too fine to have pigmentary properties. Calcined complex inorganic color pigment oxides are products of both solid-state reactions and the wet chemical precipitation methods basic to the production of most pigments. CADMIUM PIGMENTS Although various pigment manufacturers have developed proprietary methods of producing specific cadmium colorants with particular properties. the pigments are flushed with weak hydrochloric acid to remove soluble cadmium and then again washed and dried in filter presses. but also stabilizes the final product. In either case. although solid-state reactions are the method of choice in the United States. An aqueous solution of sodium (or other) alkali sulfide is introduced to precipitate cadmium sulfide in cubic crystallographic form. the precipitates are in the form of fine color particles. which contains approximately © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. are prepared by blending dry pigments. In the first. After firing. is added at a much earlier stage of the process to insure efficient mix. the pigment is milled to yield a fine powder. Because of their similar particle size and specific gravity. these methods tend to be variations on a single standard process. after washing and drying. washed. It is added to the starting cadmium sulfate (or nitrate) in place of some of the sodium sulfide.0001 R Na2Cr 2O7 + (NH4)2SO 4 PIGMENTS ∆ Pigments Page 44 (NH4) 2Cr 2O7 + Na2SO4 (NH4) 2Cr2O7 Cr2O3 + N2 + 4 H2O The product is filtered. The entire coprecipitate. barium. plant locations and specific pigments produced: U. Henry. whose opacity and color are determined by the particle size. is then calcined. Louis. for it is at this stage that the crystal structure is changed to yield a pigment of bright color. VA New Riverside Ochre Company. PA East St. Cartersville.May 2001 575. The following table lists natural iron oxide–producing companies. Milwaukee. they range from major chemical companies to small independent colorant operations and iron ore mining companies. Inc.S. The calcination step is a particularly important part of cadmium pigment manufacture. Thus. careful process control is required not only at the precipitation stage but also throughout the calcination process. It is this calcination that is responsible for the stability of cadmium pigments at temperatures of up to 800-900°C. Producers of Finished Natural Iron Oxide Pigments—April 2001a Umber (brown) Company and Plant Location Arizona Oxides LLC El Mirage. AZ Blue Ridge Talc Co. VA Dynamic Color Solutions. Inc. WI Elementis plc Elementis Pigments Easton. Inc.0001 S PIGMENTS Pigments Page 45 62% barium sulfate by weight. IL Hoover Color Corporation Hiwassee. GA Black (PBk-11) Natural Re (PR-102) Metallic Brown (PBn-7) Burnt (PBn-7:x) Raw (PBn-7:x) Burnt (red) (PR-101) Sienna Raw (yellow) (PY-42) Ocher (yellow) (PY-43) X X X X X X X X X X X X X X X X X X X X X X © 2001 by the Chemical Economics Handbook—SRI International . The final product is a homogeneous powder. SUPPLY AND DEMAND BY REGION UNITED STATES Iron Oxide Pigments Producing companies Iron oxide producers illustrate the diverse nature of pigment producers. In 1999. © 2001 by the Chemical Economics Handbook—SRI International . SOURCE: Since 1997. Producers of Finished Natural Iron Oxide Pigments—April 2001a (continued) Umber (brown) Company and Plant Location Pea Ridge Iron Ore Company Sullivan. q q q q Four U. the following changes have occurred among U. Arizona Oxides LLC began the production and sales of natural iron oxide pigments from a hematite mine in southwest Arizona. natural iron oxide pigment producers: q Soloman Colors sold its natural pigments manufacturing business to The Prince Manufacturing Company in 1999.0001 T PIGMENTS Pigments Page 46 U. In early 1997. which it owns. IL Rockwood Specialties Inc. offering for sale a broader pigment line than they produce.S. MD Davis Colors Los Angeles. New Riverside Ochre and Pea Ridge Iron Ore. Arizona Oxides in Arizona. became Elementis Pigments in 1997. Rockwood Pigments Inc.S. pigment producers are also resellers. capable of mining the ore used to produce pigments: Arizona Oxides.S. Beltsville. PA Quincy. Laporte Pigments Corporation was renamed Rockwood Specialties. Laporte Pigments Corporation was purchased by K-L Holdings in November 2000. Hoover Color. CEH estimates. companies are vertically integrated iron oxide pigment producers. Arizona Oxides merged with Cathay Pigments.May 2001 575. The company also upgrades imported synthetic iron oxide pigments. Alabama. New Riverside Ochre in Georgia and the Hoover Color in Virginia each mine and produce ocher pigments. MO The Prince Manufacturing Company Bowmanstown. New Riverside Ochre receives some of its natural red pigment supply from the Alabama Pigment mine in Dudley. CA a. Harcross Pigments Inc. Black (PBk-11) Natural Re (PR-102) Metallic Brown (PBn-7) Burnt (PBn-7:x) Raw (PBn-7:x) Burnt (red) (PR-101) Sienna Raw (yellow) (PY-42) Ocher (yellow) (PY-43) X X X X X X X X X X X X X X X Typically. Black (PBk-11) Brown (PBn-6) Red (PR-101) Yellow (PY-42) Tan (PBn-11)b X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X In addition to the companies listed.S. MD The Prince Manufacturing Companyd Quincy. MO Mineral Pigments Beltsville. Davis Colors Los Angeles. Some synthetic iron oxide pigments may be resold. Inc. VA Rockwood Specialties Inc. Hoover Color Corporation manufactures PBn-9.0001 U PIGMENTS Pigments Page 47 U.S. Producers of Finished Synthetic Iron Oxide Pigments—April 2001a Company and Plant Location Bayer Corporation Coatings and Colorants Division New Martinsville. IL BFGoodrich Performance Materialsc Cincinnati. OH Newark. c. IL a. St. d. IL Geo. producers of synthetic iron oxide pigments are listed in the following table: U. Inc. CA Easton. This is not an iron oxide pigment but rather a ferrite containing zinc oxide or magnesium oxide.May 2001 575. Company produces transparent grade only. CEH estimates. a synthetic product that is a color duplicate of natural Van Dyke brown (an imported product). SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . CA Mapico. Louis. B. Smith Color Corporationd Kirkland. WV Elementis plc Elementis Pigments Inc. Colton. PA East St.d Solomon Colors Division Springfield. Louis. IL Solomon Grind-Chem Service. NJ Hoover Color Corporation Hiwassee. b. 3 30.9 3.2 12.1 32.5c 3.0001 V PIGMENTS Pigments Page 48 Since 1997. synthetic iron oxide pigment producers: q In March 1998.8d 18.4 26.6 Exports Natural neg 13.1 CEH estimates. producers are presented in the following table: U. Producers (thousands of metric tons) Brown Naturalab 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 8.0 24. the Freedom Chemical Company. Sales of Finished Iron Oxide Pigments from U.4 34.0 29.7 30.8d 16.0 21.5 13.1 20.2 29.8 22.8 Apparent Consumption Natural 92.0d 24.0 Imports Synthetic 77. BFGoodrich Performance Materials is now a privately-owned. independent company.0e 22.2 9.0 23.7 14. the pigments business along with the performance materials segment was subsequently acquired by a private investment group consisting of AEA Investors Inc.2 26.1 14.S.4 22.4 85.4 Red Synthetic 41.7 15. DLJ Merchant Banking Partners and DB Capital Partners.7 © 2001 by the Chemical Economics Handbook—SRI International .7 29.8 33.6 18.S. (formerly Hilton Davis Company) was acquired by BFGoodrich Company.2 9.3 5.S. Salient Statistics for Iron Oxide Pigments—1999 (thousands of metric tons) Production Natural 84.S.3 Synthetic 149.3c 4.6 25..1 27.May 2001 575. The business was integrated into existing BFGoodrich specialty additives businesses.7 12.3 10.5 26.5 Natural 7.0c na na na Synthetic 1.5c 4. Synthetic 85.6 25.6 Total SOURCE: 170.6 4.3 Historical tonnage sales data for finished iron oxide pigments from U.2d 23.S.6d Natural 16. the following changes have occurred among U.3 22. Salient statistics Iron oxide pigment salient statistics for 1999 are estimated as follows: U.8 Synthetic 13.3 4.6 32. In late 2000.0 241.4 30.2 19.2 16.1 27.7 23. 4 124.9 5.7f 7.0 16.7 6.5 17.6 8.1 21.6 55.7 Red Synthetic 32.2 25.4 22.4 na na na na na na na U.0 26.6 53.3 48.9 11.5 Totalbh 89.1 94.0 194.0 49.7 21.5 19.6 24.1 4.3 13.9 115.5 Unspecified 2.0f 8.6 23. Producers (continued) (thousands of metric tons) Yellow Natural 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 4.0i 13.4 21.8 15.0 © 2001 by the Chemical Economics Handbook—SRI International .1i 16.4 112.6 15.2 17.9 19.8 83.0 Blackg Synthetic 1.3 111.3 49.6 27.6 54.6 127.6 7.0 18.6 14.4 117.5 22.2 126.7 -4.7 15.1 16.4 4. Sales of Finished Iron Oxide Pigments from U.4 Natural 26.9 5.8 9.5 28.4 Synthetic na 8.9 2.3 125.5 4.0 163.7 na na 18.7 25.4 5.8 4.6 126. Sales of Finished Iron Oxide Pigments from U.1 2.0 180.4 12.9f 18.3 4.9 72.3 25.3 28.3 2.8 117.7 18.0f 6.7 123.3 32.7f 21.8ef 15.3 49.0001 W PIGMENTS Pigments Page 49 U.S.0 9.9 4.0 20.S.8 4.6 25.8 12.4 15.2 4.1 51.2 105.0 176.8 4.8 17. Producers (continued) (thousands of metric tons) Brown Naturalab 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 na na na na na 2.6 138.3 27.8 45.6 4.5 6.6 128.4f 24.4 10.7 53.8 23.4i --j na na na na na na na na na na na na na Synthetic 13.7 23.0c na 2.5 21.2 121.1f na 7.4 5.0 7.5 Natural --------------------12.0 116.8 25.May 2001 575.6 21.8 5.S.6 4.4 16.3 16.9 145.5 115.5 16.S.8 10.0 29.3f 22. producers was 194. Amounts reported in this column exclude Van Dyke brown. Beginning in 1974.S. The following table shows the total U. data for SYNTHETIC BROWN.0001 X PIGMENTS Pigments Page 50 a. Data for 1960-1963 are not directly comparable with later years due to reclassification of pigments. h. Bureau of Mines (data for 1960. Includes data for synthetic black iron oxide. 1961.S. Sales of brown iron oxide have been withheld by the source to avoid disclosing company proprietary data. data for precipitated magnetic black were combined by the source with data for brown iron oxides. an imported crude pigment processed and sold in the United States. (A) Minerals Yearbook. e.May 2001 575.0 thousand metric tons (including U. YELLOW. Data were combined with natural red iron oxides. all data for 1985-1992). d. U. production sold domestically and imports for consumption).S. Geological Survey (data for 1994-1999). Data include black magnetite in 1960.S. BLACK and UNSPECIFIED for 1965-1984 except NATURAL YELLOW and TOTAL YELLOW for 1984. b. Department of the Interior.S. SOURCES: In 1999. Includes data for mixtures of natural and synthetic and specialty iron oxides. Bureau of Mines (data for 1992-1993).S. Data include reported sales of natural umbers only. Includes data for natural yellow iron oxides. data for black magnetite were combined by the source with data for brown iron oxides. (B) Mineral Industry Surveys. f. g. From 1962 to 1975. RED.S. Includes data for natural brown iron oxides. (C) Mineral Industry Surveys. U. j. Totals may not equal the sums of the categories because of rounding. Department of the Interior. U.S. U. producers since 1980: © 2001 by the Chemical Economics Handbook—SRI International . Data include precipitated magnetic black from 1960 to 1963. c. the United States sales of finished iron oxide pigments from U. 1976-1984 and 1995. i. Department of the Interior. sales of natural and synthetic iron oxide pigments from U. 3 125. U.4 124.2 75.0 117.3 76. 53.6 96.0 Includes some nonpigmentary consumption for all years.S.6 48.0 176.3 111.8 27. (A) Minerals Yearbook .4 68. Department of the Interior.0 194.1 43.3 126.3 46. Sales of Finished Iron Oxide Pigments from U.S.2 121.8 68.6 128.0 92.4 117.S.0 102.2 68.0 69.8 29.1 44.2 105.1 69.5 96. Bureau of Mines (data for 1980-1991).0 52.7 125.8 69. (B) Mineral Industry Surveys.9 42.0 Synthetic 70.0 163. In 1983-1984. b.1b 62. these mixtures are included in the brown synthetic iron oxides data.0 95.6 138.0 180. producers by type of iron oxide pigment since 1960: © 2001 by the Chemical Economics Handbook—SRI International . U.0 Total 123.7 76.S.1 73.8 78.2b 66. U. Producers (thousands of metric tons) Naturala 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.2 52. Bureau of Mines (data for 1992-1993). SOURCES: The following table shows historical annual dollar sales values for U. Department of the Interior.S.4 48.0 84.8 70.6 49. Data include mixtures of brown synthetic and natural iron oxides.0001 Y PIGMENTS Pigments Page 51 U.6 127.8 88.0 81.0 96.S.3 55.8 49. Geological Survey (data for 19941999). (C) Mineral Industry Surveys.0 116.7b 76.May 2001 575.9 145.2 68.S.5 115. Department of the Interior. U. 22 6.8 3.73 4.60 1.40 6.S.56 5.21 3.41 3.53 49.49 3.06 4.05 49.18 16.2 10.57d 28.90 56.34d 39.10 1.1 2.99 2.9 11.1 Natural 1.57 na na na na na na na © 2001 by the Chemical Economics Handbook—SRI International .20 22.40 47.61e 3.26 6.82 12.16 2.7 11.99 na na na na na na na na na 2.24 50.91 4.20 11.71 4.93 34.07f 15.07 5.10d 34.60 9.11 4.49 10.13d 25.95 45.60 na 14.78 52. Sales Values of Finished Iron Oxide Pigments from U.51 13.79 40.02d 36.7 Red Synthetic 10.May 2001 575.09 4.72 3.S.82f 13.7 18.01 31.48 18.0001 Z PIGMENTS Pigments Page 52 U.88 1.81c 4.60 13.83 54.03 8.79 3.79 38.05d na 15.1 3.82 3.0 17.20 9. Producers (millions of dollars) Brown Naturalab 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 1.25 4.87 6.74 5.3 Synthetic 0.21 8.9 18.50 50.61 4.78 3.12c 2. 28 93. Includes data for synthetic black iron oxide.89 23.15 19.9 1.10 143.9 3.12 28.43 24. Beginning in 1974.00 147.6 0.2 2.85 8.70 107.j na na na na na na na na na na na na na Synthetic 3.S.51 134. e.44 26.8 0.2 77.70 75.0 0.9 Unspecified 0.12 46. data for black magnetite were combined by the source with data for brown iron oxides.0 81.00 10.9 1.May 2001 575.4 44.14 7.5 38.1 41.4 Natural -------------Blackg Synthetic 0.63f 29.08 27.1 1.0 2.37 143.11 1.4 43.37 30. f. b.9 1.1 45.80 27.78 1.50 29. The source included brown value with natural yellow.00 21.2 54.40 0.9 Totalbh 17.29f 36. 0.0002 A PIGMENTS Pigments Page 53 U.5 27.10 1.4 -0.22 10.89 10.0 43.0 169. 1984 and 1995.53 28.60 37.20 74. Data include precipitated magnetic black for 1960.59 11.6 0. data for precipitated magnetic black were combined by the source with data for brown iron oxides.39 136.21i 4.52 7.34 0. g.98 24.09 19. Includes data for natural brown iron oxides.72 126.9 0.00 14. Data combined with natural red iron oxides.53 8.13 132.0 ------2. i.0 207.56 6.84 11.0 23.49 5.8 34.08 140.97 110.7 Values reported in this column exclude the value of imported Van Dyke brown. © 2001 by the Chemical Economics Handbook—SRI International .1 3. Includes data for mixtures of natural and synthetic and specialty iron oxides. Sales Values of Finished Iron Oxide Pigments from U. d.31 4.72i -. h.00 183.12 2.89 147.34 na na 32.51 0.18 28.70 5.14 96.42 25. c.0 193. Producers (continued) (millions of dollars) Yellow Natural 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.52 1.98 110.59f 33.60 42.57 139. From 1965 to 1975.23 36.S. Totals may not equal the sums of the categories because of rounding.18 12.57f 34.38 122. Data for 1960-1963 are not directly comparable with later years due to reclassification of pigments. Data include black magnetite in 1960.43 122. Includes data for natural yellow iron oxide.0 25.1 1.25 1. Value of brown iron oxide was withheld by the source to avoid disclosing company proprietary data.70 97. j. Department of the Interior.5 4.7 40.0 37.1 41.1 13.0 7. U.7 30.1 11.2 27. U.6 1.S.7 5.3 7.2 33.S.S. Reported Consumption of U.5 11.S.9 5.0 27.5 Animal Feed and Fertilizers 8.9 32. (C) CEH estimates based on Mineral Industry Surveys.5 15.0 11.0 31. Department of the Interior.8 39.3 34. Geological Survey (data for 1994-1999.7 16.4 13.7 42.8 43.4 6.3 6.S. (C) Mineral Industry Surveys.3 44. U.5 7.9 23.S.9 29.0 4.6 5.7 21. consumption of U.6 7.8 5.2 6. Consumption The reported U.0 8.3 5.8 na na na na na (A) Minerals Yearbook.5 41.3 59.S.5 21.7 na na na na na na na na na na na na na na na na na Surface Coatings 45.9 6. Bureau of Mines (data for 1992-1993).4 5.S.S.2 14. Ceramics 13.0 Plastics.S.5 2.1 15.2 49.7 6.7 7.9 5.0 38. Department of the Interior.3 6.7 15.8 44.6 13. Department of the Interior. TOTAL BROWN and TOTAL and 1966 datum for BLACK). Bureau of Mines (data for 1980-1988). data for SYNTHETIC BROWN. Glass.0 27.0 7.6 12.6 45. (B) CEH estimates (data for 1963-1984 for NATURAL BROWN.8 13.7 40.6 16.2 29.0 15. U.7 7.5 Ferrites and Other Magnetic Applications 11.2 15.0 15. Rubber.3 na 14.0 5.8 7.0002 B SOURCES: PIGMENTS Pigments Page 54 (A) Minerals Yearbook .9 13.1 7.8 14.9 11.4 Foundry Sands 6. U.4 21.1 13. (B) Mineral Industry Surveys.6 6.6 14.7 9.0 36.4 36.0 10. Department of the Interior.-produced iron oxide pigments by market segment is shown in the following table and pie charts.7 5. RED.0 32.7 na na na na Industrial Chemicals 8.3 18.9 na na 8.1 6.2 42.9 6.0 14. U.-Produced Iron Oxide Pigments by Market (thousands of metric tons) Other Construction Materials 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCES: 27. Department of the Interior.8 20.1 38.3 10.4 51.6 64. Bureau of Mines (all data for 1960 and 1985-1991. Bureau of Mines (data for 1989-1993).7 5.4 7.4 6. U.8 49. © 2001 by the Chemical Economics Handbook—SRI International . Textiles.8 7.0 6. U.9 10.7 45.8 12.0 17. (D) Mineral Industry Surveys.9 21.6 19.2 24. YELLOW.7 na na 18.9 5.5 8.8 25. Paper.5 Miscellaneous 2.May 2001 575. BLACK and UNSPECIFIED for 1984).S.2 7.3 16.1 29.7 3.5 44.8 12.S. U.6 30. Geological Survey (all data for 1994-1999). Ceramics 9% Surface Coatings 13% © 2001 by the Chemical Economics Handbook—SRI International . Textiles. Ceramics 7% Surface Coatings 24% U. Paper.May 2001 575. Rubber.0002 C PIGMENTS Pigments Page 55 U.S. Market for Synthetic and Natural Iron Oxide Pigments—1999 Other 27% Construction Materials 42% Plastics.S. Textiles. Paper. Glass. Rubber. Market for Natural Iron Oxide Pigments—1999 Other 56% Construction Materials 22% Plastics. Glass. 3 59.5 29. Construction material producers use iron oxide pigments to color concrete blocks and roofing tiles.S. Market for Synthetic Iron Oxide Pigments—1999 Construction Materials 22% Other 56% Surface Coatings 13% Plastics.0 37.0 © 2001 by the Chemical Economics Handbook—SRI International .S.3 11.5 21.0 31.1 19.S.6 30.1 29.0002 D PIGMENTS Pigments Page 56 The U.2 10.3 na na na 34.0 Synthetic 14. market for synthetic iron oxide pigments is as follows: U. Paper.9 10.8 13.5 35. bricks.9 13.6 64.2 27.9 32. Reported Consumption of Iron Oxide Pigments in Construction Materialsa (thousands of metric tons) Natural 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 13.4 45.5 13.1 24.1 12. The following table shows reported sales of iron oxide pigments by U.0 18.0 10.May 2001 575. producers to the construction materials market since 1980: U.5 41. Glass.2 33.8 43.9 9.8 29.0 33. the increasing popularity of colored building materials and product innovations.4 20.2 42. Growth in this market segment is influenced by the overall cyclicity of construction activity.8 49.0 Totalb 28.3 44.9 na na na 14.9 15. Rubber.8 9.8 14.6 12. paving stones.1 18.7 45.8 44.4 51. stucco and mortar.2 19.0 32.9 39.6 10.1 10. Textiles. Ceramics 9% Construction materials.7 40. It is estimated that this segment consumed 101 thousand metric tons of synthetic and natural iron oxide pigments from all sources (including imports) in 1999.8 39.S.1 21. brick. U. Geological Survey (data for 1994-1999). b. It is estimated that this segment consumed 57 thousand metric tons of synthetic and natural iron oxide pigments from all sources (including imports) in 1999.S.S. For black coloration. providing advantages in bulk handling and easier mixing and dust elimination. consumption of natural and synthetic iron oxides in roofing tiles and paving stones has been growing strongly. Total may not equal the sum of the categories because of rounding. (B) Mineral Industry Surveys .4-1.5 million units. concrete roofing tiles. Most concrete is colored by adding the iron oxide directly to the wet mix prior to pouring. paving stones.May 2001 575. Surface coatings.S.S. Of all the segments. synthetic iron oxide is used since the tinting strength of natural black is not high enough to achieve satisfactory coloration. (A) Minerals Yearbook and preprints.0002 E PIGMENTS Pigments Page 57 a. U. the U. Bureau of Mines (data for 1992-1993). Slurries can be easier to work with. but each holds a smaller market share than colored concrete blocks. Includes sales of imported finished iron oxide pigments. Red and yellow are the most popular colors. construction industry has shown the strongest growth since 1995 as housing starts rose from 1. the growth rate for iron oxide pigments in construction for 1999-2004 should only slow or flatten. This product reduces dust problems and is easier to mix. Department of the Interior. poured concrete and stucco. The following table shows the consumption of iron oxide pigments (including imports) per segment within the surface coatings market: © 2001 by the Chemical Economics Handbook—SRI International . mortar. Concrete block is the largest construction material application for natural and synthetic iron oxides.S. (C) Mineral Industry Surveys. followed by brown and black. Data may include some mixture of naturals and synthetics.S. U. U. roofing granules. Department of the Interior. Free-flowing dry forms of iron oxide are available for the construction material market.67 million units in 1999 and home resales and remodeling remained strong. Either natural or synthetic iron oxides or pigment blends may be used to color concrete. as product innovation and more intensive use of pigmented concrete products cause broader use of iron oxide pigments. U. Bureau of Mines (data for 1980-1991). Despite the expected lower construction activity rate of 1. Department of the Interior. SOURCES: The building materials that consume iron oxides include concrete block. Iron oxide pigments are available in both dry and slurry forms.35 million units to a rate of 1. but not imported finished iron oxide pigments sold directly to consumers. stains and trim.7 31.S.1 35.0 36.9 11.7 10.0 17.0 29. interior. Producer’s Sales of Iron Oxide Pigments for Surface Coatings (thousands of metric tons) Natural 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.0 26.9 41.9 27.6 30. Mainly for maintenance and auto refinishing.2 24.3 8.3 21. sheet.6 Totala 43.3 38. Consumption of Iron Oxide Pigments for Surface Coatings—1999 (percent) Product Finishes.9 27. water-based flat house paints.3 29.5 22. primers and underbody components and parts.3 8.2 7.9 15.5 39.5 44. b.9 23.9 26.0 29. © 2001 by the Chemical Economics Handbook—SRI International .4 12. metal furniture and fixtures.8 24.8 Synthetic 30.2 49.0 12. producers to the surface coatings market since 1981: U. Mainly exterior. OEMsa Architectural Coatingsb Special-Purpose Coatingsc Total a.4 31. CEH estimates. 46 37 17 100% Includes automotive topcoats. water-based flat and semigloss paints.8 29.9 13.S. machinery and equipment.0 8.5 34.0 26.3 8.5 39.0 8.5 29.2 8.0 9.8 30.8 10.4 Totals may not equal the sums of the categories because of rounding.8 19.7 36. strip and coil.4 17.7 9.0002 F PIGMENTS Pigments Page 58 U.0 10.7 33. SOURCE: The following table reports the sales of iron oxide pigments by U. 12.6 19.S.May 2001 575.8 10.6 45. c.2 7. the particle size.S. Growth in the consumption of natural and synthetic iron oxides depends upon growth in the surface coatings market. the world market is served by two producers: BASF Aktiengesellschaft in Europe and the Hilton-Davis Company in the United States. thus providing a barrier to moisture and corrosive ions. It can utilize waste wood and uses primarily low-cost imported pigments. platelike shape of its particles. where color consistency is less critical.S. Geological Survey (data for 19941999). Micaceous iron oxide helps to protect the paint binder from ultraviolet radiation. Although synthetic iron oxides are the preferred pigment in the paints and coatings industry. Bureau of Mines (data for 1981-1991). U. resulting in reproducible colors. They are of extremely fine particle size and have low covering power. but this parallel to the growth in GDP may become disconnected as the U. When a micaceous iron oxide paint is applied to a surface. a small percentage is used for wood stains and OEM furniture finishes.0002 G SOURCES: PIGMENTS Pigments Page 59 (A) Based on Minerals Yearbook and preprints. but are ideal for covering metallized finishes requiring long durability. Department of the Interior. Department of the Interior. (B) Based on Mineral Industry Surveys. The easily dispersible synthetic yellow and red iron oxides are the most frequently used iron oxide pigment in paints. Some examples of uses include roof coatings and structural steel coatings on highway bridges. © 2001 by the Chemical Economics Handbook—SRI International . Blacks and browns are of less importance. U. its use in the United States is relatively recent. U. market for transparent iron oxides has remained relatively flat for the last decade. This application has quickly grown to use nearly 10 thousand metric tons per year. there is still a significant market for natural iron oxides in paints. Primers function not only to promote adhesion but also to provide protection against corrosion. Over the past several decades. An iron oxide known for its anticorrosive properties is micaceous iron oxide (mined from micaceous hematite).S. The U. Although micaceous iron oxide has been used for decades in Europe on bridges and other metallic structures. Most of the transparent oxides find use in OEM automotive topcoat finishes and automotive repair finishes. market for transparent iron oxides is estimated to have been about one thousand metric tons in 1999. the loadings of iron oxide pigments in paints and product innovations. it has protective properties because of the thin.S. (C) Based on Mineral Industry Surveys. additional specialty product group used in the paints and coatings industry. the thin platelets orient themselves in a plane parallel to the substrate. particularly in primers and undercoats. Synthetic iron oxides are among the most useful pigments to formulators of paints and coatings. In the United States. Currently. distribution and shape can be accurately duplicated.S. economy has become increasingly characterized by service industries. Since these pigments are manufactured under controlled conditions. The total estimated U. Bureau of Mines (data for 1992-1993). One new product to emerge over the last few years is a chipped wood landscaping product that is colored red with an iron oxide-based coating.May 2001 575.S. Transparent (low-opacity) synthetic iron oxides are a small-volume. surface coatings consumption growth has tended to follow the growth in the overall manufacturing economy.S. Department of the Interior. U. (C) CEH estimates based on Mineral Industry Surveys. Paper.5 Total may not equal the sum of the categories because of rounding. U. in conjunction with oxygen.S. and rubber industries. U.S. paper. reported sales by U. paper and textiles. rubber.0 17. (B) CEH estimates based on Mineral Industry Surveys. The addition of Fe2 O3 to molten glass results in the presence of ferric and ferrous ions in the solution. Bureau of Mines (data for 1992-1993).May 2001 575.S.S. by the plastics. Department of the Interior.2 Totala 14 19 15 15 13 14 14 15 21 22 21 19 21 16 17 17 na na 18. leads to a yellow-brown colorant.0002 H PIGMENTS Pigments Page 60 Plastics.S. However. 4 7 6 6 5 5 5 5 8 11 10 9 11 7 8 7 na na na 6. Rubber.5 thousand metric tons of synthetic and natural iron oxide pigments from all sources (including imports) in 1999. It is estimated that this segment consumed about 17.3 Synthetic 9 12 9 9 7 8 8 10 13 11 11 10 10 10 8 9 8 na na 11. Textiles. U. in order of rank. Bureau of Mines (data for 1980-1991). producers are as follows: U. Consumption of Iron Oxide Pigments for Plastics. (A) CEH estimates based on Minerals Yearbook and preprints. glass and ceramics. A quantitative consumption breakdown for this group by application is not available. Department of the Interior. © 2001 by the Chemical Economics Handbook—SRI International . U. Data may include some mixture of naturals and synthetics. Glass and Ceramics (thousands of metric tons) Natural 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a. and a preponderance of ferrous ions. glass and ceramics. SOURCES: Natural iron oxides (96% Fe2O3 ) are used as rouge in flat glass batches to impart a greenish cast. The ferric ions in conjunction with oxygen result in green coloration. Geological Survey (data for 1994-1999). textiles. Department of the Interior. Synthetic red is often used as a stain to color glass and ceramic bodies or as a component of decorative glazes.S. Overall. Synthetic reds. Polyethylene trash bags are a growing end-use application for iron oxides. Other . textiles.5-2. but no quantifiable information is available.) In 1999. which are concentrated mixtures of colorant in resin. the presence of higher quantities of impurities can catalyze resin degradation in some plastics. candy box inserts) and in some other food wrapping materials. slowing the breakdown of the polymers and. polypropylene. which are green. There are several iron oxide markets. Hefty® plastic bags. for which little information is available. too.0002 I PIGMENTS Pigments Page 61 Following titanium dioxide. the plastics industry was believed to have used as much as 7-8 thousand metric tons of iron oxide pigments. however. Natural iron oxides are used less often than synthetics in plastics. iron oxides are the inorganic pigments used most in plastics. Burnt umber is frequently used to give a brown tint to phenolic resin–based electrical components. Synthetic reds are often used because they are the most thermally stable. dry pigments. brighter pigments to attain the required color. Yellows tend to change color to red at high temperatures and.g. encapsulates. tends to oxidize to red at high temperatures. yellow and black) is frequently used in plastics. These sands are granular materials. Iron oxide pigments for plastics (or textile) use are generally not sold directly by the producer to either resin manufacturers or plastics fabricators. particularly for simulated leather or for producing wood grain effects. glass and ceramics is 1. are overwhelmingly the form preferred by fabricators. At © 2001 by the Chemical Economics Handbook—SRI International . textiles and rubber is believed to be small. However.May 2001 575. The colorants may be provided as concentrates (pellets. In addition to their low tinting strength. prolonging the life of the plastic products. (The ratio of TiO2 use to iron oxide use is about 30:1.. other pigments (and dyes) are usually preferable. some of which are nonpigmentary. must be baked at comparatively lower heats. to be marketed to plastics fabricators. contain yellow iron oxide and phthalo blue (an organic pigment). Yellows can be safely incorporated into polyethylene. Synthetic brown is used in kraft paper and paperboard for food applications (e. polystyrene and polyvinyl chloride (PVC)—and the thermosets. resins for which iron oxide coloration is appropriate include the thermoplastics—polyethylene. while the more recently available red polyethylene bags are colored only with iron oxide. because of their weak tinctorial strength and drab shades. At this rate of growth.0% for 1999-2004. They in turn manufacture color systems. The consumption of iron oxides in paper. Foundry sands consumed about 14 thousand metric tons of natural red iron oxides in 1999. solvents and alkalies. ochers and umbers can be used. which often contain other plastics additives such as modifiers and fillers. Synthetics sometimes are combined in plastics with other. Concentrates. Black. In phenolic resins. primarily silica. paste dispersions or liquids. browns and yellows are used in rubber. 2004 consumption would total about 19 thousand metric tons. thus. the pigments are marketed to independent formulators. that are mixed with binders to make molds for casting metals. Instead. natural siennas. Estimating the market for iron oxides in the plastics industry is difficult because manufacturers of formulated colorants for the plastics industry also produce fiber concentrates for the textile industry. The combined average annual growth rate for iron oxides in plastics. rubber. paper. Synthetic brown (a blend of red. although it is also safe in polyethylene. granules and powders). Iron oxides are used to some extent in textile applications because of their lightfastness and resistance to heat. thus. Both yellow and red are strong absorbers of ultraviolet radiation. Price The following table presents recent U. About 9 thousand metric tons of iron oxides were consumed in animal feed and fertilizers in 1999.9000 0. Prices for Finished Iron Oxide Pigments (dollars per pound) 1990a Low Black Natural Synthetic Micaceous Red Domestic Primer. origin. However.S. the most important is the reduction of veining and gas defects in the final product.S. High 1997 1999 -0.6900 ------- 0.S.0002 J PIGMENTS Pigments Page 62 least 60% of U. Iron oxide can be used as a dehydrogenation catalyst as well as function as the base material for formulated catalyst products. unless otherwise noted. b. Iron oxides are also used to color surgical gloves.39 na Bulk truckload shipments.08 na na 0. Natural. Iron oxide is also used as a catalyst in the conversion of butenes to butadiene.60 na na 0. it is believed that use of natural iron oxides greatly exceeds that of synthetics. Synthetic Spanish Yellow Synthetic Ocher.2700 0. Micronized Pure. food additives and pharmaceuticals. Although many reasons are given for these additions.May 2001 575. Domestic a.2700d na 1. All fertilizer consumption was of natural oxides. Synthetic iron oxides have FDA approval for use in food contact and special grades are available for use in cosmetics.36 na 0. © 2001 by the Chemical Economics Handbook—SRI International . printing ink.S. In the artist’s colors segment.2875 0. natural oxides can be used only in large-animal feeds. including the synthetic black pigments in the ink used for printing all U. FOB U. currency and artist’s colors. primarily as catalysts in the production of styrene. About 9 thousand metric tons of iron oxides were used in the production of industrial chemicals in 1999.7400b 0. particularly catalysts. Most of this consumption was natural iron oxides. The average addition of oxide to sand mixture is between 1% and 2%. also consume small quantities of both natural and synthetic oxides. Carload shipments of bagged material. prices for iron oxide pigments: U. Industrial chemicals.6875 0. Consumption has been growing slowly in this application for the past decade and is expected to remain fairly flat from 1999 to 2004.46 na na 0.3350c 0. The primary pharmaceutical application is as a colorant for capsules. foundries are believed to add iron oxides to foundry sands. Among the miscellaneous applications for iron oxide pigments are jeweler’s rouge. so there is a small market for synthetics as a colorant in small-animal feeds.8800b 0.33 na 0.S. 9 30.1 2. Imports.2 25. Bureau of the Census.9 37. Prices are for one short ton minimum.5 55. bagged material.4 77.7 21. Unit Import Values (data for 1997 and 1999).0 15.8 7.4 18.5 11.5 37.S. SOURCES: Trade Imports. the highest annual quantity on record.0 19. Reported quantities are thought to be inflated.7 45.5 13.7 16.2 60.9 36..3 5.2 35.3 8.0 19.5 20.0 52.5 53.4 18.7 31. 50 pound bag.6 72.6 74.1 34.4 4.4 61.6 21.2 25.3 Totalb Thousands of Metric Tons 13.S.4 1.7 1.1 Millions of Dollars 1.6 77. (B) U.1 29.7 20.S.0 Data exclude Van Dyke brown for 1960-1982.4 59.4 3. Imports of Iron Oxide Pigmentsa Natural Thousands of Metric Tons 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.1 5.4 0.3 1.4 5.7 9.1 31. U.4 2.4 49.4 2.1 19. as some of the imports are thought to be regenerator or magnetic oxides.7 1.9 29.4 62.4 6.8 1.2 28.3 3.5 51. (A) American Paint & Coatings Journal (data for 1990).0 2.9 15.8 9. imports of synthetic iron oxide pigments were over 85 thousand metric tons.4 38.1 1.6 1.0 27.6 68.6 Millions of Dollars 1.4 64.1 43.4 41.7 34.2 21.2 31.0 1.4 7.4 4. New York warehouse.3 1.3 39.1 2.0 3. Department of Commerce.2 35. U.6 2.2 73.2 16.0 23.7 32.9 57.7 21.8 9.0 6.3 27.7 5.0 29.1 35.9 19.2 30.1 2. d.0 75.6 7.7 7.7 48.7 36.3 61.5 85.4 0.0 70.8 6.7 Synthetic Thousands of Metric Tons 6.0002 K c. In 1999 reported U.8 69.S. 6.2 6.2 67.7 5.3 5.1 30.4 3.7 7.8 4.4 Millions of Dollars 0.May 2001 575.3 8. PIGMENTS Pigments Page 63 Carload shipments.3 0.3 75.8 18.9 34.1 26.4 2.1 33.4 7.7 27.3 62.8 45.4 38.4 1.S.0 2.9 7. © 2001 by the Chemical Economics Handbook—SRI International .9 59.6 38. not exclusively pigments.1 1. import data are shown in the following table: U.6 3.6 18.5 22. S.95 4.00 8.89 10.2 22.0 Red 4. Bureau of Mines (data for 1989-1993).S. U. PIGMENTS Pigments Page 64 Totals may not equal the sums of the categories because of rounding.92 5.23 30.40 5. 0.08 29. (D) U.S.6 Other 8.07 26. Geological Survey (data for 1994-1999).29 5. U. Bureau of Mines (data for 1960-1988).55 8.44 41. (C) Mineral Industry Surveys.9 26.87 6.75 9.56 0. SOURCES: In 1999.70 15. 51% of the natural iron oxide pigments imported into the United States came from Cyprus while China accounted for 52% of the synthetic iron oxide pigment imports. (A) Minerals Yearbook.93 11.60 11.02 11.27 5.80 45. U.19 6. (A) Minerals Yearbook .68 11.94 4. Department of the Interior.30 11.64 31. Import data for synthetic iron oxide pigments are reported by category in the following tables: U.8 28.44 16. Bureau of Mines (data for 1989-1993). (B) Mineral Industry Surveys.S.74 10.14 31. Geological Survey (data for 19941995). (C) Mineral Industry Surveys .00 52.0 Totala 20.1 2.12 11.90 15.S.40 21.60 6.66 0.21 31.S.88 1.2 12.28 27.80 9. U. U. Imports.S. Department of the Interior.34 9.18 17.50 53.25 3.3 3.77 13.S. Bureau of Mines (data for 1983-1988).6 77.85 9.13 12.80 19.94 8.62 11.65 38.4 62. Bureau of the Census (data for 1996-1999).12 10. Department of the Interior.14 1.90 10.38 9. Department of the Interior.04 5.20 25. U.May 2001 575. Department of the Interior. Department of the Interior.90 16. Department of Commerce. Imports of Synthetic Iron Oxide Pigments (thousands of metric tons) Black 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International . U.92 10.S.18 10.71 32.0 Yellow 6.19 11.16 5. U.20 60. (B) Mineral Industry Surveys.80 14.46 0.6 Totals may not equal the sums of the categories because of rounding.0002 L b.S.32 2.9 10.04 3. U.S.4 35.69 4.86 1.11 7.80 24. 10 26.8 16.1 Totala 14. Geological Survey (data for 1994-1999). SOURCES: In 1999.72 21.10 11.92 37.69 2.43 11. (C) Mineral Industry Surveys.68 7.49 55.52 6.30 75. Bureau of Mines (data for 1983-1988). In 1999.19 35.04 3.0 25.44 15.50 6. 0.4 24.84 2. Bureau of Mines (data for 1989-1993).7 3.10 30.20 15.00 10.72 1.39 0.48 2.May 2001 575. (B) Mineral Industry Surveys.5 20.68 23.74 10.7 5.00 29. Imports of Synthetic Iron Oxide Pigments (millions of dollars) Black 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.8 69.7 Other 6.10 12. U.06 4.70 25.68 6.23 25.30 18. Historical export data follow: © 2001 by the Chemical Economics Handbook—SRI International . supply of iron oxide pigments.24 25. U.58 4.74 48.56 23.38 18.63 2.8 thousand metric tons.00 70.96 3.S.98 19.01 7.66 4.26 0. while the balance is sold to end users and resellers.0002 M PIGMENTS Pigments Page 65 U.7 Yellow 5. U.17 12.50 16.59 10. (A) Minerals Yearbook.90 22. followed by Germany.84 7.73 4. West Virginia plant.87 7.50 6. U.S.22 20. Exports.47 11. supply of iron oxide pigments originated in China. iron oxide pigment consumption.S.S.7 thousand metric tons respectively.29 11. Department of the Interior.60 0. exports of pigment-grade iron oxide were 13.39 0.4 61.S.60 72. U.90 10. Some of these pigments are further processed by Bayer at its New Martinsville.90 20. The major destinations for 1999 iron oxide exports were Mexico and Japan at 7.90 59.85 8.S.7 15. Much of the U.90 16.77 5.12 7.52 5.67 8.12 8.15 19. Imports will continue to be an important source of the U.4 19. Department of the Interior.7 and 1.S.80 8.00 19.29 7. Department of the Interior.S.S.8 Red 2.3 Totals may not equal the sums of the categories because of rounding. imports accounted for about one-third of U. May 2001 575.0002 N PIGMENTS Pigments Page 66 U.S. Exports of Pigment-Grade Iron Oxide Thousands of Metric Tons 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCES: 3.5 4.3 4.2 8.0 4.5 4.5 8.3 11.5 29.4 26.9 26.1 20.1 22.0 10.0 9.5 20.6 21.1 22.4 21.3 17.5 14.8 16.6 14.6 13.8 Millions of Dollars 1.0 1.3 1.5 2.3 8.3 10.6 16.1 18.8 28.8 25.0 27.9 28.8 29.9 15.7 18.7 33.8 32.2 32.0 30.7 24.9 22.5 20.6 18.2 15.2 (A) Minerals Yearbook, U.S. Department of the Interior, Bureau of Mines (data for 1960-1988). (B) Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1989-1993). (C) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 1994-1999). Chrome Pigments Producing companies The following table lists the U.S. producers of the major chrome pigments, their plant locations and specific pigments produced: © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0002 O PIGMENTS Pigments Page 67 U.S. Producers of Major Chrome Pigments—April 2001 Lead Chromates Chrome Yellow (PY-34) Molybdate Orange (PR-104) Chromic Oxide Green (PG-17) Hydrated Chromium Oxide Green (PG-18) Zinc Chromate (PY-36) Company and Plant Location Elementis plc Elementis Chromium LP Corpus Christi, TX Engelhard Corporation Specialty Pigments and Additives Louisville, KY Nichem Corp. Chicago, IL Rockwood Specialties Inc Rockwood Pigments Inc Beltsville, MD SOURCE: CEH estimates. X X X X X X X X Since 1997, the following changes have occurred among U.S. chrome pigment producers: q In October 1997, K-L Holdings purchased Laporte Inc’s Mineral Pigments Corporation and changed its name to Rockwood Specialties Inc. National Industrial Chemical of Chicago, Illinois changed its name to Nichem Corp. In 1997, American Chrome & Chemicals Inc became Elementis Chromium LP. q The 1995 closure of Cookson Pigments’ chrome pigment production reduced U.S. chrome pigment capacity by at least 50%. To replace some of the chrome pigment production capacity following the closure, Dominion Colours of Ajax, Ontario, Canada, expanded its capacity by 65%. The largest remaining U.S. producer is Engelhard Corporation, with an estimated annual capacity of 7 thousand metric tons. The two remaining lead chromate producers have annual capacities of less than 5 thousand metric tons each. U.S. chromium pigment production capacity exceeds current production by a multiple of about 3. Salient statistics Production of chrome pigments has been declining since the 1980s and is now about 10% that of the 1970s. The decrease is caused by increasingly restrictive environmental, health and safety regulations, which in turn have increased production expenses and decreased the allowable uses of chrome- and leadbased pigments. © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0002 P PIGMENTS Pigments Page 68 Historical production data for chrome pigments by volume and value are presented in the following table: U.S. Production of Chrome Pigments (thousands of metric tons) Lead Chromates Chrome Yellow and Orange 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a. b. 19.4 26.5 29.4 23.7 25.3 25.4 18.5 19.6 21.2 18.8 17.8 19.8 21.3 15.4 14.7 13.5 11.6 14.1 10.4 9.0 6.0 5.5 5.5 5.0 Molybdate Orange 5.7 8.6 10.0 8.7 8.9 9.2 6.0 5.9 6.7 5.6 5.5 5.1 5.1 4.9 4.4 3.9 3.5 Chrome Greena 2.8 2.8 2.3 ---------------------Chromium Oxide Greenb 4.7 5.8 6.1 5.1 5.2 4.8 3.9 4.7 7.5 ---------------Totalc 32.7 43.7 47.9 37.4 39.3 39.5 28.4 30.1 35.4 24.4 23.2 24.9 26.4 20.2 19.2 17.5 15.1 14.1 10.4 9.0 6.0 5.5 5.5 5.0 Beginning in 1972, data are withheld to avoid disclosing figures for individual companies. Category includes primarily anhydrous chromic oxide although the data also include a small amount of hydrated chromium oxide green. Beginning in 1985, data are withheld by the source in order to avoid disclosing figures for individual companies. Totals may not equal the sums of the categories because of rounding. Total does not include chrome green after 1971 or chromium oxide green after 1984. Data includes hydrated oxide. (A) Current Industrial Reports, Series M28A, U.S. Department of Commerce, Bureau of the Census (data for CHROME YELLOW and ORANGE for 19601990, MOLYBDATE ORANGE for 1960-1987, CHROME GREEN for 19601971, CHROMIUM OXIDE GREEN for 1960-1984 and TOTAL for 19601987). (B) Lead Chromate Pigments Market Position and Possible Substitutes, David Waldron, Cookson Pigments Inc., 1992 (all other data 1972-1992). (C) CEH estimates (data for 1993-1999). c. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0002 Q PIGMENTS Pigments Page 69 Zinc chromate (or zinc yellow) production in 1999 is estimated to have been less than 2 thousand metric tons. Production of this pigment is expected to decline over the next five years as less toxic alternatives such as zinc phosphate gain in popularity. Consumption Estimated U.S. consumption of lead chromate pigments in 1999 was 12 thousand metric tons, less than 30% of the average annual consumption level during the 1970s. The estimated 1996 U.S. consumption of chromium oxide, including the hydrated form, was less than 5 thousand metric tons. This is down from the estimated 9.8 thousand metric tons consumed in 1988. Data for chrome green or the specialty chrome green are unavailable. Consumption is estimated to be less than one thousand metric tons per year. Zinc chromate consumption totaled less than 2 thousand metric tons in 1999. Like other chromates, health and environmental concerns have led to a decline in zinc chromate consumption as consumers seek alternatives. The following table shows the estimated consumption per market segment for lead chromate and chromium oxide pigments in 1988 and 1999: U.S. Consumption of Chrome Pigments by Market Segment (percent) 1988 Lead Chromates Paints and Coatings Plastics Metalsa Ceramic Materials Roofing Printing Inks Other Total a. 60 28 ---12 neg 100% Chromium Oxide 27 10 29 12 9 -13 100% Lead Chromates 65 35 ---neg neg 100% 1999 Chromium Oxide 18 7 43 12 11 -9 100% Chromium oxide is available in three grades, two of which are nonpigmentary (metallurgical and refractory). These two grades are included in the consumption breakdown, as the chemical composition is identical, with differences in particle size, surface area, particle size distribution and shape of the particle. CEH estimates. SOURCE: Essentially all normal lead silicochromate is used in traffic paints or heavy-duty coatings for bridges. Paints and coatings. The largest single application for chrome pigments in the United States is in the surface coatings industry. Historical estimated consumption of chrome pigments in surface coatings is shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International 7 12.7 3.2 2.2 2.8 1.3 2.2 3. machinery and equipment finishes and OEM transportation vehicle finishes—are increasingly switching to non–lead chromate alternatives.1 3.3 2.0 26.8 8.0 9. in rustinhibiting paints. Includes chrome green (a lead chromate) and normal lead silicochromate as well as corrosion-inhibiting pigments strontium chromate. SOURCE: Lead chromate–based pigments are prohibited from use in architectural consumer paints because of regulation by the Consumer Product Safety Act (see ENVIRONMENTAL ISSUES ).9 24.5 4.7 Data for 1984-1988 include about 0.5 3.6 14.5 5. The majority of chrome pigments are used in special-purpose coatings and OEM product finishes.0 1.5 5.3 Molybdate Orange 4.4 19.0002 R PIGMENTS Pigments Page 70 U. Although more resistant to alkali attack than chrome yellow.0 5.6 Chromium Oxidesa 3.5 12.3 2.1 16.8 1.5 thousand short tons annually of specialty-grade chromium oxide green used in camouflage coatings. Consumption of Chrome Pigments for Paints and Coatings (thousands of metric tons) Lead Chromates Chrome Yellow and Orange 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a. chromium oxide green has some application in outdoor industrial coatings.6 8.S. A unique feature of chromium oxide green is that it reflects infrared radiation in a manner similar to © 2001 by the Chemical Economics Handbook—SRI International .8 1.0 7.5 12.8 8.7 31.1 3.0 2.1 4. The major markets consuming chrome yellows— traffic paints. molybdate orange has been used in machinery and equipment finishes.4 13.2 3.3 2.1 4.May 2001 575.5 10.6 4.2 16.1 17.5 1.5 1.5 11.2 3.3 8. CEH estimates.3 2. barium chromate and calcium chromate. the need for larger particles of chrome and molybdate orange pigments makes over-grinding a problem.3 2.9 3.5 1. b.8 1. Totals may not equal the sums of the categories because of rounding. magnesium chromate. The current market for chrome orange.4 26.3 2. is negligible. 18. are less restricted.5 1.4 31.7 8. c.8 9.3 5.8 32.2 3. chromium oxides for example. Because of its brilliance.8 30.9 13. durable automotive finishes.2 3.9 1.8 1.5 4.8 2.8 1.5 8.6 3.1 4.1 3.7 1.3 2.0 2.1 4.0 1.6 15.3 28.1 3. lightfastness and low cost.1 12.3 na na na na na na na na na na na Totalc 32. Since it weathers well.6 na na na na na na na na na na na Zinc Chromate 4. In the past it was often blended with organic reds and violets to produce low-cost.8 Otherb 2.5 4.2 2.6 4. Other chrome pigments.1 8.9 2.1 4.1 18.5 3.8 18. over-grinding creates a yellower hue and results in poor hiding power.8 2. 6 5. traffic paint.9 4.4 4. 3. The consumption of chrome pigments in paints is expected to continue to decrease.7 thousand metric tons were consumed in plastics. They remain in applications where some organic replacements have lacked the performance of lead chromates. has had the greatest impact on lead chromate consumption. low-solubility Krolor® (a registered trademark owned by Dominion Colour) silica-encapsulated lead chromates.7 © 2001 by the Chemical Economics Handbook—SRI International . lead chromate’s largest market segment.S. In 1999. making it appropriate for use in the formulation of camouflage coatings resembling green foliage. Although there are health concerns about zinc chromate. Historically. Safety requirements are being addressed with the use of low-dust lead chromates and low-dust. accounting for over 70% of the paved roads of the U. Hydrated chromium oxide green has some limited use in mixtures with other chrome pigments to produce the brilliant lightfast greens of exterior architectural paints.8 5.6 4.5 6. Zinc chromate is used solely as an anticorrosive pigment.0 6.7 3.0002 S PIGMENTS Pigments Page 71 chlorophyll. such as zinc phosphate. roughly 3. (See the ENVIRONMENTAL ISSUES section for more information on lead chromate environmental regulations. consumption of zinc chromate is expected to decline as other less toxic substitutes.4 3. Estimated consumption of lead chromates by the plastics industry in recent years is reported in the following table: U. The second-largest market segment for lead chromate pigments is plastics. Plastics. Consumption of Lead Chromate Pigments in Plastics (thousands of metric tons) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCE: CEH estimates. it is less toxic and less expensive than the corrosion-inhibiting strontium and calcium chromate pigments. Over half of the states of the United States have banned its use on highways.3 5.8 6. Nonetheless.6 6. are used. with the use of hexavalent chromium and lead highly restricted.0 3.1 4.1 3. Future consumption of chrome pigments in surface coatings is primarily determined by the regulatory environment. particularly in outdoor and harsh environments.4 7.May 2001 575.3 7.S.0 4.7 6.) Organic pigment alternatives are more expensive on a per-pound basis and they may not provide equal durability. The major performance limitation of the chrome yellows and oranges in plastics is in the area of heat stability. the excellent blending characteristics of these pigments with colors of adjoining hues considerably extend their utility. It is expected that consumers will continue to substitute organic pigments where possible. porcelain enamels. which limits its use in applications where a bright green color is preferable. cellulosics. When a bright green color is desired in other resins. mortar. is the pigment of choice. In plastics the chrome yellows and molybdate oranges. This category includes a number of products ranging from industrial refractories to glass. provide high opacity. chromic oxide green is the main ingredient in most green ceramic colorant compositions and is also used to prepare many green-colored glasses. Chrome greens find some application in the plastics industry. Ceramic. a brilliant green hue that dehydrates at 200°C. rather than hydrated chromium oxide. Furthermore. since they can be used only up to 180°C. Less than one thousand metric tons of chromium oxides were consumed in plastics in 1999. The color shading of chromates is equivalent to that of cadmium pigments and they have a lower price. the nonhydrated form is drab in color and low in brightness. However. consumption of all chrome pigments in plastics for 1999-2004 is likely to continue to decline. In ceramic appli- © 2001 by the Chemical Economics Handbook—SRI International . phenolics and polyurethane.000°C. whiteware. these limitations are alleviated by the protection most resins provide at normal pigment-loading levels and/or by the use of silica-encapsulated forms of these pigments. including epoxy. this market represented less than one thousand metric tons. polyethylenes and vinyls. alkalis and sulfides imposes some additional limitations. glass and construction materials. polyesters and urethanes. Thermoset uses include epoxies. because of their outstanding chemical inertness and heat stability up to 1. U. The hydrated form. Chromium oxide greens. including ABS resins. although their reactivity with acids. silica-encapsulated lead chromates compete for a portion of the cadmium pigments market in engineering plastics. low cost and bright colors. although organic pigments may be substituted for a greater share of the market.0002 T PIGMENTS Pigments Page 72 Chromium oxide and chrome greens also find use in this market. Chromium oxide greens are used in thermoplastics. A 15-20%-by-weight coating of silica vastly improves both chemical and heat resistance (up to 320°C) as well as the lightfastness of chromate pigments.S. is used only in cellulosics. Consequently. Generally. pigments for plastics use are not usually sold directly to resin manufacturers or to plastic fabricators but are sold to independent formulators who manufacture color systems. As discussed in the Iron Oxide Pigments Consumption section of this report. china and tile. Lead chromates also are recommended for use in various thermosets. conventional chromates are used to color vinyls and low-temperature polyolefin and polystyrene resins. particularly as state governments increasingly restrict the use of lead in packaging and packaging components under the Coalition of Northeast Governors (CONEG) regulations (see ENVIRONMENTAL ISSUES). Because of its chemical and heat resistance. as well as chemically stabilized forms of these pigments. phthalocyanine green. An estimated 12% of chromium oxide green consumption is in ceramic.May 2001 575. Almost all of this was used in PVC (polyvinyl chloride resin) siding. They are used in polyesters and low-density polyethylene. glass and construction materials. However. In 1996. are appropriate for plastics use. although their sensitivity to alkaline conditions somewhat restricts their performance. Green glasses can be produced using chromium oxide in solution in a siliceous matrix.0002 U PIGMENTS Pigments Page 73 cations. elastomers. it is frequently combined with other ingredients (e. In this case. Roofing granules. Roofing granules are mineral granules. The majority of these chrome-pink pigments are stable up to 1. Chromium oxide greens are also used to color ceramic glazes. calcium. Chromium oxides can also be used in the manufacture of ceramic materials requiring pink coloration. Less than one thousand metric tons of chromium oxide green were consumed as a pigment in roofing granules in 1999. without it the chromium oxide tends to develop a yellow-orange color. pigmented leather finishes and floor coverings. Historically lead chromates have been used in printing inks as they have good hiding power. although it can be used for coloring high-baking enamels. CONEG legislation and rulings by the Food and Drug Administration regarding lead chromate use in inks in food packaging have led to a rapid decline in the total consumption of lead chromates in inks since 1988.350°C. Because of the deleterious health effects of lead chromate pigments. mortar and concrete. No growth is expected during 1999-2004. chromium oxide can be used alone. magnesium. which range in hue from pink through crimson to lilac. aluminum. it is a component of the vitreous coating applied to the metal surfaces of bathtubs and appliances. such as range tops. However by the mid-1990s. coated with silicates mixed with various pigments. Printing inks. washers and dryers. The most common industrial refractories are those composed of single or mixed oxides of chromium. This system performs best when antimony trioxide is present in the glass. However. especially in inks that could contact food or on articles intended for use by children.g. ink flow. © 2001 by the Chemical Economics Handbook—SRI International . It is expected that substitutions for chromium oxide will increasingly be sought in roofing granules. Among the various applications that provide small markets for lead chromate pigments are paper. their use in inks is restricted.. No growth is anticipated in this market. concerns about health and environmental issues had eliminated lead chromate from inks in nearly all applications in the United States. they are commonly mixed with tin oxide and calcium to form the so-called chrome-tin pinks. Green chromium oxide is the most commonly used chromium pigment.May 2001 575. The ceramics market for chrome pigments is believed to be relatively stable. Because this pigment exhibits outstanding resistance to sunlight and the other severe conditions of exterior exposure. cobalt oxide and aluminum oxide) both to modify its color and to improve its stability. Combinations of chromium and aluminum oxides also produce pink to ruby colorants suitable for application in ceramic bodies or in underglaze decorations. Chromium oxide can also be used as a source of green coloration in porcelain enamels. In this case. nonbleeding characteristics and stability. it provides excellent durability in this application. Hydrated chromium oxide green is less heat-resistant than chromium oxide and is therefore unsuited for high-temperature ceramic applications. Chromium oxides also find application in industrial refractories. Other . silicon and zirconium. 0 0.2 1.5 3.1 0.1 0. average unit import values for chrome pigments.5 0.4 2.0 5.8 2.0 2.1 0.1 5.0 6. Imports of Chrome Pigments (thousands of metric tons) Lead Chromates Chrome Green 1964 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 0.6 5.3 9.S.g.S..S.0 1.8 2.3 5.4 5.8 Molybdate Orange neg neg 0.2 1.5 2. U.6 Chromium Oxide Green 0.2 4. imports and import values since 1964 are shown in the following tables: U.9 3.4 © 2001 by the Chemical Economics Handbook—SRI International . ointments).9 6.4 8.8 1.0 6.6 8.3 2.2 1.4 4.7 3.2 0. They have some application in rubber compositions because of their tolerance for any type of cure and also have limited application in textiles and artist’s colors. Trade Imports.7 7.4 6.1 neg neg 0.1 4.5 3.6 3.8 0.1 0.9 0.0 1.8 1.4 0.9 5.9 5.1 neg neg 0.0 6.2 -----------Chrome Yellow 0.3 1.0 3.7 0.7 0.8 6.1 0.8 1.7 0. Price See the trade section for U.9 0.2 0.9 1.4 4.0002 V PIGMENTS Pigments Page 74 Chromium oxides are among the most important inorganics used in cosmetics (particularly in eye makeup and soaps) and also have FDA approval for use as colorants in externally applied drugs (e.2 4.0 0.2 1.8 1.1 neg 0.2 0.9 1.3 3.6 0.May 2001 575.8 8.9 0.8 2.6 2.0 -----------Totala 1.4 6.0 3. No quantitative data on these other markets are available.1 1.5 0.4 6.7 1.5 1.3 6.9 9.8 4.7 4.1 1. S. In 1999. Exports.8 thousand metric tons of the total.0002 W PIGMENTS Pigments Page 75 a. following the closure of Cookson Pigment. chromium pigments plant.S.8 thousand metric tons imported in 1996. export quantities and values of chrome pigments since 1980 are shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International .4 thousand metric tons of chromium-based pigments were imported to the United States.S.30 1. Imports. U. SOURCE: U. U. After 1988. Totals may not equal the sums of the categories because of rounding.93 Zinc Chrome Yellow na 0. Chrome pigment imports from Canada increased beginning in 1996.S.S. a decrease from the 9.75 0. accounting for 6. Chrome yellow was the major import. U. Average Import Values for Lead Chromate Pigments (dollars per pound) Chrome Yellow 1997 1998 1999 SOURCE: 1. 8. Bureau of the Census.S.75 1. Canada was the origin for 55% of the chrome yellow imported. Department of Commerce. U. Imports.May 2001 575. Bureau of the Census.S. total includes zinc yellow and all other pigments and preparations based on chromium compounds.30 1.43 U.65 1. the largest U.28 Molybdate Orange 1. Department of Commerce. 83 7. U.9 1. Exports.62 7. Department of the Interior.S.8 2.5 Value (millions of dollars) 9.S.65 9.S.2 2. Exports of Chrome Pigments Quantity (thousands of metric tons) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCES: 2.S.01 na na 13. Each producer manufactures other products in addition to those specified in the table. Bureau of Mines (data for 1993-1994). production capacity was closed. (C) Mineral Industry Surveys.S. Geological Survey (data for 19951996).07 7.0 2.S.3 1. U. (B) Mineral Industry Surveys.7 2.3 1. Canada and Mexico supply most of the export markets formerly served by the United States.May 2001 575.3 na na 3. U.21 6.3 1. © 2001 by the Chemical Economics Handbook—SRI International . U.2 3.40 6.0002 X PIGMENTS Pigments Page 76 U.0 2. (D) U.1 8.S.S.44 8.25 7.S.50 8.6 2. U.62 9.2 (A) U.3 2.34 9.4 2.8 2.44 7.2 6. lead chromate pigment exports declined after 1996 when over 50% of U. Complex Inorganic Pigments Producing companies U. trade (data for 1997-2000).3 3.53 11. Department of Commerce. producers of complex inorganic pigments (formerly known as mixed-metal oxides) are listed in the following table.S. Department of the Interior. Bureau of the Census (data for 1980-1992).42 11.7 2. PBk.0002 Y PIGMENTS Pigments Page 77 U. New York complex inorganic pigments plant.PBk.and pigment-grade complex inorganic pigments. Production U. OH Toccoa. PA Engelhard Corporation Specialty Pigments and Additivesb Elyria. production data for complex inorganic pigments are not published. Colors. GA The Shepherd Color Companyb Cincinnati.PBR27 28 30 PB28 PB36 PBn24 PBn33 PG26 PG50 PBr35 PY53 PY164 X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Only selected complex inorganic products are shown.S. SOURCE: In December 2000.S. BASF closed its Rensselaer.S.May 2001 575. CEH estimates. Company also produces PG-17. For 1999.9 thousand metric tons. Producers of Major Complex Inorganic Pigments—March 1997 a Company and Plant Location Cerdec Corporation Drakenfeld Products Washington. © 2001 by the Chemical Economics Handbook—SRI International . production was an estimated 7. & Ceramics Group Pigments Division Cleveland. All producers listed in the table manufacture both ceramic. U. OH Ferro Corporation Coatings. Color key: PBk-27 PBk-28 PBk-30 PB-28 PB-36 PBn-24 PBn-33 PG-26 PG-50 PV-14 PY-53 PY-164 = = = = = = = = = = = = Black 27 (iron cobalt chromite black) Black 28 (copper chromite black) Black 30 (chrome iron nickel spinel) Blue 28 (cobalt blue or cobalt aluminate blue spinel) Blue 36 (cobalt chromite blue-green spinel) Brown 24 (chrome antimony titanium buff rutile) Brown 33 (nickel ferrite brown spinel) Green 26 (cobalt chromite green spinel) Green 50 (cobalt titanate green spinel) Violet 14 (cobalt violet phosphate) Yellow 53 (nickel antimony titanium yellow rutile) Yellow 164 (manganese antimony titanium buff rutile) b. OH a. the leading plastics application was in polyvinyl chloride (PVC) for exterior siding. Chrome antimony titanium buff rutile (PBn-24) is often the colorant of choice. appearing black in higher concentrations is typically used as a substitute for carbon black for siding since it absorbs less energy and.0 0. Their excellent stability at high temperatures can make them a good choice in certain plastics applications.1 7.0002 Z PIGMENTS Pigments Page 78 Consumption Estimated U. Coextruded siding not only requires less pigment than traditional PVC siding but also results in a more durable product. therefore. spark plug cables and computer cables where color coding is important. rare earth–based pigments from Rhône-Poulenc in France show significant promise in the thermoset plastics market segment. 4. weakening some plastics. a laminate surface of color containing complex inorganics and titanium dioxide is coextruded over a nonpigmented PVC base profile. For overall plastics use.6 thousand metric tons of complex inorganic pigments were consumed in the plastics and rubber industries in 1999. lowers air-conditioning costs. An estimated 4. cap stock. Nickel and chrome titanates are the most frequently used complex inorganics in PVC. The PVC siding market accounts for approximately 75% of total complex inorganics used in the plastics and rubber market segment. This cerium containing pigment line.1 0.May 2001 575.S. Instead of pigmenting the entire piece of siding.6 thousand metric tons. consumption of complex inorganic pigments in 1999 was 7. Manganese titanates may be used in place of iron-containing pigments.6 1.6 1999 Market Share (percent) 60 24 13 3 100% Plastics and rubber. Nickel titanates in combination with high-performance organic pigments have replaced some lead chromates and cadmium yellows.2 7. thermosets and high-temperature engineering resins. PVC siding has traditionally been used for remodeling and for mobile homes.S. which sometimes compromise the stability of some resins. Although these pigments were used for coloring a variety of thermoplastics. uses only an outer layer of pigmentation.S. The leading rubber applications include the coloration of silicon rubber used in high-temperature hoses.8 1. Imported. The major PVC siding application for complex inorganic pigments. known as Neolor™. PG-17. However.6 Market Share (percent) 60 24 15 1 100% Quantity (thousands of metric tons) 4. is available © 2001 by the Chemical Economics Handbook—SRI International .6 1. their poor tinctorial strength can require a heavy loading. but it has recently gained acceptability in new residential construction.8 1. both chrome and nickel titanates have attained prominence as colorants. U. consumption for 1996 and 1999 is segmented as follows: U. Consumption of Complex Inorganic Pigments 1996 Quantity (thousands of metric tons) Plastics and Rubber Ceramic and Glass Materials Paints and Coatings Other Total SOURCE: CEH estimates. because of manufacturing relocations and rising imports. Ceramic and glass materials.S. To withstand these extremely high temperatures. Overall. To some extent. they lack the brilliance and intensity of cadmium colorants. a blue color results. auto enamels and coil coatings for outdoor applications.) The spinel complex inorganics have a cubic structure and vary in color from blues to greens to browns and blacks depending upon the metal ions introduced into the crystal structure. Tile and sanitaryware applications differ from one another in the heat required to fuse the glaze to the ware. Applications for complex inorganics include ceramic bodies.S. forehearth colors (strongly colored glass added to molten uncolored glass) and on-glass decorations. This product is a suitable. particularly from Italy. has decreased U. ceramic production and the overall demand for pigments in ceramics. the zircons are employed.May 2001 575. Thus. Some spinels fail to withstand the 1. porcelain enamels. Paints and coatings. nickel titanates are used as substitutes for chrome yellows.8 thousand metric tons. albeit expensive alternative to cadmium pigments with a price of $17-18 per pound.S. Although these types of pigments possess a wider range of temperature stability than the cadmiums (which are also used to color ceramics). They actually dissolve. They are consumed in exterior house paints.300°C. Nickel titanates are probably the most important single group of complex inorganics used in paints. Zirconium silicate is an extremely stable oxidic compound with a cubic lattice into which metallic ions may be introduced to generate color. © 2001 by the Chemical Economics Handbook—SRI International . the increased imports of ceramics. Complex inorganics were first used in ceramics and glass applications because of their high heat stability. complex inorganics are often the pigments of choice. complex inorganics of the spinel and zircon families are commonly used. ceramics production has been declining in the U. Tiles are normally heated to about 1. the two applications can overlap. however. for higher-temperature firings. if vanadium is substituted for silicon in the crystal structure. Spinels are used extensively in wall tile and in some sanitaryware.300°C. Cobalt chromite green is the second complex inorganic pigment of significance in the coatings industry.0 thousand metric tons.0003 A PIGMENTS Pigments Page 79 in orange (PO-75) and red (PR-265).300°C temperature. A coral or peach color is generated when iron oxide is encapsulated by zircon and a yellow results when praseodymium is substituted for some of the zirconium ions in the lattice. destroying the crystal lattice. overglaze decoration. Consumption in 1999 was an estimated 1. colored glasses. Consumption of complex inorganics in paints and coatings in 1999 was estimated at 1. In particular. it is valuable as a camouflage coating and has been approved for use in U.140 °C while sanitaryware is fired to about 1. resulting in disappearance of the color. Since clay-based products are often coated with glazes. underglaze decoration. Reductions in the use of cadmium because of environmental regulations continue to create increased demand for complex inorganics over cadmium . military applications. accounting for about 15% of total consumption. colored glazes. (See the following section on Cadmium Pigments. Since this pigment simulates the reflectance properties of chlorophyll. The ceramic and glass materials colorants category includes both colorants used in clay-based products and colorants used in glass manufacture. For example. The processing temperatures required in these applications may be as high as or higher than 1. Porcelain enamel has also been declining as white goods are increasingly manufactured with painted metal. 60 none 1. in coating machinery. including cobalt-based complex inorganics. Price The following table presents representative list prices for selected complex inorganic pigments: U. cement grouts. complex inorganic pigments in paints and coatings have nearly completed their growth because of replacement of chrome yellows and cadmium pigments.50 --none 0. These coatings are used primarily on aluminum and steel sidings for residential homes. In the United States.20 5. The urethane finish lasts much longer than the alkyd.00 5.06 na none 2. tent materials and truck tarps.00 ---- na 4. ceramics.68 12. depending on cobalt market conditions. Cobalt Surcharge March 1997 Prices Cobalt Surcharge March 2001 Prices Cobalt Surcharge 19. Limited quantities of complex inorganics are used in adhesives.00 none 1. CEH estimates.60 ---3. camouflage coatings have evolved from alkyds to two-component urethane systems.95 16.29 ---- na 18. brown and black pigments. plus small quantities of organic pigments. SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . Often the blends include black iron oxide. strips and coils of aluminum or steel and baked at high temperatures.May 2001 575. chromium oxides. mobile homes and commercial buildings. Cobalt surcharge is included in price and is subject to change without notice. concrete swimming pools.07 none 1.60 24.25 none Prices based on one thousand pound quantities. List Prices for Complex Inorganic Pigmentsa (dollars per pound) March 1994 Prices Dry Black (PBk-27) Paint Grade Ceramics Grade Black (PBk-28) Paint Grade Blue (PB-36) Paint Grade Brown (PBn-33) Paint Grade Green (PG-50) Violet (PV-14) Brown (PBn-24) Paint Grade Yellow (PY-53) a.S. inks (including food contact inks for plastics). camouflage coatings are generally blends of green.00 1. roofing granules.25 11. containing complex inorganic colorants. are liquid resin systems applied at high speeds to continuous sheets. The primary complex inorganics used in coil coatings are nickel and chrome titanates.00 13. Coil coatings are believed to consume the largest percentage of the complex inorganics used by the surface coatings industry. However. zinc ferrites and cobalt chromite green. artist’s colors and cosmetics (particularly violet).50 ---- --5. Other . The coatings. reducing the need to refinish as frequently.25 11.0003 B PIGMENTS Pigments Page 80 In practice.60 3.86 na 5.60 6.02 6. which possess color stability at high temperatures.57 ---- 2. Camouflage pigments are used in fabrics for netting. The size of this market segment was about 200 metric tons in 1999.65 36.40 ---none 0.00 13. salient statistics for cadmium-based pigments are shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International . Color key: PO-20 PR-108 PY-35 PY-37 = = = = Cadmium sulfoselenide orange (Cd[S/Se]) Cadmium sulfoselenide red (Cd[Se/S]) Cadmium/zinc sulfide yellow ([Cd/Zn]S) Cadmium sulfide yellow (CdS) Orange (PO-20) Orange (PO-20:1) Red (PR-108) Red (PR-108:1) Yellow (PY-35) Yellow (PY-35:1) Yellow (PY-37) Yellow (PY-37:1) X X X X X X X X X X X X X X X X A colon followed by “1” denotes the lithopone form of the pigment. Englehard Corporation is the largest-volume producer. Baltimore.May 2001 575.S. Salient statistics U. Inc. Taiwan. MD a. primarily from Japan and Germany.0003 C PIGMENTS Pigments Page 81 Trade Trade data for complex inorganic pigments are not reported. Asia (China. Ferro blends pigments at the Cleveland. It is estimated that just over 450 metric tons were imported by the United States in 1999.S. Mexico. KY Millennium Inorganic Chemicals. with destinations primarily in Western Europe. Exports are estimated at 675 metric tons in 1999. Producers of Cadmium Pigments—March 2001a Company and Plant Location Engelhard Corporation Specialty Pigments and Additives Louisville. Ohio plant that are produced in Celaya. Malaysia and Singapore) and South America. the Republic of Korea. SOURCE: CEH estimates. producers of cadmium pigments.S. Cadmium Pigments Producing companies The following table lists U. followed by Canada. plant locations and specific products manufactured: U. (C) CEH estimates (all other data). (B) U.5 0.2 0.5 0.7 0.7 0. Bureau of the Census (data for EXPORTS). U.3 thousand metric tons.4 0.1 0.4 0.3 0.0003 D PIGMENTS Pigments Page 82 U.2 0.4 0.2 0.9 0.2 Exports na na na neg neg 0.S. Exports.6 0. U. CONEG requirements and EPA regulations increasingly restrict the use of cadmium.4 Imports na na na 0.8 0. 13% of the amount consumed in 1988.4 0.5 0.5 0. Department of Commerce.S.1 0.9 0. Imports.6 0.S.2 0. Consumption of Cadmium Pigments by End Use 1996 Quantity (metric tons) Plastics Ceramic Materials Paints and Coatings Other Total SOURCE: CEH estimates.S. 325-350 100-125 neg 25-40 450-515 Market Share (percent) 65-70 20-25 neg 5-8 100% Quantity (metric tons) 180 30-40 30-40 30-40 270-300 1999 Market Share (percent) 60 10-15 10-15 10-15 100% © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575.4 0. Estimated market shares of cadmium pigments by end use in 1996 and 1999 are presented in the following table: U.9 0. consumption of cadmium pigments in 1999 was about 0.2 0.4 0.3 (A) U.3 Apparent Consumption na na 2.3 0. U.9 0.8 0.4 0. Bureau of the Census (data for IMPORTS). gross weight basis) Production 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCES: 0.8 0.2 0.8 0.3 1.S.3 0.S.2 0. Cadmium pigment consumption and production is expected to fall further as OSHA limits on cadmium exposure in the workplace.S.1 0. Supply/Demand for Cadmium Pigments (thousands of metric tons.7 1.6 0. Department of Commerce.6 0.4 0.2 0. 2 2. plastics compounders introduce © 2001 by the Chemical Economics Handbook—SRI International . cadmium pigments work well in practically all plastics.S.2 0. More often. nylons. The plastics industry is the largest U.2 2. market for cadmium pigments. Much of this consumption is of the lithopone form of cadmium pigments.3 0. Polyvinyl chloride (PVC) and engineering resins such as polycarbonates. ability to tolerate high temperatures (800-900°C).4 0.1 1.2 Historically. They are weak only in their resistance to acidic conditions or moisture. because of their opacity.7 0. low-density polyethylene (LDPE). resistance to migration. excellent lightfastness. Consumption of Cadmium Pigments by the Plastics Industry (thousands of metric tons) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCE: CEH estimates.1 2.0 2.5 1.0003 E PIGMENTS Pigments Page 83 Plastics. Estimated consumption of cadmium pigments in plastics in recent years is reported in the following table.May 2001 575. although mixtures of complex inorganics and organic pigments may also be used. cadmium has been the pigment of choice. cadmium pigments have been consumed mainly in the following plastic resins: acrylonitrilebutadiene-styrene terpolymer (ABS).8 0. Bayer reformulated its cadmium-containing pigments and substituted organic dyes in its inorganic and organic pigments.4 0.1 0. As is true for other pigments.2 2. Bayer Corporation ceased cadmium pigment use in its thermoplastics in 1990. brilliant clear colors and easy dispersibility. On a functional basis.2 2.2 0. polypropylene (PP) and polystyrene (PS).S. cadmiums are not generally introduced into plastics through direct dispersion of dry pigment into the host resin material. thermoplastic polyesters and polyphenylene oxides have historically accounted for less than 5% of the plastic market for cadmium pigments. Other plastics producers such as General Electric have also replaced cadmium pigments in their products. In the higher-processing-temperature plastics such as HDPE and the engineering resins.2 2.5 2.5 0. 2. polyacetals. high-density polyethylene (HDPE). U. Paste dispersions. Cadmium colorants work well because they are capable of withstanding extremely high ceramic processing temperatures (up to 900°C) and because of the bright. the consumption of cadmiums in paints and coatings was dominated by primers. some machinery and equipment coatings. Paints and coatings. auto refinishing and various specialty coatings. The largest portion of cadmium pigment consumption for ceramics applications has traditionally been in porcelain enamels for aluminum. liquid color and encapsulated pigments have also found wide acceptance among plastics formulators as a means of introducing color to resins. this is estimated to have been less than 40 metric tons. An estimated 30-40% of the total market for cadmium pigments is in the ceramic materials area. in porcelain enamel coatings for metal and in underglaze and overglaze decorations and glaze stains for ceramic clay objects. Cadmium yellows and reds are used both in mass coloration of glass (e. In 1999. Historically. Currently. pigment stability and chemical durability are used in conjunction with the cadmium colorants.0003 F PIGMENTS Pigments Page 84 pigments in a predispersed form. the largest portion of cadmium pigments consumed in ceramics is in ceramic tiles and artware.g. railway signal glasses and marine navigational lights) and in on-glass decorations (e. because of their good resistance to chemical attack. All these pigment vehicles reduce the problem of dusting and provide higher color consistency. There was a market for cadmium pigments in aluminum cookware. process equipment and general interior plant use. exhaust systems and heater parts. In 1999. which hold cadmium colorant in a compounded resin. permitting plastics fabricators to add color at the optimum stage of the manufacturing process. Such glazes are low in alkali content and usually contain cadmium oxide..g. labels on soda bottles). varied colors they offer.May 2001 575. as well as resistance to heat. cadmium pigment consumption per volume of plastic produced is expected to decline despite growth in plastics output. Cadmium reds. reds for traffic signals. Such aluminum products as gas barbecue grills may be coated with enamels containing cadmium sulfide or sulfoselenide pigments. as components of glaze stains and in overglaze and underglaze decorations. This may also occur with cast iron stove parts. known as masterbatch pellets. The overall decline in this market is expected to continue. sheet steel and cast iron. Over the next five years. oranges and yellows have been used extensively (usually in the form of colored frits) in the mass coloration and external decoration of glass. cadmium pigments were used in the manufacture of industrial coatings (particularly coatings used for anticorrosion maintenance) for steam and process chemical pipes. the cadmium pigment particles are colloidally dispersed and produce colors by selective absorption and scattering of light. Smaller applications included use in metal coil coatings. In these transparent glass applications. Ceramic materials. Glazes formulated to be compatible with the pigments and to promote color development. thereby enhancing the stability of the pigment in the final glazed product. The presence of the oxide reduces the chemical potential of the cadmium in the molten glaze during firing. but this has declined significantly as imports have replaced domestic products and consumer preference has changed from bright colors to browns. © 2001 by the Chemical Economics Handbook—SRI International .. particularly from alkalis. (B) Chemical Marketing Reporter (data for 2000). 400-pound barrels.18 4. reflecting weak demand.31 5.64 0.May 2001 575.18 4.43-4. other uses accounted for less than 40 metric tons of cadmium pigments in 1999. Cadmium-Selenideb Light Medium Light Medium Deep Maroon Yellow Pure Red Yellow a.75-5. (A) American Paint & Coatings Journal (data for 1989 and 1995). Prices for cadmium pigments are expected to soften as demand continues to decay.S. synthetic fibers.63-9.76 5.88 5.31 5.46 4.14b na na na na na na na na c. FOB shipping point. freight allowed east of Rocky Mountains. Price U.35-4. cadmiums are rarely the pigment of choice. Between 1995 and 1996. Cadmiums were also used to color some printing inks. One-ton lots. such as rubber flooring and silicone rubber cable. 1995 2000 3. use in these applications is believed to be extremely limited and likely to decrease. because other less expensive pigments also satisfy rubber requirements.43-4.0003 G PIGMENTS Pigments Page 85 Other .S. Altogether.70-0.76 2.74 6.70 4.64 na 6. However. lightfastness and sulfide stain resistance.15c 8.35-4.65-7.88 5.46 4. prices doubled for some lithopone cadmium-selenide reds. SOURCES: On a price-per-pound basis. However. Cadmium pigments also have some limited use in rubber products. paper laminates and leather finishes.63-9. 500-pound bags. Cadmium-Selenidea Deep Red. freight allowed east of Rocky Mountains. Prices for Finished Cadmium Pigments (dollars per pound) 1989 Lithopone Orange.10 4. cadmium pigments are generally more expensive than other inorganic pigments (except complex inorganics). Cadmiums are stable to the curing conditions of rubber and do not stain or bleed.15-4. oranges and reds offer pleasing hue. year-end prices for cadmium pigments in selected years were as follows: U. FOB shipping point. while prices for other cadmium pigments remained relatively unchanged. Most of the other uses are believed to be in artist’s paints where cadmium yellows.15-4.75-5.34c 8.23-3. © 2001 by the Chemical Economics Handbook—SRI International . b. 6-1.May 2001 575.8 Cadmium neg neg Trade Complete data are not available for Canadian trade in inorganic pigments. According to U.9 21. Lead Chromate 1. Lead chromates production capacity was expanded by 65% at this plant in 1996. trade statistics. bismuth vanadate and rare earth sulfides. consumption of minor pigments not produced in the United States.8 1. Other Inorganic Pigments See the “World Market Value of Color Pigments by Region—1999” and “World Consumption of Pigments by Region—1999” tables for U.0003 H PIGMENTS Pigments Page 86 Trade Trade data for cadmium pigments are reported in the Salient statistics section. No detailed information is available on the supply and demand for other inorganic pigments. Ontario is the world’s largest lead chromate plant and the only site of lead chromate production in Canada. Canadian exports of inorganic pigments to the United States are as follows: © 2001 by the Chemical Economics Handbook—SRI International . CANADA Producing Companies Dominion Colour Corporation’s plant in Ajax. Consumption Canadian consumption of inorganic color pigments is estimated in the table below. In 1997 the Ajax facility began production of silica-encapsulated lead chromate pigments.S. The company produces chrome yellow (PY-34) and molybdate orange (PR-104). The majority of Canada’s pigment exports are to the United States. iron blues.S.6-1. including ultramarines. Canadian Consumption of Inorganic Color Pigments (thousands of metric tons) Iron Oxide 1996 1999 SOURCE: 17. using technology purchased from Cookson Pigments. Further information about the manufacture of these pigments and trade can be found in the Western European section.3 CEH estimates. V.S. Chrome pigments The following table lists the chrome pigments producers of Mexico: Mexican Producers of Chrome Pigments—April 2001 Lead Chromates Company and Plant Location Pyosa.S.V.May 2001 575. shifting lead chromate supply to imports from BASF’s plant in Germany. Nuevo León SOURCE: CEH estimates. Department of Commerce.A. U.A. S. chromium exports grew significantly following the closure of half of the U.568 5. Chrome Yellow (PY-34) Molybdate Orange (PR-104) X X BASF’s lead chromate pigment plant at Santa Clara closed in 1997.S. MEXICO Producing Companies Iron oxide pigments De Mateo y Compañía.967 6. de C. lead chromate production capacity in 1996. Bureau of the Census. S. Imports. Canada’s U. México produces synthetic black (PBk-11) and Synthetic Brown (PBn-6).0003 I PIGMENTS Pigments Page 87 Canadian Exports of Inorganic Pigments to the United States (metric tons) Synthetic Iron Oxide 1993 1994 1995 1996 1997 1998 1999 SOURCE: 394 5.209 Cadmium 30 54 34 29 77 47 62 U. Monterrey. © 2001 by the Chemical Economics Handbook—SRI International .064 Chromium 18 na 321 7.056 7.S. de C.380 6.030 4.001 5. in Zumpango.260 6.940 4. PB-35. PB-71).5 Cadmium neg neg © 2001 by the Chemical Economics Handbook—SRI International . PR-235.7 17.A.8 16. Lead Chromate 2.5 14. PY-160) pigments. PR231. S. Production Mexican inorganic color pigment production between 1994 and 1999 is as follows: Mexican Inorganic Pigment Production (thousands of metric tons) 1994 1995 1996 1997 1998 1999 SOURCE: ANIQ.5 12.8 Estimates for consumption of other inorganic pigments are not available.V. Mexican Consumption of Inorganic Color Pigments (thousands of metric tons) Iron Oxide 1996 1999 SOURCE: 16-17 19-20 CEH estimates. PR-232.5 2. Consumption Mexican consumption of inorganic pigments is estimated in the table below. PR-236) and yellow (PY-158. This plant produces black (PBk-28). PY-159. blue (PB-28. in Mexico City. 15. de C.6 8.May 2001 575.0003 J PIGMENTS Pigments Page 88 Complex inorganic pigments Only one company is known to produce complex inorganic pigments in Mexico: Ferro Méxicana. red (PR-230. PR-233. 2 2.May 2001 575.1 3.2 3. 44% of Mexico’s chromium pigment exports went to the United States. while weakening U.1 neg neg Other 1.1 0.3 5.8 6.3 2.7 (A) Sistema de Información.2 0.3 0.2 0. Banco Nacional de Comercio (data for 1993-1995 and TOTAL all years).4 5.2 2.3 5. Comercial de México.7 Total 1.5 5.1 3.7 3.1 0.3 5.4 3.5 3.0 1.2 2.5 2. Comercial de México. In 1995.2 2.1 3.1 0. © 2001 by the Chemical Economics Handbook—SRI International .3 0.1 2.0003 K PIGMENTS Pigments Page 89 Trade Import data are available for Mexican inorganic color pigments in the following table: Mexican Imports of Inorganic Color Pigments (thousands of metric tons) Chromium Pigments 1993 1994 1995 1996 1997 1998 1999 SOURCES: 0. Export data are available for Mexican inorganic color pigments in the following table: Mexican Imports of Inorganic Color Pigments (thousands of metric tons) Chromium Pigments 1993 1994 1995 1996 1997 1998 1999 SOURCES: 1.3 0. (B) CEH estimates (all other data).1 0. Chromium pigment exports rose rapidly following the peso’s devaluation in 1994.4 3. Banco Nacional de Comercio (data for 1993-1995 and TOTAL all years).9 2. Total inorganic color pigment exports more than doubled between 1996 and 1999 to 6 thousand metric tons.2 0.4 Total na 3.1 3.0 (A) Sistema de Información.3 Cadmium Pigments 0.S. demand for cadmium pigments led to a decline in cadmium exports.5 5.3 Cadmium Pigments neg neg neg neg neg neg neg Other na 2. (B) CEH estimates (all other data).3 2. followed by Canada at 17%.2 2. The United States was the sole destination for cadmium pigment exports in 1995.1 3. São Paulo Cleomar Química Indústria e Comércio Ltda. São Paulo Chile Pigmentos Marathon S. Venezolana de Pigmentos in Valencia.A. Región Metropolitana de Santiago X ___________________ a. Buenos Aires Brazil BASF S. plant locations and specific pigments produced: South American Producers of Synthetic Iron Oxide Pigments—March 2001a Company and Plant Location Argentina Química Sudamericana S. Carabobo. Black PBK-11 Red PR-101 Brown PBn-6 Yellow PY-42 X X X X X X X X Chrome Pigments The following table lists the chrome pigment producers in South America: South American Producers of Lead Chromate Pigments—March 2001 Chrome Yellow (PY-34) Molybdate Orange (PR-104) Chromium Oxide Green (PG-17) Company and Plant Location Argentina ARCOLOR S. Pilar.I.A.A. C.A.I.May 2001 575. São Paulo X X X X X © 2001 by the Chemical Economics Handbook—SRI International . Quinta Normal. Sumaré. Indaiatuba.A. São Caentano do Sul. Buenos Aires Brazil Bayer S. Porto Feliz.A. SOURCE: CEH estimates. São Paulo Química Brasil-Sumaré Ltda. C. Venezuela also produces a number of iron oxide pigments. Berazategui.0003 L PIGMENTS Pigments Page 90 SOUTH AMERICA Iron Oxide Pigments The following table lists synthetic iron oxide–producing companies.A.F. A.I.I. Pilar. at Pilar. © 2001 by the Chemical Economics Handbook—SRI International .F. Carabobo SOURCE: CEH estimates. C.I.May 2001 575. Sao Bernardo do Campo Sao Paulob a. Argentina.I.A.F. SOURCE: Cadmium Pigments Cadmium pigments PO-20. X X X Complex Inorganic Pigments At least two companies produce complex inorganic pigments in South America: South American Producers of Complex Inorganic Pigments—April 2001 Company and Plant Location Argentina ARCOLOR S. Ferro also produces PR-233. Venezolana de Pigmentos Valencia. b. Buenos Aires a Brazil Ferro Enamel do Brazil Industria e Comercio Ltda. PR-236 and PY-159.A. PR-108 and PY-37 are produced by ARCOLOR S. Black (PBk-28) Blue (PB-28) Blue (PB-35) Brown (PBn-24) Brown (PBn-33) Red (PR-231) Yellow (PY-53) Yellow (PY-160) X X X X X X X X X Arcolor also produces PB-36. Girardota.A. C.A.A. CEH estimates. PR-235. Buenos Aires. Antioquía Venezuela C.0003 M PIGMENTS Pigments Page 91 South American Producers of Lead Chromate Pigments—March 2001 (continued) Chrome Yellow (PY-34) Molybdate Orange (PR-104) Chromium Oxide Green (PG-17) Company and Plant Location Colombia Pigmentos y Productos Químicos S. Micronized iron oxide pigments have a number of advantages over the standard grades: q Higher tinting strength Lower oil absorption Easier dispersing Lower processing costs for end users because of the lower volumes required q q q In addition. yet only a few companies account for the major share of production and Bayer is by far the world’s largest supplier. is carried out by a vast number of companies. iron oxide pigments are now being produced in a granular form. an increasing number of manufacturers are now also offering higher value-added micronized granular grades.0003 N PIGMENTS Pigments Page 92 Consumption See the “World Consumption of Pigments by Region” table for South American inorganic color pigment consumption. Although there are only a few basic producers of synthetic iron oxide pigments in Western Europe. a large number of companies produce different grades and shades of iron oxide pigments from either purchased pure natural pigments or mixtures of natural and synthetic iron oxides. WESTERN EUROPE Iron Oxide Pigments Producing companies Western European producers of iron oxide pigments have been facing a number of challenges from the following reasons: q Relatively mature markets Large number of producers and traders Considerable oversupply and low overall capacity utilization Decreased profitability in most sectors Increased Asian competition (particularly China and India) q q q q Iron oxide pigments are the single largest-volume group of color pigments produced in Western Europe. Production of these pigments. which includes natural iron oxide. The advantage of using granular pigments is the low-dust emission and free flowability of the product.May 2001 575. Whereas companies manufactured only ground pigments in the past. © 2001 by the Chemical Economics Handbook—SRI International . Product is byproduct from magnetite and haematite ores. [Belgium]) Chaillac Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Remarks X -- -- -- Barite by-product from feldspar production.0003 O PIGMENTS Pigments Page 93 Natural iron oxide pigments. A 4 thousand metric ton-per-year red iron oxide pigment plant came on stream in mid-1994.A. the most important of which are Spain and Italy for the color iron oxide pigments. natural iron oxide pigments are produced in a number of countries. In Western Europe. Produces primarily synthetic iron oxides. The following table lists the Western European producers of natural iron oxide pigments: Western European Producers of Natural Iron Oxide Pigments Company and Plant Location France Barytine de Chaillac SA (owned by Solvay S. Marius Lamy & Companie SARL Apt Oxymine S. KG Bruchsal Dr.A. X -- X -- Plant started in 1990. Spain Agroquímica del Vallés. Austria is the leading producer of micaceous iron oxide pigments. Veneta Mineraria SpA Alagna Valsesia Norway Rana Gruber AS Mo i Rana X -- -- -- By-product from feldspar production. (owned by Poortershaven [Netherlands]) Poissy Germany Bruchsaler Farbenfabrik GmbH & Co. Pigment used primarily in the construction industry. SA Las Franquesas del Vallés X -- -- -- © 2001 by the Chemical Economics Handbook—SRI International . KG Langelsheim. Hans Heubach GmbH & Co.May 2001 575. Niedersachen Italy Società Italiana Ossidi Ferro SpA Pozzolo-Formigaro Piemonte -- -- -- X X X X X X -- -- -- X -- -- -- X X -- X Small output only. © 2001 by the Chemical Economics Handbook—SRI International . b. Termoplásticos Villafranqueza Oxidos del Sur SA Huercal de Almeria Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Remarks -- -- X -- -- X X X A smaller company producing a range of iron oxide pigments.A. Micaceous iron oxide. United Kingdom Elementis UK Ltd. Produces superfine and micronized iron oxide pigments for primarily the paint. CEH estimates. Peterlee Winford Red Oxide Co.. Company is associated with Oxhinsa. (owned by Golden Valley Colours Ltd. The company accounts for approximately 50% of total world synthetic iron oxide pigment output. ceramic enamels and frits industries. Haley & Son Ltd. Oxidos Rojos de Andalucía Ramon Alcade Zorrilla Jaén Oxidos Rojos de Málaga.0003 P PIGMENTS Pigments Page 94 Western European Producers of Natural Iron Oxide Pigments (continued) Company and Plant Location Spain (continued) Asensi.May 2001 575. Elementis Pigments Milton Keynes Laminox Ltd. [United Kingdom]) Málaga -- -- X -- Mining and processing plant. S.L. glass. Ocher surface mine. Iron oxide content is 40-50%.—PROMINDSA Sopuerta Tierga X X --- -X X -- Combined capacity for black magnetic iron oxide and yellow pigments. (100% owned by W. SOURCE: Synthetic iron oxide pigments. Spain. Productos Minerales para la Industria.) Duffield Winford -- X -- -- -- X -- -- --- --- --- X -- Processing plant. a. S. Ltd. -- -- X -- Produces micronized and superfine red pigments. The most important producer of synthetic iron oxide pigments in Western Europe and the world is Bayer AG. SA. the company has operated a 20 thousand metric ton-per-year plant at Langelsheim. The company is manufacturing a wide range of different grades and hues of iron oxide pigments and recently started manufacturing granular pigments. as well as micronized and encapsulated pigments. Synthetic iron oxide pigment producers are listed in the following table: © 2001 by the Chemical Economics Handbook—SRI International . including twenty standard-grade reds. five blacks and the micronized grades (Bayferrox™).0003 Q PIGMENTS Pigments Page 95 Bayer produces a range of more than sixty different varieties of iron oxide pigments. The range includes four reds. seven yellows and one black. ten yellows. which include ten reds. Through acquisitions and capital investments. Since 1997. Germany. K-L Holdings (the acquirer of Laporte) has advanced to the number two position worldwide. BASF is producing a range of transparent iron oxide pigments that are used in higher-value-added products. four reds and one black. Heubach is a relatively new and aggressive iron oxide pigments producer. Heubach’s iron oxide pigment range includes one yellow. two yellows and one orange. nine browns. Recently the company initiated a major upgrade and expansion program for its iron oxide pigment operations at Uerdingen. Apart from color pigments. the company is also producing three grades of magnetic pigments.May 2001 575. Hans Heubach GmbH & Co. brown and black iron oxide) and Ferroxide® (yellow iron oxide). Penniman-Zoph process. Primarily blending.0003 R X X X X Trade names are Duploxide® (red. KG Langelsheim X X X Rockwood Pigments Breckhurs Italy Rockwood Pigments Rockwood Italia SpA Silo Division Torino X X X X May 2001 575. Micronized grades. FDA grades (Sicomed ® for cosmetics and Sicopharm® for pharmaceutical applications). © 2001 by the Chemical Economics Handbook—SRI International . Heucorox ® . Aniline. Start-up in January 1997. Mainly for plastics and paint systems. Also orange and magnetic pigments. X X X X X Dr. X X X Transparent pigments. X X PIGMENTS Köln Bayer AG Krefeld X X Transparent pigments (Sicotrans™).Pigments Page 96 Western European Producers of Synthetic Iron Oxide Pigments Company and Plant Location Austria Krems Chemie Aktiengesellschaft Krems an der Donau France Cappelle Frères SARL Halluin Germany BASF Aktiengesellschaft Ludwigshafen Black (PBk-11) Brown (PBn-6) Red (PR-101) Yellow (PY-42) Remarks X X By-product route. X X X X Penniman-Zoph process (Deanox™). Molina de Segura Oxhinsa.Pigments Page 97 Western European Producers of Synthetic Iron Oxide Pigments (continued) Company and Plant Location Italy (continued) Società Italiana Ossidi Ferro SpA Pozzolo-Formigaro Black (PBk-11) Brown (PBn-6) Red (PR-101) Yellow (PY-42) Remarks X X X X Spain Cremades y Compañía. Spanfer™.0003 S © 2001 by the Chemical Economics Handbook—SRI International Used mainly in cements and mortars. PIGMENTS . Laminox Ltd. May 2001 575. Materials Division Pigments & Dispersions Stoke on Trent Elementis UK Ltd. precipitation. S. (ultimately owned by Plüss Stauffer AG) Peterlee SOURCE: CEH estimates. Black iron oxide pigments are resold from the United States. SA Alicante X X Purofer™. a synthetic black pigment. X X X Scrap iron.A. Elementis Pigments Milton Keynes X X Transparent pigments. United Kingdom Cookson Matthey Ceramics & Materials Ltd. X Micaceous synthetic iron oxide. Also supplies natural iron oxide pigments. paints and coatings and plastics. Österreichisches Statistisches Zentralamt. The company’s main production plant is located in Krefeld.May 2001 575.0003 T PIGMENTS Pigments Page 98 The following pie chart shows the estimated market share for synthetic iron oxide pigment producers in Western Europe: Western European Producers of Synthetic Iron Oxide Pigments—2001 Other 20% Heubach 5% Bayer 58% Elementis 8% K-L Holdings 9% Salient statistics Synthetic iron oxides account for the largest percentage of color pigment production in the world and Western Europe is by far the leading producer. particularly in the traditional areas—building materials. (D) CEH estimates. particularly for synthetic pigments. Below is a summary of 1999 supply/demand for iron oxides in Western Europe. Statistical Office of the European Community. Serie 1A. Western European production of iron oxide pigments has reached very high levels. Bayer accounted for about 74%. (B) Der Aussenhandel Österreichs . (C) National foreign trade statistics. Production During the last five years the overall capacity utilization for iron oxides has improved for most producers. Western European Supply/Demand for Iron Oxide Pigments—1999 (thousands of metric tons) Natural Production Imports Exports Apparent Consumption SOURCES: 58 neg 2 56 Synthetic 327 83 116 294 Total 385 83 118 350 (A) Eurostat. Of the total iron oxide pigment production in Western Europe. Germany but the © 2001 by the Chemical Economics Handbook—SRI International . Some of these niches are primarily in the building materials industry and in fertilizers. Because of product consistency. In other applications natural iron oxide pigments. particularly micronized grades. lead. as well as the considerably lower content of problematic heavy metals (e. which are more economical. Natural iron oxide pigments.g. The following table lists official production data for iron oxide pigments produced in Spain: © 2001 by the Chemical Economics Handbook—SRI International . however. with a nameplate capacity of 20 thousand metric tons per year.g. Scrap iron oxide is used almost entirely in applications where quality of the pigment is not overly critical. This group of iron oxide pigments includes the intentionally produced iron oxides as well as the low-grade by-product pigments obtained from scrap iron from metal works.. Natural iron oxide pigments have some market niches in which they can compete very well with the synthetic grades. Bayer obtains crude iron oxide pigments as a coproduct of aniline production (only a small portion of Bayer’s aniline production is based on the reduction process with iron scrap). arsenic. In Western Europe. synthetic iron oxide pigments have further increased their share over natural iron oxide pigments in most markets. The production of iron oxide pigments from the aniline process is governed by the demand for aniline and the economics of the processes. It can be argued. Aniline is generally manufactured through different processes. that the iron oxide pigment obtained through this process is the main product and not the aniline. Synthetic iron oxide pigments. In 1999. primarily in the construction industry for the production of bricks and concrete. down from 17% in 1996. This large volume of lowgrade iron oxide pigments have been excluded from this report.0003 U PIGMENTS Pigments Page 99 group also has plants in the United States and at a joint venture plant in China (Bayer Shanghai Pigments). Over the last ten years this share has decreased because of lower output and plant closures that have been only partially offset by new capacities (e. The next-largest market participants are Elementis and K-L Holdings (acquirer of Laporte). For example. the Western European production of natural iron oxide pigments accounted for about 15% of global iron oxide pigment production.. Particularly.May 2001 575. can also compete with synthetic pigments. cadmium). synthetic iron oxide pigments are produced by a variety of processes and raw materials. higher tinting strengths and more intense color shades. Rana Gruber. taking the value of the coproduct iron oxide into account. Norway). output from Spain has dropped to less than half the output of the early 1990s. 0 20.0 2.0003 V PIGMENTS Pigments Page 100 Spanish Production of Iron Oxide Pigments (thousands of metric tons) Natural 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1993 1996 1997 1998 1999 SOURCES: 51.5 3.1 3.0 4. Geological Survey (data for NATURAL.S. U.0 22.0 22. (B) Mineral Industry Surveys.0 2.0 2.9 na na na na na na na na 40. (C) CEH estimates (all other data).0 2. Department of the Interior.2 4. 1997-1999). Federación Empresarial de la Industria Química Española (data for 1970-1996).0 2.0 1.S.0 4.0 (A) La Industria Química en Cifras.0 4.2 2.May 2001 575.2 2. The following table shows Western European production of both natural and synthetic iron oxide pigments by country since 1983: © 2001 by the Chemical Economics Handbook—SRI International .0 22.0 4. U.6 51.0 Synthetic 1.0 25. May 2001 575.3 0. The following table shows a breakdown of 1999 production of natural and synthetic iron oxide pigments in Western Europe by country: © 2001 by the Chemical Economics Handbook—SRI International .3 0.7 1 1 1 1 1 1 na na 1 -- Total 420 416 420 419 427 427 415 403 410 394 334 340 340 345 383 CEH estimates.3 0.0003 W PIGMENTS Pigments Page 101 Western European Production of Natural and Synthetic Iron Oxide Pigments (thousands of metric tons) Belgium/ Luxembourg 10 10 10 10 10 10 4 3 3 3 2 na na 2 -Germany.4 0. Federal Republic of 274 270 269 264 264 265 260 250 255 240 221 na na 226 282 United Kingdom 45 45 48 50 55 50 45 40 38 35 32 na na 32 34 Austria 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1999 15 15 15 15 15 15 15 14 12 12 8 na na 8 8 France 19 18 18 18 19 17 16 15 16 15 13 na na 16 2 Italy 18 19 20 22 23 24 26 24 25 25 24 na na 32 33 Norway 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1999 SOURCE: neg neg neg neg neg neg neg 1 2 3 4 na na 4 -- Spain 38 39 40 40 40 45 48 55 58 60 29 na na 24 26 Sweden 0. because of their low toxicity. however. Other markets are considerably smaller. The largest market segment is construction. Geological Survey (data for NATURAL). U. have partially replaced heavy metal–based inorganic pigments in certain applications where the low brightness of iron oxide pigments is not a critical issue. but more attractive in terms of price premiums. The increased supply of low-grade pigments from by-product sources (such as from iron works that recover scrap iron oxide from metal pickling operations) has pushed traditional suppliers even more into the higher-value-added markets. (Iron oxide pigments. (B) CEH estimates (all other data).May 2001 575. are the second-largest group of black pigments (after carbon black) produced and consumed in Western Europe. and the process is almost complete.) The volume gained from this substitution process has been small. Black iron oxide pigments. Iron oxide pigments. and in particular iron oxide yellow. at least in Western Europe.S. particularly PBk-11. An estimated 35 thousand metric tons of black iron oxides were produced in Western Europe in 1999. Department of the Interior. The following table shows the Western European consumption of natural and synthetic iron oxide pigments: © 2001 by the Chemical Economics Handbook—SRI International . U.0003 X PIGMENTS Pigments Page 102 Western European Production of Natural and Synthetic Iron Oxide Pigments—1999 (thousands of metric tons) Natural Austria France Germany Italy Spain United Kingdom Total Percent SOURCES: 7 1 4 1 22 -35 9% Synthetic 1 <1 278 32 4 34 348 91% Total 8 2 282 33 26 34 385 100% (A) Mineral Industry Surveys.S. Consumption It is estimated that Western Europe consumed approximately 350 thousand metric tons of iron oxides in 1999. are often mixed with organic pigments in order to match the standard shades in the final products. These applications do not depend on the coloring properties of iron oxide pigments. Includes colorants for cosmetics and pharmaceuticals. 367 363 376 348 365 351 352 302 272 280 290 306 320 334 350 The table and graph that follow give a breakdown of Western European consumption of iron oxide pigments by end use for 1999: Western European Consumption of Iron Oxide Pigments by End Use—1999a Quantity (thousands of metric tons) Building Materials Paints and Coatings Plastics Magnetic Applicationsb Paper Industry Foundry Sandsb Food Colorants/Nutritional Additivesb Enamels and Ceramics Catalystsb Otherc Total a. CEH estimates. 210 87 16 10 9 6 4 3 3 2 350 Market Share (percent) 60 25 5 3 3 2 1 1 1 <1 100% c. SOURCE: © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575.0003 Y PIGMENTS Pigments Page 103 Western European Consumption of Natural and Synthetic Iron Oxide Pigments (thousands of metric tons) 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCE: CEH estimates. b. Natural and synthetic iron oxide pigments. for wood painting) and plastics industry and for specialty applications such as cosmetics. Total consumption of FDA-grade iron oxide pigments. This volume is included in the above table. which are sold primarily to the paints (e.g. micronized grades (with a diameter between 0. pharmaceuticals or special paper. is estimated at about 4 thousand metric tons in 1999.01 and 0.0003 Z PIGMENTS Pigments Page 104 Western European Consumption of Iron Oxide Pigments by End Use—1999 Enamels and Ceramics 1% Paper Other 2% 1% Plastics 4% Paints and Coatings 27% Building Materials 65% One of the higher-value-added forms of iron oxide pigments are the transparent..May 2001 575. © 2001 by the Chemical Economics Handbook—SRI International . Total consumption of transparent iron oxide pigments in Western Europe is estimated at less than 4 thousand metric tons in 1999. The following graph shows the estimated breakdown by market: Western European Consumption of Transparent Iron Oxide Pigments—1999 Other 7% Pharmaceutical Colorants 7% Cosmetics 10% Piants and Coatings 50% Special Paper 13% Plastics 13% Another higher-value-added form of iron oxide pigments is FDA-grade synthetic iron oxide. including transparent and nontransparent grades.001 micrometer). It is estimated that in 1999. preformed concrete blocks for paving and noise-abatement (sound) walls. The building materials industry is one of the largest consumers of pigments.e. particularly in applications with lower-quality requirements (e. in © 2001 by the Chemical Economics Handbook—SRI International . The pigments are used for a wide variety of applications.May 2001 575. bricks. It is expected that construction activities will continue to increase over the next few years and that consumption of iron oxide pigments will increase accordingly. micaceous iron oxide). During the 1992-1993 European economic recession. but natural iron oxide pigments are also widely used. demand for color building products such as concrete interlocking paving blocks and other products declined. The main use of transparent pigments is in the production of metal-effect coatings (i. particularly iron oxide pigments.. some 87 thousand metric tons of iron oxide pigments were consumed for the manufacture of paints and coatings. particularly from China. Paints and coatings. both natural and synthetic iron oxide pigments are used in this application.g. Western European consumption for this application was less than 2 thousand metric tons. paints and coatings represent the second-largest segment for iron oxide pigments.0004 A PIGMENTS Pigments Page 105 Western European Consumption of FDA-Grade Iron Oxide Pigments—1999 Special Paper 12% Pharmaceuticals 16% Cosmetics 47% Pet Food 25% Total = 4 Thousand Metric Tons Building materials.g. The larger share of iron oxide pigments used in paints and coatings are synthetic pigments. In Western Europe. Between 1996 and 1999. In many of these end uses intentionally produced synthetic pigments have come under pressure from low-grade pigments. In these coatings. In particular. mortar. In Western Europe. consumption of iron oxide pigments was particularly hard-hit by lower construction activity and lower-volume purchases of pigmented materials by the private and public sectors.. primers and undercoats). and other building materials.. iron oxide pigments often function as an anticorrosion inhibitor rather than as a coloring matter (e. A specialty group of iron oxide pigment used in paints and coatings are the transparent pigments. It is estimated that in 1999. consumption increased steadily as the main consuming applications recovered. cement. the most important of which are for colored asphalt and for coloring roof tiles. g. Food colorants/nutritional additive. which are available in brown. however. yellow. demand for colored pet foods will increase. there is a clear swing away from the use of synthetic organic pigments toward the use of iron oxide pigments in food and feed products. such as chrome oxide Migration of media production to lower-cost countries in Asia q q q q q It is expected that these trends will continue and future consumption of magnetic iron oxide pigments in Western Europe will eventually stagnate and decline. wrapping paper. cigarette paper). the volumes gained are small—particularly in relation to the changes in consumption in other sectors. and thinner coatings on. been developed that can be used with practically any plastic. One of the larger applications of iron oxide pigments in this segment is the production of plastic trash bags. Also. Because of toxicological concerns.. They are used particularly in pet foods. However. Plastics. Iron oxide pigments have also been used to replace the toxic chromate pigments wherever possible. coated pigments have. such as the production of ferrites and magnetic information carrier materials. FDA-grade micronized pigments are used in special papers which are likely to get in contact with lips (e. Paper.g. However. It is unlikely that iron oxide pigment consumption in this application will grow more than 2-3% per year in the near future. the use of certain iron oxide pigments was often problematic because of their relatively low temperature stability during the plastics processing step. Although the number of carrier material pieces (e. Plastics are the third-largest application for iron oxide pigments in Western Europe. In the past. gray and black colors. but future growth is difficult to determine.. because of an increase in the number of pet owners. The use of pigments in paper has grown. In this application iron oxide pigments are used primarily for the production of decorative laminates destined for the furniture industry. Iron oxide pigments are among the main coloring pigments in food and feed products. the carrier products Use of other. the volume of magnetic iron oxide pigments consumed in Western Europe is expected to decrease for the following reasons: q A sharp decline in demand for audio cassettes because of replacement by CDs Growing migration from video cassettes to DVDs Replacement of computer floppy disks and other magnetic media with recordable CD-ROMs Reduced size of. Recently there has been substitution pressure from luster pigments. this substitution is believed to be complete. Magnetic iron oxide pigments are used in a wide range of applications. some of which are also based on iron oxide. Newer. more effective magnetic materials.May 2001 575. Other smaller applications include the production of kraft paper and paper board used by the packaging industry. Understandably.0004 B PIGMENTS Pigments Page 106 combination with aluminum pigments) and for coloring PET bottles and spin-dyed fibers. where they serve as a coloring agent as well as a nutritional additive. Magnetic applications (ferrites and other uses). © 2001 by the Chemical Economics Handbook—SRI International . It is believed that. magnetic cards) produced has increased significantly. discs. in food products only FDA-grades of iron oxide pigments are acceptable. Other . The consumption volume of iron oxide pigments used for cosmetics is unlikely to change significantly. particularly in relation to mucous membrane exposure. fashion trends and the still-decreasing age at which cosmetics use begins will also have some impact on the consumption of iron oxide pigments. compact makeup. have also had a negative impact on prices.0004 C PIGMENTS Pigments Page 107 Cosmetics. Various grades and types are used to color lipsticks. Pressures from consumers. In cosmetics.072 675 569 © 2001 by the Chemical Economics Handbook—SRI International . The total Western European consumption of iron oxide pigments in cosmetic products in 1999 is estimated to have been about 400 metric tons. has become very competitive. since it is related to the growth of the Western European population.May 2001 575. prices are expected to remain unchanged or decline in inflationadjusted terms for the next few years. Iron oxides have a number of other applications but they are much smaller than the building materials and the markets discussed above. with increased imports (especially from China) having caused prices for iron oxide pigments to decline considerably during the past ten years. Because of the current business climate and the new capacity that has been built. 728 740 792 1. eyebrow pencils. Obviously. cover ointments and so forth. although dominated by a few domestic producers. Natural and especially synthetic iron oxide pigments are the most important of the color pigments used in cosmetic products in terms of volume consumed. such as the paints and coatings industry. The following table gives an estimate of the average Western European prices for iron oxide pigments: Western European Average Import Trade Values for Iron Oxide Pigments (Euros per metric ton) Synthetic Iron Oxide Pigments 1997 1998 1999 Iron Oxide Earth Colors 1997 1998 1999 SOURCE: Eurostat. micronized iron oxide pigments are favored over organic pigments because of lower concern about toxicological aspects of their consumption. Price The Western European iron oxide market. 1 73. d. Actual data are believed to be lower. Bureau of the Census (data for UNITED STATES). Western European imports of iron oxide pigments in selected years are shown in the following table: Western Europe Imports of Iron Oxide Pigments by Region of Origina (thousands of metric tons) North America United States 1985 1990 1995 1999 26.2 0.2 Middle East -0. c.1 0.6 0.0 1.4 Africa -neg 0.3b 3.1 0. Eurostat. iron hydroxides and earth colors.1 0.7 6.7 60.8 Other 0.7 Canada -neg neg neg Asia China 1985 1990 1995 1999 a.1 2. Department of Commerce.3 0. the total volume imported was 85 thousand metric tons. Statistical Office of the European Community.4 3.1 Total 28.9 2. (A) U. Included in OTHER.1 Includes iron oxides. b.May 2001 575.4 Central and South America -0. (C) National foreign trade statistics. Analytical Tables of Foreign Trade: Products-Countries.2 Japan 0. of which 70% came from China. (B) NIMEXE.9 52.0 6.1 85. (D) CEH estimates.1 0.1 Eastern Europe 0.1 15.S.0004 D PIGMENTS Pigments Page 108 Trade Imports.7 4. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International . Includes non-EU suppressed imports.1 16. Data exclude intra–Western European trade. --c 8.8d Australia and Oceania -0. In 1999.3 0. Western European imports of iron oxide pigments increased significantly in recent years.1 0.6 4. with a 20 thousand metric ton-peryear iron oxide pigment grinding and mixing plant.May 2001 575. Of this group. the largest single-volume product exported was synthetic iron oxide yellow (PY-42) produced by Bayer AG.0004 E PIGMENTS Pigments Page 109 Bayer started a joint venture pigments project in Shanghai in 1995. Chrome Pigments Producing companies The following table lists Western European producers of chromium pigments in 2000: © 2001 by the Chemical Economics Handbook—SRI International . Total volumes exported in 1999 were reported at 118 thousand metric tons. Some production from this plant accounts for part of the exports from China to the European market. Western Europe is a large net exporter of iron oxide pigments. More than 98% of all iron oxide pigments exported were synthetic pigments. Exports. 0004 F Bruchsaler Farbenfabrik GmbH & Co. KG Bruchsal X X X © 2001 by the Chemical Economics Handbook—SRI International PIGMENTS .Pigments Page 110 Western European Producers of Chrome Pigments—2001 Lead-Containing Chrome Pigments Chrome Orange (PO-21) Basic Lead MolybSilicodate chromate Orange (PO-21:1) (PR-104) Chrome Yellow (PY-34) Chrome Green (PG-15) Barium Chromate (PY-31) Zinc Chromate (PY-36) Strontium Chromate (PY-32) Chromium Oxide Anhydrous Hydrated Green Oxide (PG-17) (PG-18) Chromium Phosphate (PG-17:1) Company and Plant Location Austria Habich Pigments Chemische Farbenfabrik H. Habich AG Leiben Belgium Fabrique de Couleurs Hilaire Grootaert Drongen X X X X X Gebroeders Cappelle nv Menen France Cappelle Frères SARL Halluin Société Nouvelle des Couleurs Zinciques SA—SNCZ Bouchain Germany BASF Lacke + Farben Aktiengesellschart Besingheim Köln X X X X X X X X X X X X X X X X X May 2001 575. M. Pigments Page 111 Western European Producers of Chrome Pigments—2001 (continued) Lead-Containing Chrome Pigments Chrome Orange (PO-21) Basic Lead MolybSilicodate chromate Orange (PO-21:1) (PR-104) Chrome Yellow (PY-34) Chrome Green (PG-15) Barium Chromate (PY-31) Zinc Chromate (PY-36) Strontium Chromate (PY-32) Chromium Oxide Anhydrous Hydrated Green Oxide (PG-17) (PG-18) Chromium Phosphate (PG-17:1) Company and Plant Location Germany (continued) Dr. Kravis. Roberts (Laporte Italia SpA) Silo Division Torino X X X X X X Società Italiana Ossidi Ferro SpA Verona Netherlands Ciba Specialty Chemicals Maastricht B. KG Langelsheim Italy Kohlberg.V.0004 G Augusto Gomes dos Santos Vila Nova de Gaia X © 2001 by the Chemical Economics Handbook—SRI International PIGMENTS . Hans Heubach GmbH & Co. Maastricht A. Vossen Pigment BV Venlo-Blerick Norway Waardals Kjemiske Fabrikker A/S Askoey Portugal X X X X X X X May 2001 575. Spondon SOURCE: CEH estimates. SA—INTORSA Moncada i Reixach Nubiola. S.A. Barcelona X X X X X X X X X X X X X X X United Kingdom Elementis UK Ltd. X X X May 2001 575.0004 H © 2001 by the Chemical Economics Handbook—SRI International PIGMENTS .Pigments Page 112 Western European Producers of Chrome Pigments—2001 (continued) Lead-Containing Chrome Pigments Chrome Orange (PO-21) Basic Lead MolybSilicodate chromate Orange (PO-21:1) (PR-104) Chrome Yellow (PY-34) Chrome Green (PG-15) Barium Chromate (PY-31) Zinc Chromate (PY-36) Strontium Chromate (PY-32) Chromium Oxide Anhydrous Hydrated Green Oxide (PG-17) (PG-18) Chromium Phosphate (PG-17:1) Company and Plant Location Spain Colores Hispania. Barcelona Intermedios Orgánicos.A. Elementis Pigments Milton Keynes Lead Chrome Colours Ltd. S. Chromium oxide production is estimated to have been higher.8 35.5 Total 40.0 22.3 4. at 24 thousand metric tons. zinc chromate and strontium chromate). Consumption of chromate pigments has declined in Western Europe by nearly 25% over the volumes in 1993.5 15.8 13.May 2001 575. Recent consumption in selected years is shown in the following table: Western European Consumption of Chrome Pigments (thousands of metric tons) Chromate Pigmentsa 1993 1996 1999 a. chromium is less of a concern. Eurostat.5 22.0 9.0 13.5 2.0 Chromium Oxides 23. SOURCE: Lead chromates.5 Total 41. (B) CEH estimates.5 7. Because of toxicological and environmental considerations. SOURCES: Total Western European production of lead chromate pigments (including small amounts of the corrosion-inhibiting barium chromate.0 Chromium Oxides 24. zinc and strontium chromate corrosion-inhibiting pigments.5 Includes lead chromates but also small volumes of barium. 17.5 35. it can be assumed that the consumption of lead© 2001 by the Chemical Economics Handbook—SRI International .5 Includes lead chromates but also small volumes of barium. is estimated to have been 17.0 0. CEH estimates.3 thousand metric tons in 1999. Analytical Tables of Foreign Trade: ProductsCountries . the production and consumption of chrome pigments have decreased and this trend is expecte to continue for some time. Statistical Office of the European Community. zinc and strontium chromate corrosion-inhibiting pigments. 17. As legislation regarding the production and use of pigments becomes more severe and as regulations will be increasingly implemented.0 22.3 3.0004 I PIGMENTS Pigments Page 113 Salient statistics Western European Supply/Demand for Chrome Pigments—1999 (thousands of metric tons) Chromate Pigmentsa Production Imports Exports Apparent Consumption a. While lead represents a clear toxicological and environmental problem.5 37. Consumption Chromium-containing pigments are an essential group of pigments with a wide range of applications. (A) NIMEXE. down from about 17.4 0. larger consuming countries will follow suit. Some of the organic pigments substituting for yellow and orange chrome pigments are based on benzimidazolone yellow and DPP red. Chromium oxide. One of the inorganic substitution pigments is bismuth vanadate. zinc and strontium chromate. are also used as a substitute in certain applications. will decrease further. In the Netherlands.5 thousand metric tons in 1993. the most important one being that they are clearly more expensive than chrome pigments. the Western European consumption of lead chromates has decreased substantially during the last decade. it is expected that the consumption of lead chromate pigments. The end-use consumption pattern is shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International . Major companies that had used chrome pigments in the past are gradually substituting chromates with pigments that do not contain lead. however. As a result of these environmentally driven changes. The excellent chemical and heat stability of chromium oxide make it a very versatile pigment with outstanding fastness properties. One of the obvious drawbacks of chromium oxide is.9 4. Consumption of green chromium oxide pigment in Western Europe in 1999 is believed to have been 22 thousand metric tons.0004 J PIGMENTS Pigments Page 114 containing chrome pigments will gradually decrease. a segment in which lead chromates have outstanding properties. Western European consumption of lead chromate pigments in 1999 is estimated to have been about 13 thousand metric tons. CEH estimates. Even in traffic-grade paints. its dull shade.May 2001 575. SOURCE: During 1999-2004. Iron oxide pigments.1 13. These organic pigments all have a drawback of one kind or another. the use of leadcontaining pigments were phased out in the year 2000 and it is expected that other. for example. substitution is still taking place.6 0. chromium oxide pigments are unlikely to be influenced much by regulations. especially in the paints and coatings segment. 7.0 Market Share (percent) 61 34 4 1 100% Includes small volumes of corrosion-inhibiting barium. While lead chromate pigments pose environmental and toxicological problems. The following table lists the Western European consumption of lead chromate pigments by market segment: Western European Consumption of Lead Chromate Pigments —1999a Quantity (thousands of metric tons) Paints and Coatings Plastics Laminates Printing Inks Total a. These figures include small volumes of the anticorrosion pigments barium. a yellow pigment that has properties similar to chrome yellow. such as bismuth vanadate or in the corrosion-protection pigments segment. mixed with organic pigments to achieve higher brightness. zinc and strontium chromate pigments. with products such as aluminum and zinc phosphates. Consequently. Prices are expected to decline as consumption falls. still considered an excellent pigment. chromium oxide pigments are used to color cement and chalkbased products. 11. Strontium chromate is.5 neg 1 22. demand for this pigment has been quite strong. Consumption of these anticorrosion pigments has been under environmental pressure and use has started to decline in certain applications. There is.0004 K PIGMENTS Pigments Page 115 Western European Consumption of Green Chromium Oxide Pigments—1999 Quantity (thousands of metric tons) Paints and Coatings Building Materials Plastics Enamel and Ceramics Printing Inks Other Total SOURCE: CEH estimates. (This shortcoming is solved in many cases by adding highperformance organic yellow pigments. which can create a problem in some applications because of abrasion. Often.39 euros per kilogram. Chromium oxide pigments are being used in practically every possible pigment application.g. heat stability.5 6 2 1.0 Market Share (percent) 52 27 9 7 neg 5 100% Chromium oxide is also used in technical nonpigment applications. It remains the specified anticorrosion pigment for aircraft and military primers. communal trash containers.May 2001 575. The paint and coating industry is clearly the largest market for chromium oxide pigments. © 2001 by the Chemical Economics Handbook—SRI International . In the building products industry. Barium. consumption of strontium chromate will likely decline as new anticorrosion pigments or systems become accepted. This use of chromium oxide is not discussed here and the data shown are for pigment-grade chromium oxide only. Price The average price of chromium-based pigments imported to Western Europe in 1998 was 3. in the long term. which have a brighter color shade and combinations of yellow and blue pigments. garden furniture. whose properties are unmatched by any other anticorrsion pigment. etc. particularly in technical goods (e. however. In plastics. zinc and strontium chromate. machinery parts. other pigment combinations are formulated in order to derive the required shade. chromium oxide pigments are widely used. chromium oxide pigments are used particularly where the fastness properties are required and where its relatively dull shade is acceptable. In this application. bottle crates).) will keep demand growing slowly in Western Europe. Nevertheless. however. competition from other green pigments.) A further characteristic of chromium oxide pigments is their high hardness. which change the hue to a brighter green.. the product has found acceptance even in cosmetics.38 euros per kilogram. The generally excellent properties of chromium oxide pigments (fastness. such as phthalocyanine pigments. in 1999 the average price rose slightly to 3. Analytical Tables of Foreign Trade: Products-Countries. Statistical Office of the European Community.0004 L PIGMENTS Pigments Page 116 Trade Imports.896 1999 1. 1995 588 459 217 456 360 444 4. The majority of imports originated from Canada (Dominion Colour Corporation) and were shipped mainly to the United Kingdom.272 9. Exports of chrome pigments from Western Europe totaled about 9. NIMEXE.752 European Union tariff code number is 3206. Eurostat. Republic of Other Total a. EU imports of chrome-containing pigments have grown since 1995. The following table gives an indication of chrome-containing pigment imports into Western Europe in 1995 and 1999: EU Imports of Chrome-Containing Pigments and Pigment Preparations—1995 and 1999a (metric tons) 1995 Canada Hungary Colombia United States China Other Total SOURCE: 1. The following table gives an indication of chromebased pigments exports by major destinations for 1995 and 1999: EU Exports of Chrome-Containing Pigments and Pigment Preparations—1995 and 1999a (metric tons) Destination United States Japan Saudi Arabia Turkey Taiwan Korea. up from about 7. while the United States has grown. Exports. Imports of chromium-containing pigments into Western Europe represent about 13% of consumption. Analytical Tables of Foreign Trade: Products-Countries. Statistical Office of the European Community.886 7.953 NIMEXE.4 thousand metric tons in 1995.May 2001 575. and Colombia has also emerged as an important source.410 1999 879 609 590 576 438 388 6.2000.776 462 215 179 54 1.267 3. despite declining consumption.8 thousand metric tons in 1999. Eurostat. There were also shipments received from Hungary (Holland Colours Hungaria Kft). SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . China has decreased its share since 1995.169 351 na 112 145 119 1. 1 0.0004 M PIGMENTS Pigments Page 117 Exports are expected to eventually decline as lead chromate paint bans become enforced in developing countries.5 8. is in the plastics applications.0 3. complex inorganic color pigments (formerly known as mixed-phase or mixed-metal oxide pigments) are a small but increasingly important group of inorganic pigments.0 15. Western European Supply/Demand for Complex Inorganic Pigments—1999 (thousands of metric tons) Rutile Pigments Capacity Production Imports Exports Apparent Consumption a.5 4. SOURCE: Producing companies The following tables list Western European producers of cobalt-based and other-than-cobalt-based complex inorganic pigments: Western European Producers of Cobalt-Based Complex Inorganic Pigments—2001 Company and Plant Location Germany BASF Aktiengesellschaft Ludwigshafen BASF Pigment GmbH Köln Bayer AG Leverkusen Cerdec AG.1 3. sometimes combined with organic pigments. CEH estimates.3 7.2 4. Complex Inorganic Pigments Summary In Western Europe. Keramische Farben (owned 70% by Degussa AG and 30% by Ciba Specialty Chemicals AG) Bonn Black (PBk-27) Blue (PB-28) Blue (PB-36) Green (PG-19) Green (PG-26) Green (PG-50) X X X X X X X X X X X © 2001 by the Chemical Economics Handbook—SRI International .1 Includes cobalt-based complex inorganic pigments. as in developed countries. Because of the decreasing acceptance of cadmium-based pigments as a result of environmental and toxicological concerns. na 9.2 Total 18.3 0.May 2001 575.9 Spinel Pigmentsa na 6.2 0. the use of complex inorganic color pigments. Hans Heubach GmbH & Co. Keramische Farben (owned 70% by Degussa AG and 30% by Ciba Specialty Chemicals AG) Bonn Dr.0004 N PIGMENTS Pigments Page 118 Western European Producers of Cobalt-Based Complex Inorganic Pigments—2001 (continued) Company and Plant Location Germany (continued) Dr.May 2001 575. Black (PBk-27) Blue (PB-28) Blue (PB-36) Green (PG-19) Green (PG-26) Green (PG-50) X X X X X X X X X Western European Producers of Other-Than-Cobalt-Based Complex Inorganic Pigments—2001 Spinel-Structured Pigments Company and Plant Location Germany BASF Aktiengesellschaft Ludwigshafen BASF Pigment GmbH Köln Cerdec AG. KG Langelsheim Netherlands Ferro (Holland) BV Rotterdam X X Brown (PBn-29) Brown (PBn-31) Yellow (PY-119) Rutile-Structured Pigments Brown (PBn-24) Yellow (PY-53) Yellow (PY-157) Yellow (PY-164) X X X X X X X X X X © 2001 by the Chemical Economics Handbook—SRI International . Hans Heubach GmbH & Co. KG Langelsheim Netherlands Ferro (Holland) BV Rotterdam United Kingdom Johnson Matthey Colour and Coatings Division Ceramics Division Stoke on Trent SOURCE: CEH estimates. 9 1. Brown (PBn-29) Brown (PBn-31) Yellow (PY-119) Rutile-Structured Pigments Brown (PBn-24) Yellow (PY-53) Yellow (PY-157) Yellow (PY-164) X X X X Production The Western European production of complex inorganic color pigments is estimated at about 15. This volume accounts for the rutile and spinel type of pigments. Heubach has recently introduced encapsulated rutilestructured pigments that can withstand even higher temperatures.0004 O PIGMENTS Pigments Page 119 Western European Producers of Other-Than-Cobalt-Based Complex Inorganic Pigments—2001 (continued) Spinel-Structured Pigments Company and Plant Location United Kingdom Johnson Matthey Colour and Coatings Division Ceramics Division Stoke on Trent SOURCE: CEH estimates. BASF and Cerdec both offer a wide range of complex inorganic color pigments and pigment mixtures.3 0.May 2001 575. Consumption Western European consumption of complex inorganic color pigments was about 8. The following table gives an estimate on Western European consumption of complex inorganic pigments by specific pigment: Western European Consumption of Complex Inorganic Pigments—1999 (thousands of metric tons) Rutile Pigments Chrometitan Yellow (PBr-24) Nickeltitan Yellow (PY-53) Manganetitanium Yellow (PY-164) Total Spinel Pigments Cobalt Blue (PB-28/36) Cobalt Green (PG-50) Other Total Total SOURCE: CEH estimates.0 3.9 1. which also includes cobalt pigments. followed by Cerdec AG (owned 70% by Degussa AG and 30% by Ciba Specialty Chemicals AG).1 0.2 8.1 © 2001 by the Chemical Economics Handbook—SRI International . The major producer of these pigments is BASF. 3.1 thousand metric tons in 1999.3 1.5 4.3 thousand metric tons in 1999. This volume also includes pigments that are sold to the enamels and ceramics industry. 5 0. the consumption of Ni-Cr-Ti-based pigments is growing steadily. Currently. Complex inorganic color pigments are increasingly important in applications where cadmium. Imports of ceramic goods (and in particular tiles) continue to grow. Western Europe (in particular.0 2. As a result. Western European Consumption of Complex Inorganic Pigments by End Use—1999 (thousands of metric tons) Rutile Pigments Ceramics and Glass Plastics Paints and Coatings Building Materials Other Total SOURCE: CEH estimates. 0. The expected growth rate is slightly higher than the estimated production growth of the ceramic products industry. During the last few years. is believed to be for camouflage paints for military applications.2 Total 3. auto enamels and coil coatings. The largest volumes are used in PVC and polyethylene. it is expected that during 1999-2004.3 8. as there will be some substitution of cadmium pigments.5 2. followed by the United Kingdom. impacting the Western European growth potential of pigments for ceramic and glass materials. because of environmental and toxicological legislation.0004 P PIGMENTS Pigments Page 120 The main applications of complex inorganic color pigments in Western Europe are shown and discussed briefly below. The pigments are used in a variety of commodity and high-performance plastics.and chromatebased pigments.1 Ceramic and glass materials. It is estimated that during 1999-2004 the consumption of complex inorganic color pigments for plastics will grow at an average rate of about 3-4% per year.3 1. These pigments show good to excellent performance.8 1.1 -0. In particular.3 0. Complex inorganic color pigments are increasingly important in the paints and coatings industry. since they have special characteristics. The ceramic goods industry is faced with increasing import penetration. complex inorganic color pigments are used for coloring glass and ceramic materials. as well as from Eastern Europe and Brazil. Plastics is one of the major industries consuming complex inorganic color pigments in Western Europe. Spain and France) is the world’s largest producing region for ceramic goods and consumption of complex inorganic color pigments in this segment is the most important in volume terms. some of these complex inorganic color pigments have taken a small.May 2001 575.2 4. the only application of significance. chromate and molybdate pigments can no longer be used.3 0. Plastics.7 0. Italy and Germany.9 Spinel Pigments 2. particularly in exterior high-grade house paints. The consumption of complex inorganic pigments in this segment will grow by only about 2. © 2001 by the Chemical Economics Handbook—SRI International .6 0.1 3.5 0. Paints and coatings. production of standard-grade ceramics will stagnate and that a gradual shift towards more premium ceramic products will take place. particularly from China and other Asian countries. Because of their heat stability.0% per year. Particularly the various shades of PY-53 have gained in importance. however. but increasing market share from cadmium. 5 14.3 10. which can be produced in shades of blue.0004 Q PIGMENTS Pigments Page 121 Trade No data on Western European trade in complex inorganic pigments are reported.6 3.5 3.5 0. is energy-intensive and time-consuming—it can take up to twenty days to produce a batch.1 1. There are some imports of complex inorganic pigments from the United States (primarily from Ferro). with a combined annual production capacity of approximately 14 thousand metric tons. however. violet or red.0 5.3 6.7 5. however. they were replaced by organic optical brightners. The next biggest producer is Nubiola.May 2001 575. It is estimated. is the largest ultramarine pigments producer in the world.3 (A) NIMEXE. It is thought that the United States is one of the main export destinations and that exports to Asian countries and Brazil are also significant. Spain and the second in Agualva.4 1999 16. (B) CEH estimates. The fairly good performance characteristics of these pigments and their relatively low price led to widespread use.2 1996 16. Analytical Tables of Foreign Trade: Products-Countries. Holliday Pigments (formerly Reckitt’s Colors). which operates two plants. Producing companies The following table lists producers of ultramarine pigments in Western Europe: © 2001 by the Chemical Economics Handbook—SRI International . The production process. that Western Europe was a net exporter of approximately 7. one near Barcelona. with works in France and the United Kingdom. Between 1996 and 1999 the Western European ultramarine pigments market shifted from being export oriented to being import reliant. have a long history of use in Western Europe. This transition coincided with the loss of the detergent market segment that had used low-grade ultramarine pigments.4 9.5 14. Ultramarine Pigments Summary Ultramarine pigments. The following table summarizes Western European supply/demand for ultramarine pigments: Western European Supply/Demand for Ultramarine Pigments (thousands of metric tons) 1993 Capacity Production Imports Exports Apparent Consumption SOURCES: 16. The time factor is one of the main reasons many companies have stopped producing these pigments. green.0 0. Statistical Office of the European Community. Portugal. Eurostat.2 thousand metric tons in 1999. Western Europe consumed an estimated 6. M.A.3 thousand metric tons of ultramarine pigments and preparations.A. S. Western Europe produced about 4 thousand metric tons of ultramarine pigments and preparations. S. Ultramarine pigments have been produced in two grades—a low grade. Blue (PB-29) Violet (PV-15) na X 6 X X na X 2. © 2001 by the Chemical Economics Handbook—SRI International . Barcelona United Kingdom Holliday Pigments Limited Hull Total SOURCE: CEH estimates. The production and consumption of the low-grade pigment has decreased because of replacement by more effective organic optical brighteners. Production is declining in Western Europe because of high production costs. less than a third of total world production. down from about 14 thousand metric tons in 1996. Comines Portugal Nubiola . used in all other. Consumption In 1999. used primarily as an optical brightener in laundry detergent and a high grade.5 X X Production It is estimated that in 1999. Habich AG Leiben France Holliday Pigments S.May 2001 575.5 X X 8 >16. Agualva Cacém Spain Nubiola. more durable applications. Demand for high-grade ultramarine pigments has increased steadily in the last several years because of their safety and versatility.A.Produtos Químicos.0004 R PIGMENTS Pigments Page 122 Western European Producers of Ultramarine Pigments Annual Capacity as of 2001 (thousands of metric tons) Company and Plant Location Austria Habich Pigments Chemische Farbenfabrik H. 34 Euros per kilogram. The dominant country of origin was Romania. © 2001 by the Chemical Economics Handbook—SRI International . detergents. The drop is attributable to greater production in the Far East. plastics. printing inks. The excellent heat stability of ultramarine blue pigments and the pleasant color shades achieved. however. Trade Western European exports of ultramarine pigments have declined since 1996. there are only a few applications for which these pigments are not recommended (e. possibly at a rate above GDP growth. from 10 thousand metric tons to 297 metric tons in 1999.0 thousand metric tons in 1999. It is expected that consumption will be driven in part by the continued substitution of ultramarine pigments for pigments with toxic properties. cosmetics and soaps). The following pie chart shows Western European consumption of ultramarine pigments (excluding use in detergent) in 1999: Western European Consumption of Ultramarine Pigments—1999 Cosmetics 3% Other Paper 3% 4% Artist Colors 5% Printing Inks 6% Writing Inks 7% Plastics 62% Paints and Coatings 10% SOURCE: CEH estimates.g. paints. Imports of ultramarine pigments into Western Europe were negligible in the past.18 euros per kilogram in 1998.g. Imports. It is expected that Western European consumption of ultramarine pigments will continue to grow during the next few years.May 2001 575. imports increased and reached about 3.0004 S PIGMENTS Pigments Page 123 Ultramarine pigments are used in practically all types of color applications (e. Price The average Western European import value for ultramarine pigments in 1999 was 1.. air-drying paints for outdoor use in urban atmospheres). Since the mid1990s.. paper and paper coating. are reasons for their wide acceptance in plastic coloration. up from 1. 500 3.751 3.209 6.304 3.009 3. Analytical Tables of Foreign Trade: Products-Countries.793 3.4100. Eurostat. 1995 754 212 108 148 0 6 1.551 4.228 1999 1.176 3.690 3. SOURCE: The following table shows historical Western European imports of ultramarine pigments and preparations: Western European Imports of Ultramarine Pigments and Preparationsa (metric tons) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1997 1998 1999 2. EU Imports of Ultramarine Pigments by Country of Origina (metric tons) Origin Romania India Colombia Japan United States Other Total a.0004 T PIGMENTS Pigments Page 124 Shown below are the Western European imports of ultramarine pigments and preparations from outside the region.663 3.025 2.936 2.259 4.552 2.816 4.203 5.May 2001 575. Statistical Office of the European Community. NIMEXE.782 6.725 2.058 © 2001 by the Chemical Economics Handbook—SRI International .345 869 516 213 90 25 3.058 European Union tariff code number is 3206. European Community 1989-1995. 6. since exports from France are no longer reported.0004 U PIGMENTS Pigments Page 125 a.800 9. Eurostat. SOURCE: Iron Blue Pigments Summary The following table summarizes Western European supply/demand for iron blue pigments: © 2001 by the Chemical Economics Handbook—SRI International . Western Europe exported 297 metric tons. Eurostat.891 metric tons in 1995.286 8.226 7. After 1989. European Union 1997-1999. NIMEXE. NIMEXE.700 7.May 2001 575.501 7. European Union 1997-1999. Statistical Office of the European Community (data for 1985-1995 and European Union (data for 1999).891 297 European Community 1989-1995. Western European exports of ultramarine pigments are shown in the following table: Western European Exports of Ultramarine Pigmentsa (metric tons) 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1999 a. Statistical Office of the European Community (data for 1985-1995) and European Union (data for 1997-1999). Analytical Tables of Foreign Trade: Products-Countries.231 8. In 1999. Analytical Tables of Foreign Trade: Products-Countries.209 8. export data are incomplete. Exports of ultramarine pigments from Western Europe have fallen significantly.789 7.000 8.455 9. SOURCE: Exports. versus 7. ).0 9. Statistical Office of the European Community.9 4. (B) CEH estimates. Eurostat. with plants in Germany and the United Kingdom (formerly Manox Ltd.0004 V PIGMENTS Pigments Page 126 Western European Supply/Demand for Iron Blue Pigments (thousands of metric tons) 1996 Capacity Production Imports Exports Apparent Consumption SOURCES: 9. therefore.7 0.3 0. reduce the dispersion time required. Degussa uses ammonium/sodium ferrocyanide as a raw material. The company has recently started to produce granular iron blue pigments at its plant in the United Kingdom. Granular-type pigments are easily dispersible and.5 3. along with their annual capacities.5 6.0 (A) NIMEXE. Analytical Tables of Foreign Trade: Products-Countries.5 4.May 2001 575.7 1999 9.2 4. At its German plant the company has captive potassium ferrocyanide raw material available and in the United Kingdom plant. Producing companies In Western Europe only two producers of iron ferrocyanide (iron blue) pigments (PB–27) remain.5 © 2001 by the Chemical Economics Handbook—SRI International . is the main producer. SA—INTORSA Montcada i Reixac United Kingdom Degussa-Hüls Limited Manox Division Manchester Total 5. The Western European producers of iron blue pigments.6 2. Degussa AG.0 0. Western European Producers of Iron Blue Pigments Annual Capacity as of 2001 (thousands of metric tons Company and Plant Location Germany Degussa-Hüls AG Wesseling Spain Intermedios Orgánicos.2 1. are listed below. Apart from this tracking function of the pigment. By far the most important use of iron blues is in the printing inks industry. Iron blues are well suited for the manufacture of dark blue shades in coatings for the automotive industry. down from 3. Environmental concerns and reduced demand have forced companies to close their iron blue pigment plants. particularly in the Mediterranean countries. It is estimated that consumption in 1999 was approximately 4. 2. for the manufacture of inexpensive. (B) CEH estimates. which itself is colorless. Western European Consumption of Iron Blue Pigments by End Use—1999 Quantity (metric tons) Printing Inks Fungicide Coloring Paints and Coatings Paper Chrome Green Manufacture Tinting. however. © 2001 by the Chemical Economics Handbook—SRI International . the two remaining producers in Western Europe together produced some 3.000 Market Share (percent) 65 22 8 3 1 1 100% Printing inks. In 1998. Production The production of iron blue pigments has declined continually in the past decade.0004 W PIGMENTS Pigments Page 127 SOURCES: (A) 1999-2000 Directory of Chemical Producers—Europe. iron blue pigments find limited application in the automotive repair paint segment. also have a biological effect on the grapes in that they increase the production of chlorophyll in the leaves. Nevertheless. Consumption Western European consumption of iron blue pigments has eased slightly during the past decade. deep blue colors that have good lightfastness. In these combinations iron blues are used in volumes of 5-8% for gravure printing and 5-10% for black-ink book printing and offset printing.4 thousand metric tons in 1996.600 900 300 120 40 40 4. iron blues were used for the coloring of organic fungicides (mainly dithiocarbamate types). The use of this coloring pigment permits an easy method for tracking the distribution of the fungicide. Paints and coatings. Iron blues are extensively used in combination with phthalocyanine blues and for toning with black printing inks. iron blues.May 2001 575. Starting in the 1950s. iron blues are considered of minor importance because of the superior quality of organic pigments. SRI International. Food Colorants Total SOURCE: CEH estimates.2 thousand metric tons of iron blue pigments. because of their iron content. Fungicide coloring.0 thousand metric tons. used in the treatment of vineyards. In this application. while at the same time. Iron blue pigments find use in a number of other smaller applications. primarily because of China whose shipments to Western Europe increased ten-fold. Consumption of iron blue pigments for this application is less than 50 metric tons. Trade Until 1995. In these applications iron blues can be used as a single pigment or for toning carbon blacks. imports of iron blue pigments were small and accounted for 0. After China. as well as for the manufacture of one-time or multiuse carbon paper and copy paper.6 thousand metric tons or less each year (less than 15% of supply). Western European production and exports declined. They have an advantage over other pigments in that they do not bleed through color bases or olein. Iron blue pigments are sold mainly in paper bags in 20-25 kilogram quantities (Vossen Blue 705LS in 20-kilogram bags) or in large flexible containers (super sacks) of one metric ton. Up to a third of Western European production was typically exported. down from 2. The commercial importance of chrome green pigments continues to decline and it is expected that production of this particular pigment will eventually be terminated and hence the demand for iron blue pigment in this segment. © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. Beginning in 1997.44 euros per kilogram in 1998. BASF and Cappelle both manufacture chrome green pigments on a campaign basis. Western Europe is now import dependant.01 euros per kilogram in 1999. with imports accounting for over onethird of supply. India and the United States. Iron blue pigments are still used in the production of chrome green. leading countries of origin include Japan (Kyosei Chemical). Price The average Western European import value for iron blue pigments was 2.0004 X PIGMENTS Pigments Page 128 Paper. Iron blue pigments are used to a small extent in the production of colored paper. imports increased significantly. a combination pigment consisting of chrome yellow and iron blue. particularly in preparations with high volumes of mineral oils. Other. (A) NIMEXE.467 1. Statistical Office of the European Community. b. Cadmium Pigments The following table summarizes Western European supply/demand for cadmium pigments in selected years: © 2001 by the Chemical Economics Handbook—SRI International . The export business is still viable.5 thousand metric tons in 1996. (B) CEH estimates.May 2001 575.9 thousand metric tons in 1999. down from 1. The main export destination is the United States. Analytical Tables of Foreign Trade: Products-Countries.651 Romania.2 thousand metric tons in 1996 to about 0. --3b 10 --5 47 85 94 60 613 608 854 India ---------2 ----Japan 176 232 181 229 394 352 541 479 248 310 407 434 381 448 United States 42 38 15 26 13 10 5 6 7 2 10 1 2 61 Former USSR 50 61 68 -71 10 1 17 --c --c --c --c --c --c Other 4a --7a ----33 135 6 369 476 288 Total 272 331 267 272 478 372 552 549 373 543 483 1. Exports are expected to continue to decline. but declining. to which the two Western European producers together exported 486 metric tons in 1999. Western European Imports of Iron Blue Pigments by Country of Origin (metric tons) China 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1997 1998 1999 a. c. Data included with OTHER.417 1.0004 Y PIGMENTS Pigments Page 129 The table below lists import data by country of origin. Via Macao. Eurostat. SOURCES: Western Europe’s exports of iron blue pigments fell from about 2. (B) Jahresstattistik des Aussenhandels der Schweiz. producers in Western Europe have adjusted with production termination and restructuring.0004 Z PIGMENTS Pigments Page 130 Western European Supply/Demand for Cadmium Pigments (thousands of metric tons) 1988 Capacity Production Imports Exports Apparent Consumption SOURCES: 4.85 1993 3.1 1. Eidgenoessische Oberzolldirektion.05 1. Eurostat. Statistical Office of the European Community.10 1.4 neg 1.0 1999 3. particularly in plastics.1 neg 0. (C) CEH estimates. Johnson Matthey Ceramics & Materials (formerly Cookson Matthey). In 1993.May 2001 575.6 0. Analytical Tables of Foreign Trade: ProductsCountries .5 (A) NIMEXE.1 2. The remaining cadmium pigment producers in Western Europe are Société Lanquedocienne de Micron-Couleurs. It is expected that fewer Western European cadmium pigment producers will remain within the next few years as environmental regulations further limit the use of cadmium pigments. © 2001 by the Chemical Economics Handbook—SRI International .9 0.3 1996 3. Producing companies As cadmium pigment consumption has declined.9 1. James M.4 1.2 neg 0.15 2. BASF terminated the manufacture of cadmium pigments.1 2. Brown and General Quimica. A.0005 A © 2001 by the Chemical Economics Handbook—SRI International PIGMENTS .a (owned 100% by Repsol Química.850 X X X General Química. France) Narbonne Germany Cerdec AG.A.Pigments Page 131 Western European Producers of Cadmium Pigments Annual Capacity as of 2001 (metric tons) Yellow PY-35 PY-35:1 PY-37 PY-37:1 Orange PO-20 PO-20:1 PR-108 Red PR-108:1 Company and Plant Location France Société Languedocienne de MicronCouleurs SA—SLMC (owned 100% by Total. SRI International. S. Materials Division Pigments & Dispersions Stoke on Trent Total a. S.200 X X X X X X na X X X X General Química. 150 X X X X X X X X 600 X X X X X X 900 >2. (B) CEH estimates. is also producing the mercury-containing cadmium pigments PO-113 and PO-113:1. (A) 1999/00 Directory of Chemical Producers—Europe. S. SOURCES: May 2001 575. Keramische Farben Bonn Spain 1.A.) Comunión-Lantarón United Kingdom Holliday Pigments Limited Stoke on Trent Johnson Matthey Ceramics & Materials Ltd. Norway. Finland.9 thousand metric tons in 1988.850 1.May 2001 575.0005 B PIGMENTS Pigments Page 132 Production The production of cadmium pigments in Western Europe has declined considerably.1 thousand metric tons. total Western European consumption is estimated to have been 0. as shown in the following pie chart and table: Western European Consumption of Cadmium Pigments by Market Segment—1999 Other 5% ABS 30% LDPE 5% PS 10% PP 15% HDPE 20% Ceramic Materials. It is estimated that Western European production in 1999 was approximately 1. Consumption In 1999. down from 2. Consumption in selected years is shown in the following table: Western European Consumption of Cadmium Pigments (metric tons) 1988 1993 1996 1999 SOURCE: CEH estimates. The consumption pattern in Western Europe is similar to that in the United States and Japan.5 thousand metric tons. Paints and Costings 15% © 2001 by the Chemical Economics Handbook—SRI International .345 1. Sweden and Switzerland. 1. consumption of cadmium pigments has practically ceased in Denmark. the Netherlands.015 500 Because of environmental regulations and voluntary substitution by pigment consumers. Ireland. nonbleeding characteristics). cadmium pigments may not be used to give color to polymers in which it is anticipated it may be possible to demonstrate satisfactory substitution by that date.May 2001 575. CEH estimates. These polymers include: epoxy resins polyurethanes polyvinyl chloride (PVC) cellulose acetate cellulose acetate butyrate low-density polyethylene (LDPE) (except as masterbatch) q Beginning December 31. 30 20 15 10 5 5 15 100% SOURCE: Although cadmium pigments as a group are among the most versatile pigments and have considerable advantages over other pigments (e. but restricts their use where they are not seen to be essential. Paints and Coatingsa Total a.. high-temperature stability. In a number of countries the use of cadmium compounds has virtually ceased.0005 C PIGMENTS Pigments Page 133 Western European Consumption of Cadmium Pigments by Market Segment—1999 Market Share (percent) Plastics ABS HDPE PP PS LDPE Other Ceramic Materials. Includes artist’s colors. environmental concern over the use of cadmium in products has led to a series of regulations limiting their use in Western Europe. The polymers added to the above list are the following: melamine-formaldehyde resins urea-formaldehyde resins polyproplyene cross-linked polyethylene unsaturated polyester resins acrylonitrile–methyl methacrylate polyethylene terephthalate © 2001 by the Chemical Economics Handbook—SRI International . The directive does not ban the use of cadmium pigments. wide range of brilliant colors. the European Union has adopted a directive on the use of cadmium pigments that harmonizes restrictions on their use within the EU member states.g. 1992. cadmium pigments may not be used to give color to polymers in which substitution is already demonstrated as feasible. Faced with the problem of different approaches being taken throughout its member states. 1995. The following summarizes the regulations laid out in the European Union Directive 91/338 EEC: q Beginning December 31. Canada. Western European consumption of cadmium pigments is expected to drop to less than 100 metric tons by 2004. Austria. Price Cadmium pigments are relatively expensive specialty high-performance pigments. the EU Directive 91/338 takes effect only after being implemented in member countries. It is estimated that the decreased use of cadmium pigments will be substituted for the most part by organic pigments. Some inorganic pigments such as bismuth vanadate and rare earth sulfide pigments are increasingly used as substitutes. mainly as mixtures with rutile-structured complex inorganic pigments that augment the hiding power. During 1992-1994 import volumes decreased in line with © 2001 by the Chemical Economics Handbook—SRI International .83 19. dollars at the London Metal Exchange. as there appears to be no alternative for the use of cadmium pigments.25 Eurostat. the use for artist’s colors and materials will hardly be affected. Trade Western Europe has been a net exporter of cadmium pigments for many years. be used to give color to all other polymers in which substitution is currently envisaged to be impracticable. Imports of cadmium pigments and preparations have never been very important.May 2001 575. Sweden and Switzerland have also adopted similar restrictions on the use of cadmium pigments although the structure and detail of these regulations may differ in certain instances from the list of EU Directive 91/338. There are small imports from the United States (mainly from Ferro Corporation) and occasionally some material is also imported from Mexico. One use that is unlikely to be affected is glass and ceramics. Also. India and Ecuador. However. which is fixed in U. The following table gives gives average import values for cadmium pigments in Western Europe: Western European Average Import Values for Cadmium Pigments (euros per kilogram) 1998 1999 SOURCE: 24. The major exporting countries are the United Kingdom and France. however.0005 D PIGMENTS Pigments Page 134 polybutylene terephthalate high-impact polystyrene transparent/general-purpose polystyrene Cadmium pigments may. The price for cadmium pigments depends mostly on the cadmium metal price. Statistical Office of the European Union.S. Taking these regulations and trends into account. European Union 1997-1999. however. cadmium pigment exports to the United States totaled 140 metric tons. down from 308 metric tons in 1990.May 2001 575. the export business of the Western European producers still holds limited potential for a few years. Analytical Tables of Foreign Trade: ProductsCountries. The main destination for cadmium pigments is the United States. U. In 1999. The temporary increase of imports in 1995 can be explained by the fact that some consumers in Spain stockpiled cadmium pigments before they were totally phased out. Eurostat.S. 5 20 18 23 12 14 23 60 15 9 82 15 20 11 SOURCE: Although consumption of cadmium pigments in Western Europe is expected to decrease further. The following table shows Western European exports of cadmium pigments: © 2001 by the Chemical Economics Handbook—SRI International . After 1990. consumers have reduced the use of cadmium pigments in plastic products. NIMEXE. Because of more stringent regulations. Statistical Office of the European Union. decreased steadily. volumes exported to the United States have.0005 E PIGMENTS Pigments Page 135 decreasing demand in Western Europe. European Community 1989-1995. The following table shows Western European imports of cadmium pigments beginning in 1985: EC Imports of Cadmium Pigmentsa (metric tons) 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1997 1998 1999 a. 486 1. NIMEXE.539 1.660 1.0005 F PIGMENTS Pigments Page 136 Western European Exports of Cadmium Pigmentsa (metric tons) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1997 1998 1999 a. Analytical Tables of Foreign Trade: Products-Countries.547 1.797 1.214 1.072 1.523 1. SOURCE: Bismuth Vanadate Pigments Producing companies The following table shows the current producers of bismuth vanadate pigments in Western Europe: © 2001 by the Chemical Economics Handbook—SRI International .612 1. Eurostat.365 1.355 1.135 1.879 2. Statistical Office of the European Community.3000 (after 1987). 1.406 1.391 1.005 787 611 583 European Community tariff code numbers are 3207.May 2001 575.76 (until 1987) and 3206. high color strength alternative pigments will continue to grow. Germany Gebroeder Cappelle nv Menen. It can be expected that consumption of these high-saturation. as well as in water-based paints) and plastics. nitrocellulose and stoving paints. © 2001 by the Chemical Economics Handbook—SRI International . a leading producer of rare earth compounds. Six pigments. Volume increases will start from low levels and be rather modest due to relatively high prices exceeding DM50 per kilogram. Belgium SOURCE: CEH estimates. such as nylons. Maastricht. Consumption Bismuth vanadate pigments are a relatively new group of pigments introduced primarily as an alternative to lead chromate pigments. Applications are similar to those of lead chromates. KG Bruchsal. KG Langelsheim. Netherlands Dr. currently based on cerium sulfide. Rare earth sulfide pigments are likely to compete to some extent with complex inorganic pigments. Hans Heubach GmbH & Co. It is estimated that total Western European consumption of bismuth vanadate pigments in 1999 was approximately 300 metric tons.V. Germany Ciba Specialty Chemicals Maastricht B.0005 G PIGMENTS Pigments Page 137 Western European Producers of Bismuth Vanadate Yellow Pigments—2001 BASF Aktiengesellschaft Köln. Germany Bruchsaler Farbenfabrik GmbH & Co. Rare Earth Sulfide Pigments Rhône-Poulenc.May 2001 575. This figure includes the bismuth vanadate/ molybdate mixed pigments. has recently commercialized a new group of pigments based on rare earth sulfides. in paints (alkyd. have many similar properties to cadmium and lead chromate pigments: PO-78 PR-265 PR-265 PR-275 PR-275 na Orange Orange pigment Red pigment Red Red Yellow Neolor ™ Orange Light S Neolor™ Orange S Neolor ™ Red S Neolor ™ Burgundy Light S Neolor ™ Burgundy S Neolor ™ Yellow S The above-mentioned pigments are aimed primarily at replacing cadmium-based pigments in engineering polymers. the product is processed to its pigment form at Clamecy. finally.May 2001 575. has an annual nameplate capacity of 500 metric tons. where the high-temperature stability of rare earth sulfide pigments will meet the expectations of former cadmium and lead chromate users and where the relatively high prices can be better absorbed. Market prices will likely continue to decrease with increasing market penetration. At La Rochelle rare earths are separated and sent to Les Roches-Roussilon where sulfurization is carried out.0005 H PIGMENTS Pigments Page 138 Producing companies Rhône-Poulenc is the sole producer of rare earth sulfide pigments. The different production steps to produce rare earth sulfide pigments are located at three sites in France. Also it is envisaged that rare earth sulfide pigments could substitute for certain solvent dyes in outdoor polyurethane products. The processing plant. rare earth sulfide pigments were sold at about $40 per kilogram. The main applications are likely to be in engineering plastics. In Western Europe. which came on stream in mid-1997. Consumption Rare earth sulfide pigments are still in the early stage of their life cycle. Production Rhône-Poulenc is the sole manufacturer and full nameplate capacity may not have been reached. it is likely that less than 200 metric tons of rare earth sulfide pigments were consumed in 1999. Price As of March 2001. Zaklady Produkciyno-Handlowy Borowno Ferro-Pigment-Produkcija Farb i Pigmentow Kozienice Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Unspecified Remarks -- -- X -- -- -- -- 0. down from about $50 per kilogram in 1997.05 -- -- © 2001 by the Chemical Economics Handbook—SRI International . EASTERN EUROPE Producing Companies The following tables list Eastern European producers of color inorganic pigments: Central and Eastern European Producers of Iron Oxide Pigments Annual Processing Capacity as of 2001 (thousands of metric tons) Company and Plant Location Poland Bemal. Largest production facility in the CIS.3 -- -- -- -- Also manufactures micronized iron oxide pigments (annual capacity is 200 metric tons).5 X X X X X -- -- X -- -- X -- X 3. Yaroslavskoe PO Lakokraska Yaroslavlskaya -- -- -- 2.0 -- -- Synthetic iron oxide pigments from titanium dioxide manufacture.3 X Also manufactures special iron oxide pigments.May 2001 575. Lublin Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Unspecified Remarks -- -- -- -- 0.A. Krivorozhskiy Surikoviy Krivoy Rog -- -- X -- -- Natural iron oxide pigments. Ukraine Krimskoe PO “Titan” Iskhodnoe -- -- 30.0 -- X X X X -- Total capacity is about 300 metric tons per year.0005 I PIGMENTS Pigments Page 139 Central and Eastern European Producers of Iron Oxide Pigments (continued) Annual Processing Capacity as of 2001 (thousands of metric tons) Company and Plant Location Poland (continued) Kieleckie Zaklady Farb i Lakierow “Polifarb” Skarzysko-Kamienna Lubelskie Przedsiebiorslwo Przemyslowo-Handlowe “Odczynniki Chemiczne” Lublin Minochem Wytwórnia Farb i Lakierów Grójec Polifarb Blyzin Blyzin Zaklady Chemiczne “Organika-Zachem” Bydgoszcz Zaklady Chemiczne “Permedia” S. Russia NIPROINS—NauchnoIssledovatelskogo i Proektnogo Chelyabinsk 0. © 2001 by the Chemical Economics Handbook—SRI International . Uzbekistan Tashkentskiy Lakokrasochniy Zavod Tashkent SOURCE: CEH estimates.May 2001 575.5 -- © 2001 by the Chemical Economics Handbook—SRI International .5 -- Synthetic iron oxide pigments from titanium dioxide manufacture. -- -- -- 2.0 2.0005 J PIGMENTS Pigments Page 140 Central and Eastern European Producers of Iron Oxide Pigments (continued) Annual Processing Capacity as of 2001 (thousands of metric tons) Company and Plant Location Ukraine (continued) Sumskie PO “Chimprom” Sumi Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Unspecified Remarks -- -- 15. Pigments Page 141 Central and Eastern European Producers of Chrome Pigments Annual Processing Capacity as of 2001 (thousands of metric tons) Lead Chromates Chromium Oxide Green Company and Plant Location Hungary Holland Colours Hungária Kft Szolnok Chrome Yellow (PY-34) Molybdate Orange (PR-104) Anhydrous (PG-17) Hydrated (PG-18) Hydrated Zinc Chromate (PY-36) Unspecified Remarks 3.0 1.0 0.2 0.1 1.0 -- Also produces zinc chromate and zinc phosphate as well as pigment pastes. Kazakhstan PIGMENTS Zavod Chromivikh Soedineniy Aktyubinsk Poland Zaklady Chemiczne “Alwernia” S.A. Alwernia Zaklady Chemiczne “Permedia” S.A. Lublin Russia Novotroitskiy Zavod Khromovikh Soedineniy Novotroitsk -- 2.5 -- -- -- -- Zinc-molybdate chrome yellow. X 0.3 -- 0.3 X -- -- 11.0 -- -- -- 5.2 -- Also manufactures chromium phosphate in a 1.9 thousand metric ton-per-year plant. May 2001 575.0005 K Yaroslavskoe PO Lakokraska Yaroslavlskaya SOURCE: CEH estimates. 8.0 -- -- -- -- -- © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0005 L PIGMENTS Pigments Page 142 Central and Eastern European Producers of Iron Blue Pigments Annual Capacity as of 2001 (thousands of metric tons) Company and Plant Location Poland Zaklady Chemiczne “Organika Dolnoslaskie” Zarow Russia Chelyabinskiy Lakokrasochiny Zavod Chelyabinsk SOURCE: CEH estimates. 0.25 2.8 Central and Eastern European Producers of Ultramarine Pigments Annual Capacity as of 2001 (thousands of metric tons) Company and Plant Location Poland Polifarb Kalisz SA Kalisz Zaklady Tworzyw i Farb Zloty Stok Remarks 0.5 Green, pink, red and violet pigments. na New plant under construction. Capacity is not known. Russia Krasnoyarskoe PO “Khimprom” Krasnoyarsk SOURCE: CEH estimates. 0.25 © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0005 M PIGMENTS Pigments Page 143 Central and Eastern European Producers of Cadmium Pigments Annual Capacity as of 2001 (thousands of metric tons) Company and Plant Location Poland Zaklady Chemiczne “Permedia” S.A. Lublin Romania Pigmenti SA Oradea Russia na Pigments Produced 0.2 Orange, red and yellow. neg <0.5 Small production of cadmium-based pigments. SOURCE: CEH estimates. Central and Eastern European Producers of Cobalt Pigments Annual Capacity as of 2001 (thousands of metric tons) Company and Plant Location Poland Zaklady Chemiczne “Permedia” S.A. Lublin Russia na Pigments Produced 0.1 <0.2 Small production of cobalt-based pigments. SOURCE: CEH estimates. A general description of the major pigment producers in Central and Eastern Europe is presented below by country. Precheza a.s. is the sole manufacturer of inorganic pigments in the Czech Republic. The main product is red iron oxide, but limited volumes of brown iron oxide as well as pearlescent pigments are also manufactured. In Hungary, Holland Colours Hungária Kft, owned 90% by Holland Colours NV, the Netherlands, has advanced to become one of the leading inorganic pigments producers in Central Europe. About 85% of total output is for inorganic pigments (chrome yellows, molybdate orange and zinc phosphate) and the remaining 15% are pigment preparations and pigment pastes. All products are sold under the trade name Holcobatch®. The company is a large exporter to Central and Western European countries but also sells © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0005 N PIGMENTS Pigments Page 144 to other regions. There are substantial investment programs aimed at a substantial capacity increase and expansion of product range. Zavod Chromivikh Soedineniy is the only manufacturer of inorganic pigments (molybdate orange pigment) in Kazakhstan. The output is sold primarily on the domestic market. The booming crude oil industry may lead to increased demand for anticorrosion paints and coatings also requiring inorganic pigments. Zaklady Chemiczne “Permedia” S.A. (also known as Permedia Chemical Works) is Poland’s main inorganic pigment producer, with a domestic market share of approximately 40%. The company is 100% owned by local municipalities. Apart from pigments, Permedia also produces nickel oxide, nickel sulfate heptahydrate and nickel copper oxide. In Romania, Pigmenti SA at Oradea is the leading pigment manufacturer. The product range includes chromate and chromium pigments, anticorrosion pigments (e.g., zinc phosphate, barium chromate), as well as iron oxide pigments. The company’s main trading partner is Policolor SA at Bucharest, to which the company sells about 65% of its output. Other key accounts of Pigmenti are Sinteza Color SA at Oradea and Azur SA at Timisoara. The severe economic downturn in Russia has forced a number of pigment producers to shut down their operations altogether. The two most important producers of inorganic pigments are Novotroitskiy Zavod Khromovikh Soedineniy at Novotroitsk, manufacturing lead chromates, zinc chromate and chromium phosphate and Yaroslavskoe PO at Yaroslavsk manufacturing yellow chrome and iron oxide pigments. Apart from these companies there are about five smaller manufacturers of color inorganic pigments. Although the severe shortage of inorganic pigments in Russia would suggest many business opportunities, there are significant barriers for newcomers in this country. Possibly the most critical barrier is the difficulty in obtaining payment for delivered goods because of the desolate financial situation of most of the pigment consumers. Nevertheless, it is likely that within the next decade a number of companies will attempt to enter (or reenter) the inorganic pigments market in Russia. Two of the region’s largest iron oxide pigments producers are located in the Ukraine, Sumskie PO “Chimprom” and Krimskoe PO “Titan,” manufacturing about 47% of the region’s total production. In Uzbekistan, Tashkentskiy Lakokrasochniy Zavod is the one known producer of inorganic pigments (iron oxide yellow). Production Estimated production of inorganic color pigments in 1999 is presented in the following table: © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0005 O PIGMENTS Pigments Page 145 Central and Eastern European Production of Color Inorganic Pigments—1999 (thousands of metric tons) Iron Oxide Pigments Czech Republic Hungary Kazakhstan Poland Romania Russia Ukraine Uzbekistan Total SOURCE: 8.5 --13.0 <5.5 >2.0 27.0 1.0 57.0 CEH estimates. Chrome Pigments -2.5 1.5 0.25 0.25 24.0 --28.5 Iron Blue ---0.15 -2.0 --2.15 Ultramarine Blue ---0.3 -0.2 --0.5 Cadmium Pigments --0.1 0.1 0.3 -Cobalt Pigments ---0.1 -0.1 --0.2 0.5 Production of inorganic pigments has declined significantly over the last decade and is believed to have bottomed out in 1996. The region has a severe shortage of at least 30 thousand metric tons of iron oxide pigments and a very sizable volume of other inorganic pigments. The main reason that pigment production is growing so slowly is because of the continued financial difficulties, particularly in Eastern European countries. In the medium term, however, it is anticipated that production will begin to rebound. Consumption The following table gives an estimate for inorganic pigments consumption in Central and Eastern Europe in 1999: Central and Eastern European Consumption of Color Inorganic Pigments—1999 (thousands of metric tons) Iron Oxide Chromates Ultramarines Chromium Oxide Complex Inorganic Pigments Cadmium Pigments Iron Blues Total SOURCE: CEH estimates. 30.0 2.5 1.5 1.0 0.4 0.4 0.4 36.2 Of the 36 thousand metric tons of inorganic color pigments consumed in the region, about 80% is consumed by paints and coatings with the remaining 20% consumed in other market segments, such as plastics and printing inks. © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0005 P PIGMENTS Pigments Page 146 J APAN Producing Companies The major Japanese producers of inorganic color pigments are listed in the following table: © 2001 by the Chemical Economics Handbook—SRI International Major Japanese Producers of Inorganic Color Pigments—2000 Pigments Page 147 Company Daiichi Kasei Kogyo Co., Ltd. Hyogo Prefecture Shiga Prefecture Ferro Enamels (Japan) Ltd. Osaka Prefecture Ishihara Sangyo Kaisya, Ltd. Mie Prefecture Iron Oxide (Hematite) (Red 101) Iron Oxide (Magnetite) (Black 11) Iron Oxide (Goethite) (Yellow 42) Chrome Yellow (Yellow 34) Molybdate Chrome Orange (Red 104) Chromium Oxide (Green 17) Zinc Chromate/ Zinc Yellow (Unticorrosive pigment) Iron Blue (Blue 27) Ultramarine Blue (Blue 29) Other X X Metals compounds PIGMENTS Titanium Yellow X X Izumi Kasei Kogyo K.K. Osaka Prefecture Kikuchi Color & Chemicals Corp. Tokyo Prefecture Kyosei Chemical Co., Ltd. Niigata Prefecture Merck Japan Ltd. Fukushima Prefecture Morishita Bengara Kogyo Co., Ltd. Mie Prefecture Nippon Chemical Industrial Co., Ltd. Yamaguchi Prefecture X X X X Pearlescent pigments X X X May 2001 575.0005 Q X © 2001 by the Chemical Economics Handbook—SRI International Major Japanese Producers of Inorganic Color Pigments—2000 (continued) Pigments Page 148 Company Nippon Denko Co., Ltd. Tokushima Prefecture Titan Kogyo K.K. Yamaguchi Prefecture Toda Kogyo Corp. Okayama/ Yamaguchi Prefecture Toho Ganryo Kogyo Co., Ltd. Tokyo Prefecture Number of Operating Plants Annual Capacity (thousands of metric tons) a. Iron Oxide (Hematite) (Red 101) Iron Oxide (Magnetite) (Black 11) Iron Oxide (Goethite) (Yellow 42) Chrome Yellow (Yellow 34) Molybdate Chrome Orange (Red 104) Chromium Oxide (Green 17) Zinc Chromate/ Zinc Yellow (Unticorrosive pigment) Iron Blue (Blue 27) Ultramarine Blue (Blue 29) Other X X X X X 23 227.6a X 2 6.8 2 1.8 2 7.2 1 1.0 1 5.0 2 1.8 Includes plants and capacity for magnetic iron oxide/ferrites production. CEH estimates. SOURCES: May 2001 575.0005 R © 2001 by the Chemical Economics Handbook—SRI International X PIGMENTS Depending on the surface coating type and its thickness.3 micrometer diameter. In 2000. 1999. The company has a 100%-owned subsidiary. Toho Ganryo Kogyo produces heat resistant high-quality yellow and red iron oxide pigments by using purchased iron oxide. PG-19. As other producers (Dainichiseika Color & Chemicals Mfg. Titan Kogyo produces iron oxide for both pigments and magnetic media/ferrites and the company has the strength of supplying especially PY42 (yellow iron oxide) to the pigment sector. various color pearlescent pigments can be produced. Chongqing Jiangnan Kikuchi. Bayer (Japan) imports iron oxide pigments from China. and the company will concentrate on the industrial chemical business. Merck Japan Ltd. categorized as complex inorganic pigments. Reportedly. 50. black iron oxide or aluminium oxide. Nippon Inorganic Colour & Chemical Company withdrew from the pigment business itself by ceasing chrome yellow. using Kuraray’s captive hydrogen cyanide coproduced at methyl methacrylate production (by the acetone cyanohydrin process). Ferro Enamels (Japan) Ltd. 118. the company produces ultramarine pink and ultramarine violet. Canada). The flake size of pearl is roughly 20 micrometers in diameter with a 0. most of the major producers manufacture magnetic iron oxide/ferrites only. Beside ultramarine blue. 29. and hold similar market share. also produces titanium yellows. Other color inorganic pigments Kyosei Chemical. Unlike in the United States and Europe. Kikuchi Color built a chrome color pigments plant. Kikuchi Color is the only company to expand chrome color pigment capacity worldwide. one in Hyogo Prefecture and the other in Shiga Prefecture. there are no producers of natural iron oxide pigments. 36. and PY-53. 72. produces a variety of complex inorganic pigments such as PB-28. its capacity was expanded 25% in May. Fukushima Prefecture. and exports some chrome color pigments back to other Asian countries.0005 S PIGMENTS Pigments Page 149 Iron oxide pigments Although there are a great number of iron oxide producers in Japan. Nippon Chemical Industrial and Nippon Denko are the only two producing companies in Japan. which is used as green pigment. Toda Kogyo is the leading supplier of iron oxide for both pigments and magnetic media/ferrite applications. one of the leading producers of titanium oxide. Daiichi Kasei Kogyo is the sole producer of ultramarine blue. produces mica-based pearl pigments coated with titanium dioxide.4 micrometer thickness and coated with titanium dioxide particles of 0. These © 2001 by the Chemical Economics Handbook—SRI International . molybdate chrome orange and zinc chromate production in 2000. Daiichi produces ultramarine pigments at two plant sites. in China with 3. Nippon Inorganic Colour & Chemical Company and Toho Ganryo Kogyo) ceased chrome color pigments production in recent years.5 thousand metric tons of capacity. PBn-24. Dominion Colours (Ontario. Titan Kogyo and Bayer (import) are the leading suppliers after Toda Kogyo of iron oxides to the pigment sector. Chrome pigments Kikuchi Color is the world’s leading producer of chrome yellow and also the leading supplier of molybdate chrome orange in Japan. and iron blue sales are handled by Dainichiseika. Ishihara Sangyo. is the sole supplier of iron blue in Japan. Its crude iron blue production is located in Kuraray’s Nakajo plant site in Niigata prefecture. 26. a joint venture between Dainichiseika and Kuraray. at its Onahama plant site in Iwaki City. which is a joint venture with local company.May 2001 575. Germany and the United States. 33. With regard to chromium oxide. Nippon Bengara Kogyo ceased production and is now supplied with iron oxide from Toda Kogyo. 57 2.20 5.4 225.1 9.33 1. 79.18 7.24 2.2 227.48 2. These pigments are produced by Dainichiseika.34 4.97 2.4 222.9 135.0 5. Includes PG-15. (A) CEH estimates (data for 2000).38 2. Bismuth vanadate pigments are finding increasing interest in Japan as a substitute to cadmium and chromate pigments.91 2.35 2. production in Japan is expected to decrease at an average annual rate of 8-9% over the next five years.28 1.20 3. However.43 3.93 6. SOURCES: Among the iron oxide produced domestically.49 1.58 1. The production of chrome pigments is an important application for both sodium bichromate and chromic acid.20 5.5 10. mainly because of environmental © 2001 by the Chemical Economics Handbook—SRI International .47 1.9 8.71 6.51 2.4 216.05 7.39 5.4 232.0 4.0005 T PIGMENTS Pigments Page 150 pigments have been consumed mainly in automotive basecoat applications.39 2.83 1.83 3.0 211.4 4.74 2.93 8.7 10.20 6.06 7.8 138.4 3.96 1.65 1.96 1.26 5.57 3.86 3.7 10.02 1.41 5.43 1.56 5.45 2.33 1.63 3.47 2.99 3.26 6.24 Ultramarine Blue 0.0 5.77 2.60 Chromium Oxideb 1.88 2.May 2001 575.10 6.07 6.52 1.8 127.60 1.11 7. b.5 164.12 5.98 1.98 2.55 1.9 7.97 1. adding excellent luster appearance.5 3.0 127.5 7.42 1.2 207.2 8.4 3.7 3.3 190.86 2.0 4.9 250.29 1.00 1. pigment use was approximately 27 thousand metric tons.36 3.58 1.6 219. Production Historical production data for inorganic pigments are provided in the following table: Japanese Production of Inorganic Color Pigments (thousands of metric tons) Iron Oxide 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 a.44 1.50 3.52 1.43 1.34 3.42 1.13 5.0 Chrome Yellowa 11.44 Iron Blue 2.93 6.7 225.35 Molybdate Chrome Orange 2.16 5.24 2.78 5.28 3.17 3.35 2.50 6.94 1.24 1.9 169.4 9.9 8. (B) Japan Inorganic Chemicals Association (all other data).8 212.35 Includes PO-21.3 173. about 12% of total iron oxide production in 1999.84 4.7 195.3 3.51 8.6 238.62 1.08 7. 0 2.3 1.6 0.2 Ultramarine Blue na na na 1.1 4. 0.0 6.5 3.6 7.0 2.2 1.8 46.5 Average Annual Growth Rate (percent) 20002005 a.3 1.4 0.5 2.4 1.1 2.0 2.2 0.3 0. the consumption of iron oxide and ultramarine blue has been fairly stable with some fluctuation.1 62.4% The numbers for iron oxide consumption are for pigments only and excludes ferrite applications.8 49. Chrome-type pigments and iron blue have been decreasing.3 1.6 1.3 63.0 1.7 0. but most of these (89 metric tons) are for export demand. CEH estimate based on data from the Japan Inorganic Chemicals Association and import data.9 50.8 0.2 1.4 5.5 58.1 Total na na na 54.5 0. b.0 6.4 0.8 1.1 1.2 45.2 2.2 47.8% –5.2 1.3 Bismuth Vanadate ---------neg neg neg neg neg neg neg 0.9 59.4 7.0 1.5 0.7 44.6 1.4 45.9 59.5 1.0 na na na na na na na na na 0.0% –0.4 na na na na 4. red) were produced in 1999.7 3.2 5.9 0.8 4.2 1.7 4.4 65.4 7.8 1.0 0.9 1.1 neg neg neg neg Iron Oxidea 1975 1980 1985 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2005 na na na 39.3 1.4% –9.4 0.0 0.6% 0.0 9.4 0.3 0.3 1.3 3.1 2. orange.4 0.6 1. Excludes consumption other than pigment use.0 2.0 68.2 3.6 1.7 3.1 0.5 5.8 CadZirconium Chrome minium Oxideb Oxideb Pigments na na na na na na na na na na na 0.8 4.5 66.6 0.0% 0. gross weight) Zinc Molybdate Chromate/ Chrome Chrome Zinc Yellow Orange Yellow 9.7 65.8 48.2 1.3 2.4 0.9 0.6 1. Consumption The following table presents production of the major inorganic color pigments: Japanese Consumption for Inorganic Color Pigments (thousands of metric tons.3 1.3 1.4 2.8 6.7 65.0 50. © 2001 by the Chemical Economics Handbook—SRI International .8 0.0005 U PIGMENTS Pigments Page 151 issues and their replacement by organic pigments.4 2.0% –3.4 51.May 2001 575.0 0.9 66.7 1.8 1.2 0.6 1.1 4.2 1.0 Iron Blue na na na 1.6 0.4 53.5 1.3 7.4 1. SOURCE: Among the different types of pigment chemicals.0% –7.5% –9.5 7. About 100-120 metric tons of cadmium pigments (yellow.7 48.0 6.7 67.7 1.7 57.1 1.6% na 20.9 2.9 0.2 1.6 2.7 53.0 1. 1 neg neg neg 0.2 -2. including inks.8 0.7 0.1 Other (Pigment) 1996 34. which used to be consumed in screen inks.7 187. b.3 -neg 2. but some big users have switched from blue ink to black ink in this application. so that these chrome pigments only continue to use old.8 0.3 174.5 5.8 2.4 -neg -0. Iron blue is used mainly in newspaper ink for toning of carbon black.8 1996 1.6 -35. yellow pigment itself has lately been avoided in new traffic paints.0 0.4 0.5 0.2 0. coatings.9 4.3 -5. the use of iron blue has been decreasing. but poor color-quality pigments of iron oxide are used mainly in anticorrosive coatings. Japanese consumption of chrome yellow is shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International .4 1999 Non-Pigment Use 1996 1999 114. heavy-duty paint on large metal structures and traffic paint. Even though “yellow” is an important color for traffic paint.4 neg 0. the consumption of ultramarine blue has been stable in a wide variety of applications.8 ----116. such as in industrial automobiles (such as forklifts). 12.6 0.6 ----122.May 2001 575.8 1.2 0.4 0.7 4. Color pigments are used in paint applications for industrial coatings. Iron blue is also used as a color component in bluetype pressure-sensitive ink.1 neg 0.2 neg 0. Statistics for “Ink” seems to include coatings on metal (on can coatings or precoated metal [PCM]) and magnetic ink in uses such as credit card and ticket applications. pavement and paper application.7 Includes construction materials. CEH estimates. gross weight) Paints 1996 Iron Oxide Chrome Yellow Chromium Oxide Molybdate Chrome Orange Iron Blue Ultramarine Blue Zinc Chromate/ Zinc Yellow Total a. other applications replaced iron blue with organic pigments mixtures for better alkaline resistance.2 -2. and (b) paint companies do not formulate these pigments in new coating formulations anymore because of environmental concerns.4 Ink 1999 1.2 0. Meanwhile. Also.3 16.0005 V PIGMENTS Pigments Page 152 Consumption of bismuth vanadate has been quantitively small but growth is expected over the next five years from replacing chrome yellow in traffic paint applications.5 0.0 0.8 Plastics 1996 1.7 21. Chrome yellow and molybdate chrome orange. ceramics/porcelain. but as this application is cost conscious. instead being replaced with white traffic paint with double lines.3 -3.6 -35.6 1.4 -neg -0. existing formulations. plastics and others. topcoats on taxis.4 5.7b 0.6 1.4 1. Quantity used for ferrite/magnetic applications.2 2.4 1999 1.9 34. causing a further decrease in iron blue consumption.0 3.8a 0.5 1.7 neg 0.9 1.1 1999 11.6a 120. The decrease of these pigments in paint applications results from two reasons: (a) the decrease of alkyd and oil paint production itself.2b -1. These chrome-containing pigments has been used in industrial paint applications.4 1999 163. have not been used in recognizable quantities for ink applications in Japan in recent years because of toxicity concerns. The following table shows the 1996 and 1999 consumption breakdown for selected inorganic color pigments in Japan: Japanese Consumption of Inorganic Color Pigments Use by End Use (Including Non-Pigment Uses) (thousands of metric tons.5 1.1 neg 0.6 0.0 Total 1996 171. SOURCE: The major pigment application of iron oxide is in coloring concrete.9 1. 3 6.1 0.4 1.3 6.7 1.5 1.0 6.1 neg neg neg neg 0.1 0.0 1.0 5.3 0.4 5.1 5.8 0.8 1.0 2.7 3.1 Totalb 9 7. b.May 2001 575.7 © 2001 by the Chemical Economics Handbook—SRI International . CEH estimates based on import data and data from the Japan Inorganic Association.2 0.8 6.6 Plastics 0.1 1. gross weight) Paints 1975 1985 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 a.9 1.1 2.3 0.5 1.4 2.1 neg Totalb 2.4 1.6 4.1 1.4 6.2 0.2 1.5 0.2 6.0 4.2 2.4 5.8 2.0 5.0 0.0 1.1 0.3 Includes drawing paints and crayons.4 3.7 0.3 0.6 1.1 0.1 neg neg neg neg neg neg neg 0.6 1.6 0.1 0.3 0.9 1.4 1.0 0. 7.8 0.3 0.4 Printing Ink neg neg neg neg -----------Othera 0.1 1.1 0.2 1.1 3. gross weight) Paints 1975 1980 1985 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 1.8 6.3 7.5 7.9 1.1 Printing Ink neg neg neg neg neg -----------Othera 0.1 0.8 5.8 Plastics 0.3 0.1 1.1 0.1 0.3 1.6 1.5 0.0 0.7 1.1 0.3 0.4 1.2 0.5 0.7 1.1 4.1 neg neg neg neg neg 0.0005 W PIGMENTS Pigments Page 153 Japanese Consumption of Chrome Yellow (thousands of metric tons.3 0.1 0.4 7.1 2.8 1.0 2.1 0.5 7 6.0 2.2 0.8 4. SOURCE: Japanese consumption of molybdate orange is estimated to have been as follows: Japanese Consumption of Molybdate Chrome Orange (thousands of metric tons.9 0.6 3. Totals may not equal the sums of the categories because of rounding. May 2001 575. are used primarily in anticorrosive primers. 217 233 201 196 208 207 197 180 211 202 204 200 Chrome Yellow 554 484 470 491 499 503 486 491 488 486 482 485 Exchange Rate (yen per dollar) 221 239 145 135 127 111 102 94 108. (A) Yearbook of Chemical Industries Statistics. International Monetary Fund (data for EXCHANGE RATE). Zirconium oxide is white pigment used for ceramics. which has been decreasing because of environmental concerns. Domestic consumption of cadmium pigments was only around 20 metric tons. alkali and heat resistance and is used in coatings. b. SOURCE: Zinc chromate pigments. Applications are limited to use in porcelain enameled products. where it is difficult to find a substitution for cadmium pigments. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International . Price Price information on inorganic pigments is presented in the following tables: Japanese Unit Values for Selected Inorganic Color Pigments Yen per Kilogram Iron Oxidea 1981 1985 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a. Totals may not equal the sums of the categories because of rounding. Chrome oxide is excellent in acid. Includes drawing paints and crayons.8 121.9 113.0 130. porcelain enameled products and special inks.7 Average unit value including ferrites and pigments. but also consumed to produce spinel color pigment (complex). also called zinc yellow. (B) International Financial Statistics. Ministry of International Trade and Industry (data for YEN PER KILOGRAM).0005 X PIGMENTS Pigments Page 154 a. CEH estimates based on import data and data from the Japan Inorganic Chemicals Association. 34 10.79 35.49 14.34 1.64 45.57 39.83 13. The market price of iron oxide with poor color quality for anticorrosive coating use is much cheaper than the price listed.04 0.04 0.03 0.96 1.26 26. International Monetary Fund (data for EXCHANGE RATE).19 26.000 Ultramarine Blue 860-980 860-980 Zinc Chromate 550-680 550-680 Exchange Rate (yen per dollar) 109 113.64 38. Trade Import and export data for inorganic pigments are provided in the following table: Japanese Trade in Inorganic Color Pigmentsa (thousands of metric tons) Iron Oxideb Imports 1981 1985 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 5.22 0.39 1. by grade and the amount purchased.56 26.75 1.48 32.25 23.06 0.34 23.81 1.May 2001 575.61 13.39 52.62 1.10 36.29 1.82 40.34 Exports 15.23 0.35 0.29 0.18 0. much cheaper prices are available for large-volume consumers.20 0.23 14.65 51.10 0. (B) International Financial Statistics.04 0.22 0.7 Iron Blue 650-750 650-750 SOURCES: (A) CEH estimates.61 0.04 0.31 1.11 Exports 1. however.46 0.44 0.32 0.77 Chrome Yellow Imports --0.000 700-1.0005 Y PIGMENTS Pigments Page 155 Japanese List Prices for Selected Inorganic Color Pigments (yen per kilogram) Iron Oxide 1996 1999 200-460 200-460 Chrome Yellow 530-570 500-550 Molybdate Chrome Orange 700-1. Market prices for inorganic pigments vary within a broader range.05 0.35 50.01 0.84 21.10 23.04 Molybdate Chrome Orangec Imports --na na na na na na na na na na Exports 0.74 © 2001 by the Chemical Economics Handbook—SRI International .35 1.01 0.32 0. 8 thousand metric tons of iron blue.02 2.62 0.52 3. the United States (10.56 0.7%).32 0.75 1.80 Ultramarine Blue Imports neg 0.20-000 na 2819.60 1.47 0.29 2. Japan imported about 23.70 5.18 0.05 neg neg neg neg neg neg 0.18 0. Japan exported 1 thousand metric tons to Asian countries and Canada.08 0. SOURCE: In 1999.10-00 3206.53 0.67 2.65 3.19 2. data have been reported under the following harmonized trade code numbers: Imports Iron oxide Chrome yellow Molobydate chrome orange Chromium oxide Iron blue Ultramarine blue 2821.34 0.37 0.17 5. while the country exported about 35.74 2.4%) and Germany (19.4%). © 2001 by the Chemical Economics Handbook—SRI International .48 3.10-010 2841.84 2. which is about 76% of its production in 1999.39 2. --2.50 0.90 1. Imports are likely to be primarily pigments by Bayer. Japan Tariff Association.08 5.10-000 2841.May 2001 575.02 0 0 neg Exports 2.01 1. With regard to chrome yellow.15 0.50 2.52 2.29 4.3 thousand metric tons of iron oxide mainly from China (45.20 1.6%).2%) and Italy (23.20-000 3206.8 thousand metric tons mainly to the Republic of Korea (31.17 0.50 0.39 0. Japan exported 86 metric tons of cadmium pigments in 1999.00 2. mainly to the United States (31.9%) and the United States (16. while imports are very small.63 2.35 0.43-000 3206.66 2. whereas most of exports are ferrites/magnetic iron oxide.85 2.25 0. Data represent all iron oxides including ferrites and pigments.6%).24 Exports 0.10-000 3206.20 2.54 2.76 1.0005 Z PIGMENTS Pigments Page 156 Japanese Trade in Inorganic Color Pigmentsa (continued) (thousands of metric tons) Chromium Oxide Imports 1981 1985 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.43-000 3206-41-000 b.17 1.28 Since 1989.21 0.41-010 Exports 2821.20-100 na 2819.39 0. Japan Exports & Imports. mainly to Taiwan and the Republic of Korea.24 0.88 1.18 0. Japan exported 1.66 Iron Blue Imports neg 0.45 Exports 0.48 1. May 2001 575.0006 A PIGMENTS Pigments Page 157 O THER ASIAN COUNTRIES Producing Companies There are a number of producers of inorganic color pigments in Asia: © 2001 by the Chemical Economics Handbook—SRI International . Fu Tai Chemical Industry Co. Ltd. Co..0006 B Taiwan Itai Enterprises Co..Major Asian Producers of Inorganic Color Pigments—2000 Pigments Page 158 Company Korea... Sheng Yu Steel Co. Poo Nan Chemical Industrial Co.. Republic of Iron Oxide (Hematite) (Red 101) Iron Oxide (Magnetite) (Black 11) Iron Oxide (Goethite) (Yellow 42) Chrome Yellow (Yellow 34) Molybdate Chrome Orange (Red 104) Chromium Oxide (Green 17) Zinc Chromate (anticorrosive pigment) Iron Blue (Blue 27) Ultramarine Blue (Blue 29) Other Ukseung Chemical Company Ltd. Ltd. X X X X X May 2001 575. Ltd.. X X .. Ltd. X X X X PIGMENTS Ching Hua Chemical Co. Ltd. Taiwan Colors & Chemicals Co. Ltd. X X X Pearlescent pigments X New Hsin Jung Enterprise Co. Ltd. X X © 2001 by the Chemical Economics Handbook—SRI International Sambo Fine Chemicals Mfg. Ltd. Taiwan China Steel Corp. Goodwill Chemical Corp.. Yih Chen Chemical Industry Co.. May 2001 575.Ltd.0006 C © 2001 by the Chemical Economics Handbook—SRI International Yen Kwang Color Co. India Number of Companies X X X X 15 6 12 4 1 4 SOURCE: CEH estimates based on the Directory of Chemical Producers... Ltd.Major Asian Producers of Inorganic Color Pigments—2000 (continued) Pigments Page 159 Company Taiwan (continued) Iron Oxide (Hematite) (Red 101) Iron Oxide (Magnetite) (Black 11) Iron Oxide (Goethite) (Yellow 42) Chrome Yellow (Yellow 34) Molybdate Chrome Orange (Red 104) Chromium Oxide (Green 17) Zinc Chromate (anticorrosive pigment) Iron Blue (Blue 27) Ultramarine Blue (Blue 29) Other Yieh Loong Enterprise Co. SRI Consulting. Ltd. X X PIGMENTS . (A) Korean Dyestuff and Pigments Industrial Association (Korean production).9 25.5 0.5 Republic of Korea Production Cromium 1997 1998 1999 4. (B) Taiwan Dyestuff and Pigments Industrial Association (Taiwanese production).1 Taiwan Production Chrome Yellow 1997 1998 1999 a.1 Molybdenum na 0. (C) China Chemical Industry Yearbook .9 0.0 na Molybdate 0.7 0. SOURCES: China Producing Companies There are numerous pigment producers in China.4 thousand metric tons of magnetic powder in 1997 and 1998 respectively.1 0.4 Zinc Chrome na 0.0006 D PIGMENTS Pigments Page 160 The table below is the estimation of salient statistics in selected Asian countries (imports/exports are listed in the table at each country section).1 10.8 na Iron Oxidea 95.4 0. Bayer Shanghai Pigment Co.1 0.8 na Ultramarine Blue 1.3 140 Apparent Consumption 27.5 4.7 1.2 40.2 0.4 2.4 Total na 3.7 Apparent Consumption na 8. Salient Statistics of Inorganic Color Pigments in Selected Asian Countries China Production Chromium Yellow 1997 1998 1999 10.4 18.7 5.3 Apparent Consumption 19. Elementis Shenzhen (majority is owned by Elementis Pigments.4 4.5 7.1 0.1 Zinc 0.0 na Red Lead 26. formerly known as Harris & Crosfield) © 2001 by the Chemical Economics Handbook—SRI International . na 1.7 and 0.1 0.9 103.9 136. (majority is owned by Bayer) produces iron oxide pigments at a plant with a 20 thousand metric ton capacity in 1997 for concrete and asphalt applications and exported the pigments to Europe. Japan and other countries.6 na Total 133.3 na Zinc Chrome 0. China National Chemical Information Center (Chinese production).May 2001 575.4 Total 5.6 5.4 0.6 30.0 Ultramarine Blue 0.2 25. (D) CEH estimates.1 3.2 Includes 1.6 Other na 0.3 Iron Oxide na 0. Guandong province in 1998. Chinese Producers of Inorganic Color Pigments—2001 Company Bayer Shanghai Pigment Co. Harbin Paint Plant Harbin Petrochemical Industry Corp. Iron Oxide X X X X X X X X X X X X X X X X X Chrome Yellow Ultramarine The company is a joint venture of Shanghai Coatings Company and Bayer AG. Jinpeng Iron Oxide Co.0006 E PIGMENTS Pigments Page 161 produces iron oxide pigments at a plant with a 20 thousand metric ton capacity at Shenzhen. Xiangtan Chemical & Pharmaceutical Industrial Co. Inc. Ltd. The joint venture started commercial production with an annual capacity of 20 thousand metric tons in the late 1996.. Chinese producers of pigments are listed below. 2000-2001 Directory of Chemical Producers—China. © 2001 by the Chemical Economics Handbook—SRI International . Henan Province Wun County No.a Chongqing Jiangnan Chemical Factory Chongqing Xinhua Chemical Plant Guangdong Lingyang Co. Ltd... 2 Chemical Plant Hunan Three-Ring Pigments Co. Zhenjiang City Plant Factory Zhenjiang General Chemical Factory Zhenjiang General Chemical Industry Corp. a. Production statistics in 1997/1998 may be understated for iron oxides and the total inorganic pigment consumption is roughly estimated as 40 thousand metric tons in 1999. SRI Consulting. Linying County Chemical Plant Ningbo Jinbco Group Co. Ltd. Significant quantities of iron oxide have been exported..May 2001 575. Shandong Longkou Chemical Plant Shenyang Paint General Corporation Shenyang Paint Plant Wenzhou Huasu Group Co. established to produce high-quality iron oxide pigments. Ltd. Yiyang Shangyou Chemical Factory Yunnan Yanglin Chemical Plant Zhengzhou Xinda Chemical Co. SOURCE: Trade Export data for selected inorganic pigments in recent years are shown in the table below. announced the completion of a plant with a 5 thousand metric ton capacity for iron oxide pigments in 2000. at Guandong province. These European joint ventures export significant quantities of iron oxide pigments back to Europe and also export to Japan and other countries. 4 1. 21. both located at Pusan. molybdenum orange and chrome yellow.3 4. SOURCE: Approximately 39% of iron oxide imports came from Japan in 1999. The majority of ultramarine blue pigments originated in the United Kingdom (66%) and Japan (14%) in 1999.May 2001 575.1 Exports 2. (40% owned by Dainichiseika Color & Chemicals Mfg.0 0. their product lines are limited to ultramarine blue.2 0.2 29.0 0. Trade Import and export data for selected inorganic pigments are given in the following table: Republic of Korea Trade in Inorganic Color Pigments (thousands of metric tons) Iron Oxide Imports Exports 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.1 0.2 0.1 Exports 3.0 Exports 1. and Sambo Fine Chemicals Mfg. Ltd.1 na 0.5 1.5 0.7 1.9 41. are leading manufacturers of inorganic color pigments in the Republic of Korea.9 0.8 0.1 Molybdate Chrome Orange Exports Imports Exports na na na neg neg neg neg neg neg neg neg neg neg neg neg 0.1 0.8 0.7 Chrome Yellow Imports 0. General Administration of Customs of the People’s Republic of China Republic of Korea Producing Companies Uk Seung Chemical Company.2 0.1 neg 0.2 0. Iron blue pigments also came mainly from Japan (58%).7 1.1 China’s Customs Statistics..1 na neg neg neg Exports 0.2 0.1 0.5 43.8 3.7 23.7 Red Lead Imports 0.3 0.7 0.4 24.0 1.5 1.1 0.. However.1 neg neg Ultramarine Blue Imports 0. Japan).2 0. Ltd. Ltd.0 Iron Blue Imports 0.3 14.6 0.9 Ultramarine Blue Imports 0.8 0.3 neg neg neg neg neg neg neg neg neg Chrome pigments.0 4.3 136.6 23.1 0.6 0.1 0.0006 F PIGMENTS Pigments Page 162 Chinese Trade in Inorganic Color Pigments (thousands of metric tons) Iron Oxide Imports 1997 1998 1999 SOURCE: 20.9 26.8 1. Statistical Yearbook of Foreign Trade.8 1.1 0.1 0. Co.8 40.1 Exports 1. © 2001 by the Chemical Economics Handbook—SRI International .6 Exports 118.4 1.4 128.6 Chrome Yellow Imports neg neg 0. Korea Customs Research Institute.88a neg neg neg neg neg neg Exports ---neg neg neg neg neg neg Red Lead Imports 0.4 1.3 25.7 3.1 0. Co.6 0.7 4.6 2.2 0.8 Exports neg neg neg neg neg neg 0.9 2.1 neg neg Iron Blue Imports na na 0.1 0.1 0. 1 0. paint.6 0.6 0.5 2. For example.2 0.9 neg neg neg Exports 0.8 3.6 7. Taiwan’s iron oxide imports from Japan decreased from 4.1 0.3 17.1 Molybdate Chrome Orange Exports Imports Exports neg 0.47 thousand metric tons in 1997 to 1.2 9.2 26. they are usually more expensive.1 neg neg neg neg neg neg neg neg neg SOURCE: Monthly Statistics of Imports and Monthly Statistics of Exports .7 0.1 0.6 3.5 0.8 1.6 0.6 0.2 0.5 0. The People’s Republic of China—Taiwan District.4 4.5 0.47 thousand metric tons in 1997 to 2.8 2. certain plastic and other applications.0 0.0 0.5 0.6 0. However.1 0.6 0.May 2001 575. Trade Import and export data for selected inorganic pigments are given in the following table: Taiwanese Trade in Inorganic Color Pigments (thousands of metric tons) Iron Oxide Imports Exports 1991 1992 1993 1994 1995 1996 1997 1998 1999 27.7 0.8 8.. their aesthetic and performance properties have firmly established them in printing ink.2 0.1 1. imports from China increased from 1.1 0.1 0. Ministry of Finance.1 2. ORGANIC COLOR PIGMENTS DESCRIPTION Organic color pigments can provide certain advantages over inorganic pigments.4 0. They generally possess greater brightness and tinctorial strength and can serve as replacements for inorganic pigments.7 10.3 0.2 0.2 Exports 18.8 20.8 2. Statistical Department.6 21.3 1.3 0. On the other hand.1 0.1 0.1 neg neg neg neg neg neg 0.8 0.0006 G PIGMENTS Pigments Page 163 Taiwan Producing Companies Bayer Taiwan Co.9 17. they are subject to bleeding in some solvents and degradation after prolonged exposure to light or high temperatures.1 neg neg neg neg 0.2 1.9 0.0 0.3 0.3 0.4 0. is believed to be one of the leading players in iron oxide pigments.94 thousand metric tons in 1999 (25% of total iron oxide imports).6 0.1 0. Directorate General of Customs. © 2001 by the Chemical Economics Handbook—SRI International . Ltd.0 1.5 1. in contrast with the more opaque inorganic pigments. Ultramarine pigment imports were mainly from the United Kingdom (58%). organic pigments are limited in ways that inorganic pigments are not. However.0 Chrome Yellow Imports 0.4 2.0 Ultramarine Blue Imports 0. They are usually transparent or semitransparent.2 Red Lead Imports 0.4 0.1 Exports neg neg neg neg neg neg neg neg neg Iron Blue Imports 0.07 thousand metric tons in 1999 (27%).7 1.4 3.4 5. and imports pigments from China and Germany to supply the Taiwanese market.5 7.1 0. In addition. with more than one. are consumed as dispersions or presscakes (see the MANUFACTURING PROCESSES section for further description). Diarylides show good chemical resistance to both acid and alkali environments and generally also have good heat resistance. q q Essentially all organic color pigment production is synthetic. Dinitraniline orange (PO-5) is a monoazo pigment giving a bright orange shade. excellent dispersibility and good full-strength © 2001 by the Chemical Economics Handbook—SRI International . thus. Arylides are characterized by intense color. offers the maximum possible tinting strength for its type. Diarylide yellows and oranges include PY-12. but have poor bleed resistance and are sensitive to heat. but relatively poor in tints. It can be applied as a colorant free of any inorganic carrier and. 17 and 83 and PO-16. The first component of a diarylide is 3. their lightfastness in tints is even poorer than that of the arylides. Overall. q A toner is a pure organic pigment that is insoluble in and unaffected by. depending upon the functional groups substituted on either the benzidine or arylide portion of the molecule. AZO PIGMENTS Azo pigments are either monoazo. 3. produced from the coupling of beta-naphthol with 2.3′-dichlorobenzidine. A lake is an organic colorant that has been combined with an inorganic substrate (such as light alumina hydrate) to produce an insoluble pigment. as in the arylide yellows and oranges.4-dinitroaniline. 65. The major chemical classifications of commercial organic pigments are q q q q q Azo Phthalocyanine Condensation acid Quinacridone Perylene The following sections include descriptions of each of these major chemical types. with one chromophore (–NN–) group or disazo. azo pigments are the pigment of choice in many ink.0006 H PIGMENTS Pigments Page 164 Organic color pigments are classified into two categories—toners and lakes. 14. However. a diaminobiphenyl compound that reacts with two molecules of the second component to yield the diazo pigment. The second component is an arylide. As a class. which is an arylide of acetoacetic acid. having good chemical resistance. It is a low-cost pigment. Arylide (Hansa) yellows and oranges include PY-1. coating and plastics applications. most organic pigments. both toners and lakes. They are monoazo pigments. PY-12 was the largest-volume organic color pigment produced in the United States in 1999. Lightfastness is good in deep shades.May 2001 575. semiopacity and high tinting strength. 13. the vehicle or substrate in which it is incorporated (see the definition of a pigment in the INTRODUCTION of this report). of clean color and good to excellent hiding power. their nomenclature is derived from the second component of their structure. Shades range from deep reddish orange to pale greenish yellow. Bleed resistance varies from low to high. 73 and 74. Diarylide yellow and orange pigments exhibit intense color in shades from deep redorange to green-yellow and possess even greater tinctorial strength than the arylides. They show good resistance to chemicals. However. They are also used in automotive and other industrial finishes. excellent color and good bleed. 23. 185 and 208. Pyrazolone pigments are distinguished by high intensity. 9. but not in organic solvents. Although they are less expensive than quinacridones and perylenes. However. Toluidine red (PR-3) is a monoazo pigment with a second component of beta-naphthol. PV-32. 185 and 208 and PV-32) offer good brightness. as in the diarylide yellows. Available colors range from dull reddish brown (PBn-23) through bluish red (PR-144). By using a variety of components it is possible to obtain a wide range of colors in the resulting pigments. © 2001 by the Chemical Economics Handbook—SRI International . PR-3 is bleedresistant in water but not in organic solvents.May 2001 575. good hiding power and excellent chemical resistance. Toluidine reds are characterized as light. Their outstanding features are good durability and a high degree of chemical resistance. 154. and superior stability and processing capabilities. 156 and 175. PR-112. They are moderately high in price. medium and deep and include a range of yellowish red to red shades. 17. which are semiopaque. PY-93. Their cyclic carbonamide structure makes this group of pigments much more heat-resistant and light-fast than other less expensive monoazo pigments. lightfastness in tints is poor. PR-171. The red-orange. yellow and yellow-green pigments are rather dull in color. and PBn-23) are essentially made up of diazotized aromatic amines and 2-hydroxy-3-naphthoic acid (BON acid). They are all transparent except for the yellows. The second component is a derivative of pyrazolin-5-one. 60 and 62. their growth in U. has excellent lightfastness but no resistance to bleeding in certain solvents. ranging from light yellowish red to deep maroon. 7. which has good lightfastness and excellent bleed resistance in exterior conditions. orange (PR-166 and PO-31) and yellow (PY-95) to bright greenish yellow (PY-93 and 128). 5. It resists bleeding in water. They outperform the diarylide yellows and soluble azo reds in plastics and pigmented fiber applications.0006 I PIGMENTS Pigments Page 165 lightfastness. PR-144 and 166. PR-144 and PY-93 are particularly useful in pigmented fiber applications. but have become very useful in the coloring of polyvinyl chloride and other plastics because of their resistance to high heat and because they do not react with the chemicals used in plastics manufacture. Benzimidazolones are monoazo pigments that are variations on the basic benzimidazolone structure. condensed with aromatic diamines. It possesses good brightness and tinting strength. 95 and 128. with the exception of PR-170. Naphthol reds and browns include PR-2. chemicals and solvents. They are named for their second component. Their lightfastness is good for interior paint applications. Although they are expensive. Naphthol pigments are used in formulating water-based inks. bake and chemical resistance. Pyrazolone red (PR-38) and bright orange-red (PO-13 and 34) are disazo pigments whose first component is a dichlorobenzidine derivative. They include PBn-25. In general. which is an arylamide of 3-hydroxy-2-naphthoic acid. which is less commercially important than PR-170. 22. but the red to red-violet shades (PR-176. 112 and 170 and PBn-1. these pigments are more expensive than the diarylides and have low hiding power and poor lightfastness in tint formulations. highperformance coatings has been limited due to the higher-quality coatings obtained with quinacridones and perylenes.S. lacquers and certain inks. heat. 176. Disazo condensation pigments (including PO-31. excellent resistance to light. 31. but marginal for exterior use. PO-36. 151. and PY-120. There are also some other recently developed naphthol reds that show greatly improved lightfastness properties. They have been used in plastics and coatings as replacements for toxic lead-containing inorganic pigments. However. brown. they offer excellent color intensity and tinting strength. 175. they tend to bleed in certain solvents. These high-molecular-weight products were developed in order to obtain colorants with improved physical properties compared with other azo pigments. their high color strength keeps their overall cost at a more economical level. It has excellent brightness and tinting strength and fair heat resistance. it is limited by inferior acid. the calcium and manganese salts are bluer in tone. which is synthesized from phthalonitrile or from phthalic anhydride and urea. Alkali and soap resistance of Lithol® rubine and red 2G are poor and heat resistance is only fair. alkali and soap resistance and must be specially treated to reduce water solubility. The barium salt is bright yellowish red. Lithol® rubine has a first component of 4-aminotoluene-3-sulfonic acid and the first component of red 2G is 2-amino-5-chloro-p-toluenesulfonic acid. while calcium salt is growing. excellent dispersibility and relatively low price. calcium (PR-49:2) and strontium (PR-49:3). It is prepared as the barium salt of the coupling of anthranilic acid and 2-naphthol-3. All the salts have excellent bleed resistance. although the high tinting strength of these pigments makes them economical in terms of © 2001 by the Chemical Economics Handbook—SRI International . makes it a stable. This pigment is available in four salts: barium (PR-48:1). strontium is the darkest. The calcium salts of both pigments provide a clean.May 2001 575. Its color is bright yellowish red. The sodium salt is the lightest shade.6-sulfonic acid. symmetrical structure. Lithol® rubine is available as a calcium salt (PR-57:1) and red 2G is produced as either a calcium (PR-52:1) or manganese (PR-52:2) salt. fair to good heat resistance and lightfastness. In general. lightfastness. Permanent red 2B (PR-48) is prepared by coupling 6-amino-4-chloro-m-toluenesulfonic acid with BON acid. as is lightfastness in the full-strength forms. Red 52:2 can be blended with molybdate orange for use in industrial coatings. Weaknesses include poor hiding power and lightfastness and poor alkali and soap resistance. heat stability. chemical and bleed resistance. barium. fairly good bleed resistance. Lithol® red (PR-49) is produced by the coupling of 2-naphthylamine-1-sulfonic acid and 2-naphthol. In 1995. Lithol® rubine calcium salt (PR-57:1) was the third-largest volume organic pigment produced in the United States. particularly in gravure printing. Lithol® rubine (PR-57) and red 2G (PR-52) are both prepared by coupling with a second component of BON acid. calcium (PR-48:2). barium (PR-49:1). It is commercially produced in the form of four different salts: sodium (PR-49). Shades of increasingly darker red are manufactured by preparing metal salts of sodium. solvent bleed resistance is good. make it competitive with other red pigments for many applications. The latter product was the fifth-largest organic color pigment manufactured in the United States in 1995. but poor alkali and soap resistance. full of conjugated double-bonds. all the phthalocyanine pigments exhibit excellent transparency. Phthalo prices are generally moderate to high. Lithol® red’s advantages include good color intensity and tinting strength. combined with its moderate price. however. Its clear. bright red tone.0006 J PIGMENTS Pigments Page 166 Red lake C (PR-53) is prepared from 2-amino-5-chloro-p-toluenesulfonic acid and beta-naphthol. strontium (PR-48:3) and manganese (PR-48:4). The barium salt production and use is declining. calcium and strontium. However. Its large. Its drawbacks are poor chemical and bake resistance and no lightfastness. intense bluish-red color that is popular in printing ink formulations. PHTHALOCYANINE PIGMENTS Phthalocyanine blue and green pigments (including PB-15 and 16 and PG-7 and 36) are based on the phthalocyanine chromophore. good lightfastness and high bake and bleed resistance. intensely color compound that is the basis for what has become the leading group of colorants in several applications. Scarlet 3B lake (PR-60) is a monoazo lake pigment that is precipitated onto an alumina hydrate substrate. processing capabilities and durability. The resulting soluble material is precipitated with either sodium salt or barium salt to form PR-53 (sodium salt) or PR-53:1 (barium salt). They have less bronzing tendency than the alphas. Phthalocyanine blue. inks and textiles. This pigment has the reddest blue shade of all phthalocyanine pigments. Combined with carbon black. imports. is available in two crystalline modifications: the alpha form PB-15. is also increasing at a substantial rate. good dispersibility and fair heat resistance.May 2001 575. Their lightfastness is better than that of basic dye pigments but not as good as the phthalocyanine blues. mainly by BASF Corp. The alpha form often converts to the beta form in strong solvents and at high temperatures and also has a tendency toward flocculation. However. Thus. In this report. but are equal to them in their other physical properties. Phthalo blues are the “workhorse” blue pigment in every major end-use market for organic pigments. its metal-free characteristic is its sole selling point over other less expensive phthalos. PB-19 and 61 will be treated as a combined pigment and referred to as alkali blue. The beta form is already stable and noncrystallizing. The two most important pigments in this family are the alkali blues. but is growing very quickly as a specialty pigment in certain copier systems requiring metal-free color receptors. since in practice they are for the most part used interchangeably. They are suitable for use in inks. PB-16 is supplied only through U. PB-15:3 was the largest-volume organic color pigment produced in the United States in 1999. The resulting pigment is much greener than the copper modifications. One of the newer phthalocyanine pigments is PB-15:6. the yellower the color). alone or as a toner for carbon black pigments. which is the epsilon modification of copper phthalocyanine. Phthalo greens are used in coatings. copper phthalo blues are experiencing high growth rates. Consumption of PB-15:2. which is a red shade. CONDENSATION ACID PIGMENTS These pigments are acidic salts produced from dyes and are like basic dye pigments in that they contain the triphenylmethane group (or a closely related structure) for a chromophore (see discussion under OTHER ORGANIC PIGMENTS and in the MANUFACTURING PROCESSES section for further description of basic dye pigments). Alkali blue pigments are prepared by sulfonating a phenylated derivative of rosaniline. Because of their replacement of iron blue in publication gravure ink applications. Phthalocyanine green pigments (PG-7 and 36) are modifications of the copper phthalo blues. with fair to good bleed and chemical resistance. PB-15. metal-free (PB-16) is a version of the phthalocyanine molecule in which the central copper atom has been replaced with two hydrogens. plastics. with the replacement of hydrogen atoms on the molecule by chlorine atoms (PG-7) or by chlorine and bromine atoms (PG-36). which is more stable and greener in tone. The physical characteristics of these pigments are like the phthalo blues except that the greens are not subject to crystallization. They are transparent. Copper phthalocyanine blue. It is consumed in small quantities. The presence of up to fifteen chlorine atoms produces the green shade of PG-7 and the presence of two to ten chlorine atoms and four to nine bromine atoms yields the yellow-green shades of PG-36 (the more bromine.0006 K PIGMENTS Pigments Page 167 coloring value. Alkali blues are bright blue to greenish blue in color and exhibit the highest tinctorial strength of any blue pigment. because of its growth in plastics and automotive coatings applications. which is reddish blue and the beta form PB-15:3 and 15:4. the two possible beta forms are PB-15:3 (NC) and PB-15:4 (NCNF). because of toxic-metal concerns. It can be modified (by special surface treatments or by the addition of chlorine to the phthalocyanine molecule) to be noncrystallizing (NC) or nonflocculating (NF). 15:1 and 15:2. but it can be treated to be nonflocculating. The betas are greener and less intense. The product is an acidic internal salt that is insoluble in water. The metal-free pigment is available in solvent-unstable (alpha) and solvent-stable (beta) crystalline forms. PB-19 and 61.S. they increase the opacity and © 2001 by the Chemical Economics Handbook—SRI International . methyl violet is the most commercially significant. 179.0006 L PIGMENTS Pigments Page 168 covering ability of ink. 178. Though expensive. 206. although it is very expensive. brightness and tinctorial strength. The basic chromophore structure of the quinacridones is very symmetrical and stable. with PR-123. They are anthraquinone pigments. The U.4. 207 and 209. They provide excellent chemical. PERYLENE PIGMENTS Perylene reds include PR-123. a related structure. Q UINACRIDONE PIGMENTS Quinacridone pigments (PV-19 and 42. PR-122. supply of perylenes is dominated by Bayer. were introduced to the automotive market in 1986. despite their very high cost.S. Carbazole violet exhibits an exceptionally bright. 149 and 178 offering brighter colors than the comparatively dull tints PR-179. chemical and bleed resistance and good lightfastness. They are available in several transparent and semitransparent shades.May 2001 575. 190 and 224. 202 and 206) to violet (PV-19 and 42). of excellent heat. heat stability and chemical and bleed resistance make them suitable for many highperformance applications including quality paints. Today.10-tetracarboxylic diimides. as well as excellent physical properties. Colors range from deep yellowish orange (PO-48 and 49) through bright yellowish red (PR-207 and 209) through bluish red and maroon (PR-122. Carbazole violet is almost always used with other pigments. 149. although PR-149 is not light-resistant enough for exterior use. it has poor durability and bleeds in many media. they have an important role in the market for high-performance specialty pigments and find considerable use in exterior automotive coatings. The other quinacridone pigments have substituents. with the balance coming mainly from BASF. which is Pigment Violet 19. transparency and tinting strength. These pigments exhibit excellent color. O THER O RGANIC PIGMENTS Basic dye pigments contain the chromophore triphenylmethane or a similar structure. their superior aesthetics and mostly excellent physical properties make them the pigments of choice in specialty ink applications. Their lightfastness. Of these. Although they are costly. derivatives of perylene-3. such as methyl groups and chlorines attached to the quinacridone ring. strong blue-violet color. bleed and bake resistance and generally superior lightfastness. 202. two pigments are manufactured.9. or are combinations of the basic quinacridone with quinacridonequinone. Both quinacridones and perylenes (see description below) are used in conjunction with metals to produce metallic finishes. Diketo-pyrrolo-pyrrole (DPP) pigments. mostly for pearlescent automotive coatings where it provides a blue color with a red shade (or tint) to the final finish. inks and plastics. They are used mainly in automotive coatings. Carbazole violet (PV-23) is made from aminoethylcarbazole and chloranil to produce the conjugated double-bonded ring structure of the dioxazine pigment. the main pigment is PR-254 and of © 2001 by the Chemical Economics Handbook—SRI International . but as indicated by the term fugitive. Thus. these pigments possess superior color. and PO-48 and 49) are all variations on the basic quinacridone structure. discovered by Ciba-Geigy AG. Fugitive methyl violet (PV-3:3) is exceptionally bright and beautifully colored. 190 and 224. Permanent basic dye pigments include rhodamine red and violet (PR-81 and PV-1) and methyl and ethyl violets (PV-3 and PB-14). for both topcoats and refinishes and secondly in plastics. The high tinting strength and low cost of alkali blue pigments make them the most economical of the blue pigments for certain applications. particularly the bright red colors. where their shades are needed to match colors. their high degree of heat and bleed resistance is sufficient for use in most plastics and fibers and their lightfastness and chemical resistance make them useful in automotive paints and other highperformance coatings. as is done for ink and coating applications. Pigment dispersion involves thorough mixing of the dried and ground pigment with another material. Alizarine red and maroon (PR-83 and PV-5:1) are both anthraquinone pigments of very small usage. In 1992. The first component. including its physical form. However. and (2) flushing. both presscake and dry powder may undergo various treatments to further tailor the pigment’s characteristics to meet user needs. grinding and possibly dispersing. Sodium nitrite is added. The finishing step enhances and stabilizes the desired pigment characteristics. fluorescent organic pigments are discussed only briefly in this report and are not included in the data. the solid solution pigment of quinacridone and DPP entered the plastics market. Tetrachloroisoindolinones (PY-109 and 110.. Resins are based on formaldehyde. the following steps are taken in the production of azo pigments. fluorescent plastics and some inks.0006 M PIGMENTS Pigments Page 169 minor importance is PR-255. PO-42 and 61 and PR-180) are made by joining two 4. DPP pigments possess excellent coloristic properties and are used primarily in the demanding automotive market. In this case. MANUFACTURING PROCESSES Organic pigments are typically produced in two steps: the chemical synthesis of the pigment and its finishing or conditioning. the pigment is normally filtered and washed to remove impurities. a primary aromatic amine (or a diamine. which can be anything from greenish yellow to bright red. They are used for apparel/textile printing. the oil base that is used is specific to the intended use. tinting strength.7tetrachloroisoindolinone residues to a diamine. at which point it is usually referred to as the presscake. most producers sell water-wet presscake or dry color/powder. in the case of diazo pigments). Alizarine red is a bright bluish-red shade and alizarine maroon is reddish-violet. AZO PIGMENTS There are many types of azo pigments derived from a number of different starting materials and a variety of methods for manufacturing them. is dissolved or suspended in an acidic solution. Data on fluorescent brighteners are included in the CEH marketing research report on Dyes. As part of their organic pigment product line. When synthesis and finishing are complete. The nature of the diamine determines the color of the resulting pigment. In general. polyester or nylon. which forms nitrous acid in the solution and © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575. to obtain specific properties. DPP pigments are reportedly synthesized by reacting a succinic ester with a benzonitrile in the presence of sodium methylate in methanol. stability and ease of processing.5. which is presscake that has been dried and pulverized. Flushes are produced when the water content of a presscake is replaced or flushed away. This class of pigments is characterized by excellent brightness. Fluorescent organic pigments consist of various dyestuffs (e.g.6. For this reason. by an oil-based liquid. which is most often liquid. rhodamines) that have been placed on a resin matrix and are not considered lakes. Although they are very costly. Finishing of presscakes for printing ink and similar applications involves two major procedures: (1) drying. amine or methylene group. orthonitraniline and dinitraniline oranges. an arylide or arylamide of acetoacetic acid or a pyrazolone derivative. After the coupling process is complete. In one process. phthalic anhydride is combined with urea. If the pigment is soluble. the product is filtered and either washed and dried or prepared as a flush color. a copper salt (usually copper-I chloride. parachlor red and chlorinated para red. as follows: O C 4 C O O + 4 H2N O C NH2 + Cu 2+ + 2e – catalyst N C N C N C N • • • Cu • • • N C C N C N C + 8 H 2O + 4 CO2 C N © 2001 by the Chemical Economics Handbook—SRI International . naphthol. The temperature is usually held below room temperature during this step of the manufacturing procedure. brightness and such properties as dispersibility and flow of the final product. Soluble azos contain anionic groups. but copper-II chloride may also be used) and a catalyst.May 2001 575. the pH and temperature of the reaction solution. toluidine red. which is a phenol. Production factors affecting the intensity. These factors all affect the ultimate size. it will precipitate from the solution. which in turn influence color. para red. the addition of a metal salt is required to precipitate the toner. if the pigment is insoluble. examples include Lithol® red and Lithol® rubine. The unisolated diazonium salt can then be coupled under basic conditions with the second component. diarylide yellows. PHTHALOCYANINE PIGMENTS There is more than one commonly used method of preparing phthalocyanine pigments. the mixing efficiency and the drying method and temperature. the concentrations of the reactants. 3-hydroxy-2-naphthoic acid.0006 N PIGMENTS Pigments Page 170 diazotizes the amine. pyrazolone oranges and reds. such as sulfonic or carboxylic acid. Examples of this type are arylide (Hansa) yellows and oranges. Typical examples of the second component are 2-naphthol. permanent red 2B and scarlet 3B lake. shape and surface area of the pigment particles. aromatic. naphthol reds and browns. red lake C. Finally. red 2G. shade and physical properties of the finished pigment include the method and rate of coupling. to either the alpha or the beta form pigment. requiring an organic solvent or heating. After the halogenation step is completed. no washing is needed after completion. To obtain the alpha forms PB-15 and 15:1. Different methods of finishing are applied. such as a noncrystallizing or nonflocculating pigment. Other surface treatments can be applied at this point. the phthalocyanine base is dissolved in a strong chlorinated solvent (such as chlorosulfonic acid. This is followed by treatment with dilute acid to remove the metal ion. but is more commonly obtained from the salt-ground monochlor. The product may then be acid pasted or ground to produce the finished pigment. as follows: N CN C 2+ C N • • • Cu • • • N C C N C N C 4 CN + Cu + 2e– C N N C N The reaction conditions are the same as for the first method. In the synthesis of phthalo green (PG-7). PB-15:2 can be obtained from the acid-paste method. depending on the pigment form ultimately desired. Then the product is washed with hot water or hot dilute acid to remove any urea by-products formed during the reaction. © 2001 by the Chemical Economics Handbook—SRI International . sulfonyl chloride or aluminum chloride–sodium chloride eutectic mixture) to replace from thirteen to fifteen hydrogens with chlorines on each molecule. The beta form (PB-15:3. the solvent-pigment mixture is poured into water to separate the pigment from the solvent.May 2001 575. Acid pasting is then used to obtain the finished pigment. calcium or magnesium salt. However. A second method uses phthalonitrile and a copper salt for starting materials. with four to nine bromines and two to ten chlorines. Usually eleven to fourteen hydrogens are replaced. The metal-free pigment (PB-16) is usually made by following the phthalonitrile method to produce not a copper salt but a sodium. the base product is acid-pasted (mixed with concentrated sulfuric acid followed by rapid dilution with water). The reactants can be dissolved in an organic solvent or heated to 180-200°C to complete the reaction. to yield a product of upgraded physical properties. followed by application of chlorinated solvent to attach chlorines on some of the remaining sites. PG-36 is made by first applying brominated solvent until a desired number of bromines have been substituted for hydrogen.0006 O PIGMENTS Pigments Page 171 The catalyst may be a molybdate or molybdic acid derivative. 15:4) is made by grinding the phthalocyanine base in the presence of a polar solvent. The product of both of the above methods is not a finished pigment but is the basic blue copper phthalocyanine structure. © 2001 by the Chemical Economics Handbook—SRI International .May 2001 575.5-diarylamino terephthalic acid or one of its derivatives: H N COOH H N O C HOOC H N polyphosphoric acid C O N H quinacridone 2.5–di(phenylamino) terephthalic acid q Oxidation of a dihydroquinacridone: H N H H O C [O] H N O C C O H H N H C O N H dihydroquinacridone quinacridone q Reduction of quinacridonequinone: H N O C O C [H] C O C O N H C O N H H N O C quinacridonequinone quinacridone The crude product from each of these reactions is subjected to acid pasting or salt or solvent grinding to recrystallize the quinacridone. The final step in the manufacture is to apply various finishing techniques to optimize the pigment’s physical properties.0006 P PIGMENTS Pigments Page 172 Q UINACRIDONE PIGMENTS Quinacridone pigments are usually prepared by one of the following methods: q Cyclization of 2. May 2001 575.0006 Q PIGMENTS Pigments Page 173 BASIC DYE PIGMENTS Basic dye pigments are manufactured with great care to maximize brightness, color and physical properties. They are the most customized of the organic pigments. The production process begins with the dissolution of the dyestuff in mineral acid solution (usually hydrochloric or sulfuric acid). Meanwhile, the precipitating substance is prepared in a separate vessel. If a permanent pigment is desired, the precipitant is a complex inorganic acid, such as phosphomolybdic acid (PMA) or phosphotungstic acid (PTA). For a fugitive pigment, tannic acid is the most commonly used precipitant. After both the dye solution and the precipitant are prepared, they are mixed together at a controlled temperature. The precipitation proceeds rapidly and, in the case of tannic acid, is finished with tartar emetic to improve the color intensity of the finished toner. Further specialized treatments may be applied at this point to upgrade the particle uniformity and surface properties. Finally, the product is filter pressed, washed to remove soluble salts and either dried and ground or prepared as a flush color. SUPPLY AND DEMAND BY REGION UNITED STATES Producing Companies The following table lists U.S. producers of organic color pigments: U.S. Producers of Organic Color Pigments—March 2001a Azob Company and Plant Location Apollo Colors Rockdale, IL Allegheny Chemical Corp., subsidiary Ridgway, PA BASF Corporation Coatings and Colorants Division Huntington, WV Bayer Corporation Coatings and Colorants Division Bushy Park, SC CDR Cincinnati, OH Elizabethtown, KY Holland, MI Ciba Specialty Chemicals Corporation Colors Division Newport, DE Clariant Corporation Coventry, RI X X X X X X X X Red Yellow Phthalocyanin Blue Green Condensation Acid Other X X X X X X X Xc X X X X X © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0006 R PIGMENTS Pigments Page 174 U.S. Producers of Organic Color Pigments—March 2001a (continued) Azob Company and Plant Location Daicolor-Pope, Inc. Paterson, NJ Engelhard Corporation Specialty Pigments and Additives Louisville, KY European Colour Inc. Fall River, MA Galaxie Chemical Corp. Paterson, NJ BFGoodrich Performance Materials Cincinnati, OH Newark, NJ Industrial Color Inc. Joliet, IL Keystone Color Works, Inc. York, PA C. Lever Co. Inc. Philadelphia, PA Magruder Color Company, Inc. Elizabeth, NJ Indol Division Carteret, NJ Max Marx Color Corp. Irvington, NJ Nichem Corp. Chicago, IL Sun Chemical Corporation Pigments Division Cincinnati, OH Muskegon, MI Newark, NJ Rosebank, NY a. Red Yellow Phthalocyanin Blue Green Condensation Acid Other X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X An “X” indicates pigments produced in commercial quantities. Includes production for captive consumption. Excludes U.S. pigment producers whose only pigment products are organic food, drug and cosmetic (FD&C) lakes and fluorescent organic pigments (both of which are made from dyes), that are not primary producers of organic pigments. (See the CEH product review on Dyes for further information.) © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0006 S b. c. PIGMENTS Pigments Page 175 Red, yellow, blue and green designations are based on Colour Index names of the organic pigments. Include perylenes, quinacridones, carbazoles and isoindolins. CEH estimates. SOURCE: Since 1997, the following changes have occurred among U.S. organic color pigment producers: q In 1997, CDR closed its Ridgway, Pennsylvania organic pigments plant. In 1997 Hoechst merged with Clariant Corporation. In 1997, Ciba Specialty Chemicals completed the construction of a new facility to produce chromophtal diketo-pyrrolo-pyrrole (DPP) orange TRP transparent pigments in Newport, Delaware. Alex Color phased out organic pigment production. In 1999 Cookson closed its organic pigments plant in Newark, New Jersey. In November 2000, Ulich Color was purchased by Magruder Color Company Inc. In November 2000, Allegheny Chemical Corp. was purchased by Apollo Colors. In March 1998, the Freedom Chemical Company, (formerly Hilton Davis Company) was acquired by the BFGoodrich Company. The business was integrated into existing BFGoodrich specialty additives businesses. In late 2000, the pigments business along with the performance materials segment was subsequently acquired by a private investment group consisting of AEA Investors Inc., DLJ Merchant Banking Partners and DB Capital Partners. BFGoodrich Performance Materials is now a privately-owned, independent company. q q q q q q q During the past ten years, the organic pigments market has grown in volume terms, concurrent with industry consolidation, including plant closures and company mergers. Large-volume, lower-value organic pigment capacities were reduced with the closure of CDR’s Ridgway, Pennsylvania pigments plant in early 1997. BASF continued its retreat from U.S. production by selling its Holland, Michigan organic pigment plant to CDR, leaving BASF with only one U.S. organic pigment production site producing only alkali blue organic pigments. Hoechst Celanese merged its pigment business with Clariant Corporation in mid-1997. The largest U.S. producers/suppliers of organic color pigments as of 2000 are summarized in the following table: © 2001 by the Chemical Economics Handbook—SRI International May 2001 575.0006 T PIGMENTS Pigments Page 176 Market Positions of U.S. Producers/Suppliers of Organic Color Pigments—2000a U.S. Organic Pigments Sales Ranking 1 2 3 4 5 6 7 8 a. b. Sun Chemical Corporation CDR Ciba Specialty Chemicals Clariant Corporation BASF Corporation Bayer Corporation Magruder Color Company, Inc. Apollo Colors U.S. Organic Pigments Sales Revenueb (millions of dollars) 325-350 150-175 125-150 100-125 75-100 75-100 50-75 50-75 Pigment Markets Served (decending order) Ink Ink Paints and coatings/plastics/ink Paints and coatings/ink/plastics Paints and coatings/ink Paints and coatings/plastics Ink/plastics/paints and coatings Ink Excludes companies that do not produce organic pigments in the United States (e.g., distributors). Includes domestically produced and imported organic pigments. CEH estimates. SOURCE: Five of the top eight U.S. organic pigment producer/suppliers have non-U.S. ownership: four were Western European–Ciba, Clariant, Bayer and BASF—and one was Japanese, Sun Chemical. Unlike their domestically owned counterparts, U.S. producer/suppliers with foreign ownership have enjoyed both the ability to supply their U.S. pigment operations with production from overseas plants and the potentially larger pool of resources for the research and development of new products. Sun Chemical’s major organic pigment business is in inks, where it is the leading U.S. supplier of domestically produced pigments. Its line ranges from high-volume, low-value organic pigments to highperformance, high-value pigments, including quinacridones and perylenes. Roughly 40-45% of Sun Chemical’s total organic pigment sales in terms of final dollar value is in flushes, where it is again the leading U.S. supplier. Quinacridones account for 10-20% of sales and over 20% of domestic production is exported. Carbazol violet accounts for 5-10% of U.S. sales. Exports by Sun Chemical consist largely of azos and phthalocyanines. Sun is the second-largest U.S. supplier of quinacridone PV-19. CDR is the largest domestically owned U.S. supplier of organic pigments to the U.S. ink industry. CDR’s acquisition of BASF’s Holland, Michigan organic pigment plant in 1996 gave CDR a more efficient plant and significantly increased its ink market share. CDR’s pigment line includes yellows PY-12, PY-14; reds PR-57:1, PR-49:1, PR-53:1, PR-48:1; green PG-7 and blue PB-15:3. Ciba Specialty is the industry leader in technology advancement and research. It produces only quinacridones in the United States, holding the largest domestic market share of these pigments. It is characterized as a supplier of low-volume, high-value products within the organic pigments range. Exports constitute a sizable portion of its U.S. sales and it supplements its U.S. product line with imported azo, phthalocyanine and DPP pigments from its United Kingdom and Swiss operations. Clariant Corporation completed its pigments business merger with Hoechst in July 1997. This merger further concentrated European organic pigment operations but had little impact on U.S.-based pigment capacity. Clariant’s U.S. organic pigment sales are primarily to coatings manufacturers. In addition, Clariant is the largest U.S. supplier of organic pigments used in general, industrial and trade sales paints and is an important supplier of benzimidazolones. Over 40% of Clariant’s U.S. organic pigment sales are derived from imports. © 2001 by the Chemical Economics Handbook—SRI International organic pigments market segment is high performance pigments for coatings. Bayer’s second-largest organic pigments market segment is plastics. BASF’s alkali blue is made at the Huntington. automobile industry.S.S. phthalocyanines and quinacridones as well as specialty yellows. organic pigment sales. these constitute 70-80% of its total U. exports also account for a significant share.S. holding roughly 75% of the U. In sales value. particularly automotive finishes. organic pigment producer and the fourthlargest flush color manufacturer for the ink market in the United States.S. market. BASF is the second-largest U.e. A significant quantity of its organic pigment sales are from flushes made from purchased pigments. perylene supply. PR-178 and 179 (all of which are imported). BASF’s most important individual organic pigments are its phthalocyanines. Bayer supplies low-volume. high-value organic pigments. Imports by BASF account for the majority its total value of U. Magruder Color is the second-largest domestically owned U. flushes and dispersions) represent up to 30% of its total organic pigment sales.S. Value-added organic pigment products (i. gave it an additional production site and provided the ability to supply dry phthalocyanine pigments to plastics and coatings market segments as well as increase its coverage of the ink market segment. followed by its perylenes.S. Its PR-178 is used largely in the U..S. supplier of organic pigments. Bayer is the largest perylene producer and has the largest share of U. Magruder’s November 2000 purchase of Uhlich Color gave it a broader customer list as well as additional pigment production technology. Like Ciba. organic pigment sales. Apollo’s November 2000 purchase of Allegheny Chemical Corp. Apollo’s product line includes red and yellow azos and phthalocyanine blue and green.S. West Virginia plant. Magruder’s major business is organic pigments for inks. its specialty is flush colors for inks.May 2001 575. All of Bayer’s perylenes are domestically produced and significant amounts are exported. particularly perylenes.S. specialty pigment dispersions from purchased pigments and phthalocyanine pigment press cakes.0006 U PIGMENTS Pigments Page 177 BASF is the world’s largest producer of alkali blue and is the largest U. supplier of perylenes. Producing companies and plant locations for the ten organic color pigments of largest production volume in the United States are listed in the following table (pigments are generally listed from highest to lowest production volume): © 2001 by the Chemical Economics Handbook—SRI International . Bayer’s largest U.S. Apollo Colors is the third-largest domestically owned U. supplier of that pigment. KY Holland. Lake C. Producers of Largest-Volume Organic Color Pigments—March 2001 Diarylide Yellow AAA (PY-12) Phthalocyanine Blue (beta) (PB-15:3) Lithol ® Rubine. Paterson. MI Ciba Specialty Chemicals Corporation Colors Division Newport.S. OH Elizabethtown. NJ Engelhard Corporation Specialty Pigments and Additives Louisville. Ridgway.0006 V X X X X X X X X X X X © 2001 by the Chemical Economics Handbook—SRI International X X X X X X . DE Clariant Corporation Coventry. IL Allegheny Chemical Corp. Barium Salt (PR-48:1) Phthalocyanine Green (PG-7) Quinacridone Violet (PV-19) Company and Plant Location Apollo Colors Rockdale. Inc. SC CDR Cincinnati. Barium Barium Salt Salt (PR-49:1) (PR-53:1) Permanent Red 2B. MA X X X PIGMENTS X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X May 2001 575. PA BASF Corporation Coatings and Colorants Division Huntington. KY Euoropean Colour. Calcium Salta (PR-57:1) Alkali Blue (PB-19 and PB-61) Diarylide Yellow AAOT (PY-14) Red Lithol ® Red.Pigments Page 178 U. WV Bayer Corporation Coatings and Colorants Division Bushy Park. Fall River. RI Daicolor-Pope. Inc. NY X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X May 2001 575. IL Magruder Color Company. Although PR-57:1 is commonly referred to as “Lithol® rubine. Producers of Largest-Volume Organic Color Pigments—March 2001 (continued) Diarylide Yellow AAA (PY-12) Phthalocyanine Blue (beta) (PB-15:3) Lithol ® Rubine. Barium Salt (PR-48:1) Phthalocyanine Green (PG-7) Quinacridone Violet (PV-19) Company and Plant Location Galaxie Chemical Corp. NJ BFGoodrich Performance Materials Cincinnati. Paterson. IL Sun Chemical Corporation Colors Group Pigments Division Cincinnati.Pigments Page 179 U.0006 W a. NJ Nichem Corp.S. NJ Max Marx Color Corp. Joliet. MI Newark. Barium Barium Salt Salt (PR-49:1) (PR-53:1) Permanent Red 2B. Irvington. Lake C.” Lithol® for this pigment is a registered trademark of BASF Corporation. OH Industrial Color Inc. Chicago. calcium salt. Elizabeth. CEH estimates. OH Muskegon. Calcium Salta (PR-57:1) Alkali Blue (PB-19 and PB-61) Diarylide Yellow AAOT (PY-14) Red Lithol ® Red. NJ Rosebank. SOURCE: © 2001 by the Chemical Economics Handbook—SRI International X X PIGMENTS . IL PMC Inc Chicago. NJ Indol Division Carteret. 5 1-1.53 10-12 10-12 10. diarylide orange.64 3.2 1.42m 3.75 3.0-1.90 12.66 0.30 5.23 11. chlorinated para red.5 5.45 11.72 na na na na 4.49 14.76 10.73 1.2 8.3 3. Includes all specified azo pigments having yellow Colour Index names as reported in the source.55 13.11 0. pyrazolone red.5-6.18 10.0 Dyeg 0.0 60. parachlor red.20 0.0-3.68 40.0006 X PIGMENTS Pigments Page 180 Salient Statistics Time series data on the U.91 2.0 3.2 Other ---------1.57 14.42 1. drug and cosmetic lakes and fluorescent pigments.91 5.5 1-1.28 1.95 13.49 13.0 3.91 15.37 2.05 0.S.00 5. depending on the availability of individually reported figures.94 59.0 Condensation Acidf 2.63 0.80 20.2 1.96 5-6 5.7 Phthalocyaninee 2.5 5.5-7.06 14.42 8. Includes all specified azo pigments possessing red Colour Index names and unspecified naphthol azo reds as reported in the source.5 2.73 1. naphthol red. 8. production of organic color pigments by chemical type are presented in the following table: U.7 Totalj 16.84 14.5 67.67 12.88 1. permanent red.0-3.22 1.3 62.S.08 2.65 3.8 8.29 3.63 25.0 6.26 2. scarlet 3B lake.55 14.65 11. toners and active toner content of extended toners.94 13.67 0.8-1 0.5 6.69 12.77 0. Production of Organic Color Pigments by Chemical Typea (thousands of metric tons) Azob Redc 1960k 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.31 16.1 1.5-6.5 5.0 14.96 19.39 1.54 0.85 2.66 21.5-6.3 15.38 32.48 3.22 0.0-1.68 1.65 0.25 1-1.49 13.2 1. c.71 2.10 14. Data may include monoazo brown.92 15. Lithol® red.90 2.92 3.68 19.45 51.14 0.6 71.6 17. b.34 8.6 18.01 2. © 2001 by the Chemical Economics Handbook—SRI International .96 3. Data probably exclude food.69 13. para red.4 1.51 14.16 3.57 5.2 5.0 6.41 34.12 1.3 Otherh 0.6 Unspecifiedi 1.0 6. Lithol® rubine.59 3.07 5.54 22.60 45.85lm 50.5 15.01 1.5-2.5-6.03 3.00 1.5-3.75 12.22 0.5 1-1.34 10.19 1.91 4.0 2.25 1.64 38.15 42.36 53.6 14.53 31.0 15.2 60.0 2.85 36.3 1.08 5.93 5.21 1.32 35.08 3. Specific pigments included under each chemical type vary from year to year.58 0.05 4.5 The net weight of synthetic organic color pigments includes lakes. such as float and flocculation resistance.0 Yellowd ---------9. pyrazolone orange.5 1.1 1.2 1.99 18. toluidine red and unspecified red lakes.58 0.23 0.00 1.36l 2.51 6.5 9.31 56.1 16.0-1.60 61.May 2001 575.3 1. red 2G.44 6. The toner content of extended toners and flush colors represents the active coloring portion of the pigment.90 3.24 1.64 0. d.57 23. red lake C.5 13.63 0. both of which are made from dyes and are probably reported as dye production.80 13.45 0. the remainder consists of inert materials added to improve certain physical properties of the pigment.20 0.64 0.5 1-1. naphthol brown.82 22.12 6.33 10.25 1.82 13.5 3.8-1 1. arylide orange. dinitraniline and orthonitraniline orange.57 14.63 10.93 1-2 1. UNSPECIFIED and TOTAL. data for 1988 for OTHER and TOTAL. brilliant green. Data include phthalocyanine blue and green. Includes an estimated 0. all data for OTHER AZO. h. alizarine red and maroon. PIGMENTS Pigments Page 181 Data may include alkali blue. Totals are CEH estimates 1993-1999.. Growth in production over the past two decades has been concentrated in phthalocyanine pigments and the high-performance pigments. 1. g. PHTHALOCYANINE. data for AZO RED for 1993 and information in footnotes a. basic blue. CONDENSATION ACID. U. (B) Synthetic Organic Chemicals. U. production of organic color pigments by color are presented in the following tables: © 2001 by the Chemical Economics Handbook—SRI International . m. data for 1983 for AZO. ed. SOURCES: (A) CEH estimates (data for 1966 and 1991-1995 for CONDENSATION ACID. k. printing inks. green and brown toners for which individual quantities are not reported and unspecified lakes.0006 Y e. Patton. i. permanent green. c and e-h). Includes an estimated figure for 1988 unspecified red toner production. vol. orange. l and m and all data for 1996-1999).. Data also include black toners in 1973-1977 and 1981-1988 (see the following table for further information on production of black toners). l.S. f. International Trade Commission (all other data 1960-1995 and information in footnotes a. C. malachite green. fuschine. Data for 1960 are not comparable to data for later years. j and m). pigment green B (before 1974) and carbazole violet. ethyl violet. Data include some phthalocyanine green in 1984. methyl violet. Data include quinacridone violet and red. Inc. d. Pigment Handbook. (C) T. Data may include Victoria blue. UNSPECIFIED and TOTAL. Data for U. John Wiley & Sons. j. datum for TOTAL for 1989. Data include black toners in 1973-1977 and 1981-1988.May 2001 575. Data for all other blue toners in the source are estimated to be mostly for production of alkali blues. since the breakdown of production data was changed by the source beginning in 1961. Production and Sales. data for DYE and OTHER for 1991 and 1993-1995. Growth in organic pigment production is generally related to the overall economy and more directly to the largest market segment. i. rhodamine red and violet and all violet toners for which individual quantities are not reported.S.S. New York. such as quinacridones and perylenes. Totals may not equal the sums of the categories because of rounding. phloxine red and all blue toners for which individual quantities are not reported. red. peacock blue (before 1966).6 thousand metric tons of quinacridone production omitted from the quantity reported in the source. 1973 (information in footnotes b. Data include all yellow. 08 11.6 Violetb 0. e.76 1.76 9. Data for RED include some violet in 1965.0 18. Inert materials added to extended toners to contribute certain properties or reduce cost are not included in the data.6 Yellowd 2.78 7.55 15.39 0.64 25.45 51.3 21.29 1.22 12.6 71.97 18. Data for 1970 and 1980-1988 exclude lakes.8 1.54 11.6 1. data for 1988 for RED.25 14. Data probably exclude food.67 1.9 2.33 10.12 14. d.55 1.03 1.21 10.10 12.3 19.6 1.40 18.97 19.38 32.81 1.64 5.39 1.00 1.69 17. 1981 and 1983-1992 exclude lakes.32 35.5 67.10 1. Prior to 1973.04 1.62 19. RED and TOTAL.1 15.21 0.24 0.30 0.46 0.09 1. Datum for RED in 1988 includes an estimated figure for unspecified red toner production.37 0.0006 Z PIGMENTS Pigments Page 182 U. 1970.15 0.36 13.08 10.64 8.40 0.39 1.54 0.64 38. b.3 2.31 1.32 0.28 9.21 0.57 17.29 0.68 40.54 16.55 1.75 1. (B) Synthetic Organic Chemicals.8 0.S.91 1.S. both of which are made from dyes and are probably reported as dye production.51 12.06 2.03 1. full-strength toners and the active coloring portion of extended toners and flush colors.85 50.9 21.7 Otherbe 0.8 1.68 1.2 2.53 31.54 6. 1975.30 0.20 3. Production of Organic Color Pigments by Colora (thousands of metric tons) Redb 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a.42 1.11 1.56 13.28 1. Production and Sales.15 42. drug and cosmetic lakes and fluorescent pigments.44 0. Data include brown pigments and unspecified synthetic organic pigments.16 18.85 36.14 1.2 60. Data for 1965.81 2. f.81 1.42 1.1 2.56 60.81 9.27 1. U.0 Orange 0.08 9.3 1.41 34.6 thousand metric tons of quinacridone violet production omitted from the reported figure. Totals may not equal the sums of the categories because of rounding.86 13.00 0.06 1.77 0.60 45.4 Blue c 4.41 0.15 4.55 13.57 0. U.16 1.17 1.3 62.22 1. c.25 11. Datum for VIOLET in 1988 includes an estimated 0.46 1.5 The net weight of synthetic organic pigments represents the weight of lakes. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International .75 18.31 1.1 2.00 4.22 15.31 56.37 1. 7.12 1.5 19. (A) CEH estimates (data for 1983 for BLUE. International Trade Commission (all other data).41 0.7 1.81 16.15 14.S.60 63.16 18.8 0.2 2.23 19.46 1.71 1.56 13.May 2001 575.63 0.32 0.38 11.07 1.3 Green 1.5 19.94 59.4 18.34 19.33 1.38 2.02 1.66 21.7 1.23 1.24 0.15 5.31 9.10 10.22 1.91 7.57 16.16 2. and information in footnotes a and c and all data for 1995-1999).98 1.0 20.23 11.21 15.18 14.45 15. black pigments were not included in the data.26 0.46 0.38 0. VIOLET and TOTAL.6 17.00 1.0 18.36 53.62 9.01 9.40 0. data for 1989.9 Totalf 16.94 2.7 1.72 2.54 22.43 1.7 1.6 18.5 20.94 8. 02 1.61 14.47 2.87 39.91 5.59 32.34 1.25 7. BARIUM SALT for 1983.85 3.02 0.08 3. and all data for 1996-1999).5 1. (A) CEH estimates (all data for ALKALI BLUE.11 9.71 1.16 2.37 2.39 1.11 0.90 30.97 40.91 1.16 10.71 21.86 2.2 13.31 9.97 2.82 2.42 na na na na na 20.59 3.84 3.01 7.08 2.75 8.08 5.37 2.May 2001 575.08 2.92 3. datum for LITHOL® RED.16 21.91 4.95 1.42 1. Red.22 8.20 2.02 2.78 0.98 3.87 7.30 6.65 2.65 3.03 6.48 3.51 5.30 0.02 8.78 10.S.9 14.97 2.64 4. Barium Salt (PR-53:1) 1.98 8.67 12.10 35.12 0.28 5.22 0. causing production overstatement.0% -- -- 2.35 5.87 4. data for PHTHALOCYANINE BLUE and LITHOL® RUBINE.3 44.9 Phthalocyanine Blue (beta) (PB-15:3) 3.71 2.57 8.71 2.96 0.60 1.61 0. b.94 1.96 1.52 4.15 40.6 Alkali Blue a (PB-19 and PB-61) 3. Typical reporting problems included individual companies not returning replies to the USITC survey.40 35.09 35.0007 A PIGMENTS Pigments Page 183 Historical USITC reported production may have been understated or overstated. Calcium Salt (PR-57:1) 2.22 12.21 0.52 24.3 15.92 2.33 0.93 6.74 0. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International . production for most of the largest-volume organic color pigments from 1980 to 1995 and CEH estimates thereafter are presented in the following table: U.S.58 2. Published data from the USITC for U.41 1.62 9.46 27.96 10.77 1.1 15.93 2.58 39.53 3.12 1.49 9.30 na 1.36 2. All Organic Barium Barium Color Salt Salt (PR-49:1) (PR-48:1) Totalb Pigments 2.27 0.59 0.19 8.0 12.04 9.16 1.79 2.92 10. Production of Largest-Volume Organic Color Pigments (thousands of metric tons) Diarylide Yellow AAA (PY-12) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 5.69 1.6 Percent of Total Lithol ® Permanent Production.36 1.52 25.39 1.70 13.9% 5.42 6.85 3.66 1.57 12. causing production omissions.93 2.57 12.00 2.33 5.7 43.20 0.04 7.6 12.34 7.08 3. Red 2B.39 6. CALCIUM SALT for 1991 and 1995.4 Lithol ® Rubine.29 3.98 1. and production reported on a wet basis instead of conversion to a dry weight basis.76 11.96 na na na na na na na na na Diarylide Yellow AAOT (PY-14) 1.5 64 63 67 69 66 69 69 72 70 70 75 56 61 60 63 70 69 65 64 62 Average Annual Growth Rate (percent) 19951999 a. 5.6% 3.4 1.26 na na na na Red Lake C. Totals may not equal the sums of the categories because of rounding.6% -- -- 3.22 5.00 1.64 3.92 1.73 25.65 13.95 11.96 2. datum for DIARYLIDE YELLOW AAOT for 1992.85 9.7% -- Data for all other blue toners in the source are estimated to be mostly for production of alkali blues.54 2.90 0. The USITC discontinued its full reporting in 1995 and all reporting in 1996.91 na na na 0.91 1.08 39.31 4.83 30. 0007 B PIGMENTS Pigments Page 184 (B) Preliminary Report on U.7 63.S.S. U.S.S.9 * Advertising spending tends to exaggerate cycles of corporate profitability.0 53. Consumption Consumption of organic pigments is dependent on demand in three major end-use markets—printing inks. (C) Synthetic Organic Chemicals. International Trade Commission (all other data). and data for LITHOL® RUBINE.8 56. paints and coatings. U.6 54.3 42. CALCIUM SALT and DIARYLIDE YELLOW AAOT for 1993). since companies typically slash or eliminate advertising during downturns but renew spending as optimism returns with upturns. Production and Sales.7 32.4 56.S.S. © 2001 by the Chemical Economics Handbook—SRI International . Estimated consumption of organic pigments since 1980 is shown in the following table: U.S.* Paints and plastics are consumed largely in the automotive and construction industries and these markets are also tied to the growth of the U. and plastics.8 29. U.0 58.May 2001 575. production of all organic color pigments grew at an average annual rate of about 5. The dot. economy. U.9 52.8% from 1996 to 1999. advertising and packaging materials and growth within these markets resembles growth of the U. BARIUM SALT and LITHOL® RED.1 60. Inks are used primarily in publishing.7 40-44 38.S.0 52.com (e-commerce) explosion of advertising spending in 1999 to early 2000 rapidly accelerated advertising and color pigment for printing demand. Production of Selected Synthetic Organic Chemicals. data for BARIUM SALT for 1992-1993. International Trade Commission (all data for RED LAKE C.8 66. with advertising spending significantly impacted by corporate profits.1 30.3 50.4 41. Consumption of Organic Color Pigmentsa (thousands of metric tons) 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 25.8 44. economy and factors such as interest rates. This was particularly evident in the 1990-1991 recession. Includes consumption for paper. b.May 2001 575.0 2. textiles and miscellaneous uses. such as crayons.1 10. textiles and miscellaneous applications.0 2.0-38.4 2. Includes paper.S. 3. CEH estimates.9 Percent of Total 64 16 15 5 100% 1999 Value Millions of Dollars 555 255 222 78 1.8-3. Consumption of Organic Color Pigments by End Use—1999-2004a (percent) Plastics/Rubber Printing Inks Paints and Coatings Otherb Average for All End Uses a.238 Percent of Total 49-54 24-26 16-19 6 100% Quantity Thousands of Metric Tonsa 43.0007 C PIGMENTS Pigments Page 185 U. b.3 58.S. Based on consumption volumes.7 9. 2. Pigmented Fibers and Rubber Otherb Total a. CEH estimates.7 3. Data represent dry weight pigment.5 3.5-9.2-10. CEH estimates.4 66. markers and artist’s colors.110 Percent of Total 50 23 20 7 100% Data represent dry pigment weight. dry pigment weight.S.4 7.0 3. Consumption of Organic Color Pigmentsa (continued) Average Annual Growth Rate (percent) 19992004 a. 36.3 SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . Consumption of Organic Color Pigments by End Use 1996 Quantity Thousands of Metric Tonsa Printing Inks Paints and Coatings Plastics.5-3. SOURCE: Consumption of organic color pigments is expected to grow from 1999 to 2004 at the following rates: Average Annual Growth Rates for U.1 Percent of Total 62-66 16-18 13-16 5-6 100% Value Millions of Dollars 607-668 297-322 198-235 74 1.1% SOURCE: Consumption of all organic pigments by major end-use market is listed in the following table: U.4 9. 53:1. 3. 61) Green Phthalocyanine Green (PG-7. b. 48:3. 23) Toluidine Red (PR-3) Permanent Red 2B (PR-48. 48:4) Permanent Red 2B. Consumption of High-Volume Organic Color Pigments by Volume—1999 (percent) Inks Blue Phthalocyanine Blue (alpha) (PB-15. 15:1. 73.May 2001 575. 83) a. 17. 48:2. 49:3) Red 2G (PR-52. 57:1.0007 D PIGMENTS Pigments Page 186 Consumption data on end uses of selected organic pigments are presented in the following table: U. 15:2) Phthalocyanine Blue (beta) (PB-15:3) Phthalocyanine Blue (beta) (PB-15:4) Alkali Blue (PB-19. Includes alkali blue used in carbon paper. 52:2) Red Lake C (PR-53. 53:2) Red Lake C.S. Paints and Coatings Plastics Other 11 79 88 82 10 22 60 51 10 23 45 95 81 69 89 93 100 3 27 10 90 65-75 47 4 6 -58 78 29 49 78 25 8 5 19 --5 -68 25 90 --- 33 17 6 -22 -7 -3 50 45 --22 7 2 -25 48 --20-30 9 --18a 10 -4 -9 2 2 --9 4 --4 --10 5b SOURCE: Projected average annual growth rates for selected large-volume organic color pigments from 1999 to 2004 are as follows: © 2001 by the Chemical Economics Handbook—SRI International . Barium Salt (PR-48:1) Lithol® Red (PR-49. 49:2. 17. 52:1. 74) Diarylide Yellow (PY-12. 36) Orange Dinitraniline Orange (PO-5) Dianisidine Orange (PO-16) Red Naphthol Red (PR-2. Includes some textiles. CEH estimates. 49:1. 65. 57:2) Rhodamine Red (PR-81) Violet Quinacridone Red (PV-19) Carbazole Violet (PV-23) Yellow Arylide Yellow (PY-1. 13) Diarylide Yellow (PY-14. 5. Barium Salt (PR-53:1) Lithol® Rubine (PR-57. Lithol® reds and Lithol ® rubines. The major printing inks by printing processes are as follows (from greatest to smallest in domestic consumption): lithographic. sales of organic pigments (produced and imported) for inks. packaging and publication. In 1996. commercial. Printing inks Printing inks are the major end use for organic color pigments. alkali blues. organic pigments industry are based on the assumption that the industry will generally follow the growth of the U. Dry pigment weight. Lithol® rubine. red 2G and red lake C) and diarylide yellows. 20%. publications account for 34% by volume of all printing inks domestically consumed. accounting for more than half of their total consumption by volume in recent years. newsprint. consumption of all organic pigments was accounted for by imports and as much as 60% of all organic pigments domestically produced are made from imported intermediates. 10%. azo reds (including Lithol® red. economy and that environmental regulations will continue to move in their present direction (see ENVIRONMENTAL ISSUES and discussions on the individual markets).S.S. CEH estimates. commercial. In terms of end-use markets. flexographic and gravure. diketo-pyrrolo-pyrroles. New findings on toxicity of inorganic or organic products and any resulting major changes in public attitudes toward these products will greatly affect their future growth.5-4 2-3 5-7 SOURCE: The quinacridones.S. Barium Salt (PR-49:1) Red Lake C. red 2G and red lake C account for up to one-third. and phthalocyanine blues account for almost one-fourth. flexographic inks are used almost entirely in packaging. The most important organic colors in inks are phthalo blues.0007 E PIGMENTS Pigments Page 187 Average Annual Growth Rates for U. © 2001 by the Chemical Economics Handbook—SRI International . and letterpress is used mainly in newsprint.S. 32%.S. Together. 4%.May 2001 575. these pigments make up almost all of the volume of organic colorants used in ink formulations. Lithographic printing inks are used mainly in publication. Barium Salt (PR-53:1) Lithol® Rubine. On a dry pigment equivalent value basis. perylenes. newsprint and packaging markets. over 30% of U. the arylide traffic yellow PY-75 and some organic fluorescent pigments are expected to have the highest average annual rates of growth. packaging. 4 1-2 1-2 (–4)-0 (–2)-0 4-5 3. Consumption of Selected Organic Color Pigments by Volume—1999-2004a (percent) Phthalocyanine Blue (beta) (PB-15:3) Alkali Blue (PB-19 and PB-61) Phthalocyanine Green (PG-7) Lithol® Red. diarylide yellows account for more than one-fourth of total U. and specialty. Projections for the U. gravure inks are used mainly in publication and packaging. Calcium Salt (PR-57:1) Diarylide Yellow AAA (PY-12) Diarylide Yellow AAOT (PY-14) Quinacridone Violet (PV-19) a. Includes screen. PG-15:4 and diarylide yellows for gravure inks. are undercut by poor bleed resistance and lightfastness. varying between 45% and 70% of the total raw material cost. They are highly stable with excellent color and brightness. (Transparency is required for inks that are used in three. archival publications sector. PG-7.S. In the late 1980s. They also deliver good tinting strength per unit of cost. to deepen the opacity (also known as adding “jetness”) and increase the covering ability of the ink. Alkali blues (PB-19 and 61) are used mainly for the toning of carbon black inks. PR-57:1. PO-16. PR-49:1. Consumption Value of Organic Color Pigments by Printing Ink Application—1999 (percent) Lithography or Offset Flexography Gravure Letterpress Othera Total a. are generally a mixture of pigments dispersed in different oils. followed by powders. PO-5.* Because of the variable conditions in U. resins. They are usually * In radiation-curable inks. but PB15:1 and 15:2 are specially treated to be noncrystallizing and can be used in these inks. beta form (PB-15:3 and 15:4. consumption of organic color pigments by ink process is distributed as follows: U. pigments are selected to accommodate the end-use requirement. PR-57:1 and diarylide yellows for lithographic inks. green shade) have several advantages for printing ink formulators. Phthalocyanine blues. accounting for roughly 80% of all organic pigments consumed for inks. largely because of their greater stability and higher value (see discussion below on trends in the ink industry). They are suitable for use in all types of inks.S. Their advantages. intaglio and other applications. PB-15:3. aqueous dispersions.and four-color printing processes. CEH estimates. up to 80% of all ink sales are customized. which are solvent processes. high tinting strength and low price. as fluids or pastes. PB-15 cannot be used in solvent-type inks because it converts to the beta form (and hence changes color) in polar solvents. red shade) are suitable for flexographic and gravure inks. which have the greatest cleanliness and transparency. Gravure solvent processes dominate the U. PR52:1. organic solvents. 15:1 and 15:2. Pigments are the essential and most expensive ingredient in nearly all printing inks. the resins used are more expensive than the pigments typically used. In printing inks. and PB-15:3. Printing inks. which are used like aqueous dispersions.S. PR-57:1 and diarylide yellows for flexographic inks. 50 26 19 neg 5 100% SOURCE: Major organic pigments include PB-15:3. water and chemical additives. Milori blues have also been replaced by phthalo blue in publication gravure ink processes.S. Preferred grades are those with the most uniform small particle size. presscakes and concentrated chips. printing operations. © 2001 by the Chemical Economics Handbook—SRI International . Flush color is by far the largest form in which organic pigments are used in inks. phthalocyanine pigments replaced inorganic Milori blue pigments in gravure printing at several printing houses.) The alpha-form phthalo blues (PB-15.0007 F PIGMENTS Pigments Page 188 The value of U. but are more concentrated.May 2001 575. strength and printing qualities. 14. In resinated form it has excellent transparency. The size shinkage will cause some existing consumption of color pigments by newspapers to slightly decline. They are attractive to ink makers because of their bright. which have increased brightness and transparency. Like the Lithol® reds. flexographic and offset inks. in general. They have good printing qualities and are economical on the basis of cost per unit of tinting strength. Lithol® rubine and red 2G pigments can be resinated to give high tinctorial strength and glossiness and to improve color. Red lake C (PR-53) is another low-cost red pigment that is used in inks for its good color. improved brightness and cleanliness. A small amount of fluorescent ink is produced from fluorescent organic pigments. alkali and acid. they are preferred for packaging gravure inks. targeted and personalized magazines and desktop publishing. as well as for all inks that require greater heat resistance and lightfastness. strong colors. An additional trend is the shrinkage of the size of newspapers from a 54inch width to a 50-inch width. strong color and good bleed resistance. In the recent past. Digital printing/publishing—computer-operated personalized direct mail. PR-49:1 is experiencing some replacement by PR-57:1 because. In resinated form. Lithol® reds (PR-49) are low-cost pigments with bright. its inks are not fast to soap. However. good prices and good physical properties.and fourcolor printing processes. Several market developments have accelerated growth including: q Color inks in newspapers—The growth and spread of color newspapers has stimulated organic pigment consumption. because of their good fastness qualities and because they are among the standard Pantone® colors for matching ink colors.5% per year. newly developed inks containing pigments in dispersions will supplement these dye-based inks since (1) dyes are more expensive and lack the q © 2001 by the Chemical Economics Handbook—SRI International . they can be resinated to produce transparent grades for three. Naphthols are becoming increasingly popular for use in water-based inks. transparency and dispersibility. including PY-13. because of the chemical constitution of red lake C. are more heat-resistant and lightfast and less reactive with aromatic solvents than PY-12. The barium salt PR-53:1 is the most important for use in inks. Other diarylide yellows. flush formulations are preferred. Although semiopaque. because of their good viscosity and ease of dispersion. Increasingly. PR-57:1 is among the oldest and most important reds for oleo resinous printing inks (oil or paste inks). their fastness to soap. It is usually sold as a product containing 20-30% by weight resinous additives.0007 G PIGMENTS Pigments Page 189 supplied as flush colors. alkali and acid is poor. letterpress and publication gravure inks. Lithol® rubine (PR-57) and red 2G (PR-52) pigments are available in several blue-red shades. They are useful in liquid ink formulations. They may be prepared in resinated forms. With the largest volume of all organic pigments. Between 1999 and 2004. particularly gravure and flexographic inks. Diarylide yellows are popular with ink makers because of their bright shades and their outstanding tinting strength. Dry alkali blues are difficult to disperse and. dyes were largely used for these ink jet printing applications. letterpress. The nonresinated form is useful for inks requiring a more opaque colorant. Lithol® rubine has better properties for matching the colors used in interchangeable printing processes. 17 and 83.May 2001 575. red lake C is used in gravure. PY-12 is used in lithographic. overall consumption of organic pigments in printing inks is expected to grow at about 3-3. Thus. and excellent waterfastness. therefore. However. In addition to its environmental and safety benefits. As a result. Water-based inks have been used for nearly fifty years in various flexographic printing applications. which uses water-based inks.5-3 (–10) 3 Over the past ten years. and (2) in paper recycling. boxes and cups and for screen printing of textiles. Flexography is also expected to gradually make inroads into non-heat-set web printing. is growing faster than for lithography. Use of water-based pigment dispersions is growing more quickly than use of powders and presscakes. Consumption of Organic Color Pigments by Volume in Printing Ink Applications—1999-2004 (percent) Gravure Inks Publication Gravure Inks Packaging Gravure Inks Flexography Inks Lithography Inks Letterpress Inks Other SOURCE: CEH estimates. Very little color is used in letterpress printing. such as those for printing foil substrates. The advantage of using water-based inks is that fewer volatile organic compounds (VOCs) are emitted. on absorbent substrates like paper. In addition. research on organic pigments for inks is concentrated on developing inexpensive pigment forms that can be efficiently wetted and easily dispersed using anionic or nonionic dispersants. its share of the organic pigments market is small and declining. Lithography is growing as a result of growth in demand for web offset printing processes and the replacement of old letterpress equipment with lithographic equipment. © 2001 by the Chemical Economics Handbook—SRI International . plates. are not easily deinked. In packaging. More than 50% of all packaging material (mostly from flexographic printing) in the United States is printed with waterbased inks. In light of regulatory restrictions regarding VOCs. envelopes.0007 H PIGMENTS Pigments Page 190 performance qualities of pigments as they are more prone to flaking. corrugated board or cartons. thereby enabling compliance with air pollution regulations and also reducing worker health risks associated with VOCs. With the increased use of waterborne systems on nonabsorbent substrates. a small but growing market for acrylic color concentrates (in chip forms) is developing in highquality water-based inks. such as those found in most ink jet printers today. the trend has been toward the use of water-based inks instead of solvent-based inks.May 2001 575. to produce items such as sacks.5 4 2. water-based flexography is gaining market share because its print quality and color have improved. dye-based inks. most involves only black inks and. and it reduces show-through and ink rub-off. its use allows high press speeds and low paper waste. bags. therefore. Estimated market growth of organic pigments by volume for each of the major types of inks for 1999 to 2004 is shown in the following table: Average Annual Growth Rates for U. especially in flexography and packaging gravure.S. gravure printers for packaging have shifted modestly to water-based inks to reduce emissions and air pollution abatement investments. 1 1 1-1. such as polyvinyl chloride and polyolefin films and aluminum foils. these inks are increasingly applied to nonabsorbent surfaces. demand for flexography. tetrachloroisoindolinones and carbazole violet. They are popular in the trade sales paint market. sales of organic pigments (produced and imported) in paints. isoindolines.S. violets account for 10-15% and phthalo blues account for over 15-20%. They are superior to the inorganics in tinting strength and replace the chrome yellows where lead-free pigments are required. especially in water-based paints.0007 I PIGMENTS Pigments Page 191 Paints and coatings The paints and coatings industry is the second-largest U. © 2001 by the Chemical Economics Handbook—SRI International . The most important organic pigments used in paints and coatings are arylide and diarylide yellows. In North America. phthalo blues and greens. quinophthalones.to lower-price-range organic pigments. arylide yellows account for at least 15% of the total U.May 2001 575. naphthol reds. but several of the more recently developed arylide pigments have improved bleed resistance. Other industrialized coatings may use mid. market for organic pigments. Red and green have lost the most share to metallic silver. The following pie chart presents the percentage of organic color pigments consumed by each of the major surface coating categories on the basis of value: U. Consumption of Organic Colored Pigments in Surface Coatings by Value—1999 Other OEM and Special Purpose 15% Architectural 30% Automotive OEM 55% Coatings that require the highest finished quality and. where their high degree of alkali resistance is important.S. the trend in autos between 1999 and 2000 has been growth of metallic silver and white at the expense of colors. perylenes. toluidine reds. therefore. the highest-priced high-performance organic pigments are the automotive OEM topcoats and refinishes. interior solvent-based semigloss and gloss paints and exterior water-based flat house paints. On a dry pigment equivalent value basis. high-performance red organic pigments account for more than 50%. accounting for 16% of the total consumption volume. Architectural coatings containing organic pigments include interior water-based flat paints. quinacridones. The arylide yellows are the highest-volume organic yellows used in paint formulating. making them attractive to paint formulators. dinitraniline orange. Some arylides tend to bleed in certain solvent-based paints.S. but their bleeding tendencies eliminate them from use in solvent-based paints. which allows lower pigment loadings to achieve the same deep shades as with other pigments. combining excellent aesthetic properties with a high degree of durability and lightfastness. although they do find some use in interior paints and in baked finishes. Quinacridone pigments have premium qualities for the paints and coatings industry. such as PR-179. enamels and emulsion paints. alkyds. are used in conjunction with metallic flake in coatings. Quinacridone supply in the United States expanded in 2000 when Ciba completed construction of a new quinacridone pigment plant at Newport. The noncrystallizing phthalo blues are necessary in the preparation of phthalo-pigmented solvent-based paints. Currently they are applied in interior emulsion and masonry paints. whereas opaque versions like PR-178 are used in highly durable solid colors with bright red © 2001 by the Chemical Economics Handbook—SRI International . chemical stability and lightfastness. Their primary advantages are their excellent color. Perylenes have excellent chemical stability. They show good alkali resistance in aqueous paint systems. They are lightfast for exterior use. but have been replaced in this market by more durable organic reds such as the quinacridones and perylenes. They were formerly used to some extent in automotive lacquer finishes (which have been largely eliminated). in lacquers. particularly in automotive OEM paints and in coil coating applications. It is used in both industrial and architectural coatings. Delaware. This quinacridone plant shares the site of Ciba’s Diketo Pyrrolo pigment plant. Their use has grown as replacements for heavy metal pigments in coatings. Toluidine reds are available in a range of semiopaque bright red shades. especially in automotive finishes and in high-quality enamels. They are compatible with all paint formulations and so find wide application. Perylenes compete on price with some quinacridones in several applications. DPP pigments are growing in their range of applications and also compete for market share with quinacridones. Their high cost is offset somewhat by their high tinting strength. Perylenes compete by color with quinacridones in some automotive and other high-performance applications. Their use is currently concentrated in automotive coatings where the need for their unique bright red hues for styling effects outweighs their higher cost over alternative pigments. high resistance to bleeding in most solvents and excellent lightfastness. but only in full strength. Naphthol reds are notable for their excellent chemical resistance and good durability. Perylenes generally have similar premium qualities to quinacridones and can be used where greater light fastness is required (higher UV tolerance). Because of its high opacity and good fastness properties. as an alternative to lead-containing inorganic red colorants. interior and exterior architectural coatings (especially water-based paints) and special-purpose coatings such as auto refinishing. These include low cost.May 2001 575.0007 J PIGMENTS Pigments Page 192 Diarylides find only limited use in paints because of poor lightfastness. Perylenes are used to a lesser extent in high-quality industrial and architectural coatings. They are typically used in auto metallic finishes. which opened in 1997. such as for automotive topcoats and major appliances. so they find use in trim paints and farm machinery coatings. In tints they can be used for interior architectural coatings. It is sometimes blended with organic reds. They provide a wide latitude to the coatings formulator and are currently in tight supply. good chemical resistance and lightfastness in full to medium tones. PR-170 is increasingly used in full-shade applications to replace lead chrome pigments. clean color. with the exception of PR-170. Phthalocyanine pigments are used in all types of paints and coatings. Dinitraniline orange has many qualities that make it appropriate for use in the paint industry. including all kinds of OEM product finishes. tinting strength. Transparent grades. but are generally limited by bleeding and poor lightfastness. consumption is expected to increase by an average annual rate of 3-4%. PR-254 and PR-255. whereas in 1999. Although they are in the medium/high expense price tier they have claimed a major portion of the red market for plastics applications in toys and in OEM automotive coatings where the highest brightness. These pigments are typically found on school buses and heavy duty trucks and mobile equipment fleets.4-diketo-pyrrolo-pyrroles (DPPs).0007 K PIGMENTS Pigments Page 193 shades. while consumption of solvent-based paints should continue to decrease by an average annual rate of 2%. Durability is always the most important consideration for coating suppliers to the automotive industry. the demand for automobile paints with improved colorfastness and flow (during application) has also increased growth in phthalocyanine blue and perylene pigment consumption in paints. These attributes compensate for its high price. Their hues cover the color range from reddish yellow to deep orange (PO-69 and PR-260). Dioxazine (carbazole) violet.52.May 2001 575. because of their high opacity.3 thousand metric tons. Consumption of these pigments will be affected by slowing capital spending. valued in paint formulations for their transparency and outstanding fastness. The organic yellow pigments PY-75 and PY-65 are used in this market. The market share of organic yellows in the traffic paints market segment will continue to grow at the expense of lead chromates. Perylenes and quinacridones are sometimes combined in high-performance coatings applications. It is commonly used in blends with blue or white pigments. Along with demand for reds. which are being imported by Ciba from Switzerland. The surface coatings industry is relatively mature and the overall quantity of organic colorants relative to inorganics in this industry will probably not change greatly in the near future. blues and greens.S. good weatherfastness and favorable rheology.S. such as PY-138. Among water-based paints.0% and traffic paints at more than 5%. as well as industrial and architectural paints. Tetrachloroisoindolinones are premium pigments. highway miles. Isoindoline pigments. cleanness and opacity are needed. like the quinacridones. organic pigment consumption in traffic paints was only a few metric tons. U. are used in lead. They are formulated into high-quality coatings as a replacement for chrome yellow. The public’s desire to decrease exposure to lead in paints underlies the increase in organic pigment consumption. The pigment industry is investing in research to find more durable pigments. replacing lead chromate yellow pigments.0% per year. possesses high tinting strength and excellent heat and bleed resistance.and cadmium-free coatings because of their high weatherfastness. have a clean greenish-yellow shade.S. New developments include a novel class of heterocyclic pigments called 1. with industrial paints increasing at an average annual rate of 1. Growth in the consumption volume of organic color pigments in surface coatings for 1999-2004 is expected to be about 2. High-performance 1. Fifteen years ago. They are used in metallic and solid-shade automotive finishes. representing over 75% of the U. total U. Quinophthalone yellows. The consumption of organic color pigment blends in traffic paints has become the norm in over half of the states of the United States. good rheological properties and high opacity.4-diketo-pyrrolo-pyrroles (DPP) pigments compete in several perylene markets. phthalo blue and green demand is increasingly satisfied by competitively priced imports from China and India. New organics and © 2001 by the Chemical Economics Handbook—SRI International . such as PY-139. organic pigment consumption in this market was over 2. However. tint strength and bleed resistance. Environmental and Health Regulations Affecting Pigments” table). transparent shades. find only limited use in these industries. lightfastness. © 2001 by the Chemical Economics Handbook—SRI International . such as Coalition of Northeastern Governors (CONEG) legislation (see the “U. available in orange. lake red C (PR-53:1) and pigment scarlet (PR-60:1). Phthalo pigments are preferred for their bright.May 2001 575. Phthalocyanine pigments. lightfastness and heat stability of the inorganics. quinacridones. where strong curing and oxidizing agents are often used. particularly in response to environmental regulations concerning postconsumer waste. especially vinyl. However.S. such as ABS. Examples of typical polyazos used in plastics are disazo condensation pigments in yellows and reds and diarylide yellow and orange. with fair to good lightfastness.and lead-containing inorganic pigments. have better resistance to heat. Quinacridones. Perylenes are widely used in plastics. durability. permanent red 2B. so they are sold in predispersed forms. but they are very costly. mainly for plastics and to a minor extent in rubber markets. phthalocyanines tend to be difficult to disperse. most organic replacements do not have the same opacity. as well as in pigmented synthetic fibers. can be used in many plastic and rubber products because of their satisfactory performance properties in both types of materials. polypropylene and cellulosic plastics. phthalocyanine blues and greens. a few organic colorants can withstand the processing temperatures required for making plastics and rubber and also have sufficient lightfastness and bleed resistance for the finished products. perylenes and tetrachloroisoindolinones. Plastics. red and violet. such as disazos. Metallized azos typically used in plastics include permanent red 2B (PR-48:1 and PR-48:2). good color strength and bleed resistance and acceptable heat stability. such as polycarbonate and ABS. The plastics industry is increasingly using quinacridones and solvent dyestuffs as replacements for the less expensive cadmium. most of which are copper-based. Quinacridones are also used in blends with inorganic molybdate orange pigments to produce different reds with good lightfastness at a lower cost. bleeding and chemicals than the monoazos. benzimidazolones have good bleed and chemical resistance. Their superior chemical and bake resistance makes them suitable for most polymer systems. Quinacridone pigments are among the most satisfactory organic alternatives to the heavy metal inorganic pigments in new high-performance red plastics requiring pigments with high heat stability. Organic pigments. Polyazos are particularly useful for elastomeric and thermosetting systems. are useful in plastics because of their excellent color. In particular. limiting their utility in paints and coatings. Benzimidazolones have excellent heat stability for use in engineering thermoplastics. organic color pigment consumption goes into these markets.S. good lightfastness and excellent tint strength. They can be used in most plastics. clean. the calcium and barium salts of permanent red 2B have found wide acceptance in plastics because of their low cost. because of their generally poor heat resistance. In plastics. pigmented fibers and rubber An estimated 14% of total U. Polyazo organic pigments. except nylons and have limited application in polystyrenes and acrylics at low temperatures. In addition. Among them are disazo condensation and diarylide yellows.0007 L PIGMENTS Pigments Page 194 inorganics continue to be developed to replace lead and cadmium pigments in surface coatings because of environmental and health concerns. Organic color pigments used in a variety of plastics are summarized in the following table: U. and in vinyl plastisols. They are used in thermoplastics. their high cost has limited their use to specialty plastics.S. PS and ABS. Recently launched by Ciba in commercial volumes. orange and red. especially gel coats. Chromophtal DPP pigments are available in red shades varying from a very yellow red to a mid-red shade. are resistant to the high processing temperatures used in plastics manufacture and are also nonbleeding and nonmigratory in most polymer formulations. marbles. However. pearlescents. in synthetic fibers and monofilaments. in thermosetting plastics. PVC. including ABS and polypropylene. A new addition for the plastics industry is the the family of pigments known as chromophtal diketopyrrolo-pyrrole (DPP). these pigments are heat-stable to 272-288°C and can be used in polyolefins. sparkle or glitter pigments.May 2001 575. Consumption of Organic Color Pigments Used in Plasticsa Thermoplastics Acetal Blue Indanthrone Blue Phthalocyanine Blue Green Phthalocyanine Green Orange Anthanthrone Orange Diarylide Orange Disazo Orange Disazo Condensation Orange Isoindolinone Red Chromophtal diketo-pyrrolopyrrole Red BP Permanent Red 2B Perylene Red Quinacridone Red Violet Dioxazine Violet Quinacridone Violet Yellow Diarylide Yellow Disazo Yellow Disazo Condensation Yellow Flavanthrone Hansa Yellow Isoindolinone Nickel-Azo Yellow Acrylic ABS Cellulosic Nylon Polycarbonate Polyester X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X © 2001 by the Chemical Economics Handbook—SRI International .0007 M PIGMENTS Pigments Page 195 Tetrachloroisoindolinones. in yellow. and “neon” or “edge glow” types. New trends developing in the plastics coloration market include granite or speckle colorants. such as those in automotive applications. Consumption of Organic Color Pigments Used in Plasticsa (continued) Thermoplastics (continued) LDPE Blue Indanthrone Blue Phthalocyanine Blue Green Phthalocyanine Green Orange Anthanthrone Orange Diarylide Orange Disazo Orange Disazo Condensation Orange Isoindolinone Red Chromophtal Diketo-pyrrolopyrrole Red BP Permanent Red 2B Perylene Red Quinacridone Red Violet Dioxazine Violet Quinacridone Violet Yellow Diarylide Yellow Disazo Yellow Disazo Condensation Yellow Flavanthrone Hansa Yellow Isoindolinone Nickel-Azo Yellow HDPE Polypropylene Polystyrene Flexible PVC Rigid PVC X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Thermosets X Epoxy Blue Indanthrone Blue Phthalocyanine Blue Green Phthalocyanine Green Orange Anthanthrone Orange Diarylide Orange Disazo Orange Disazo Condensation Orange Isoindolinone Red Chromophtal Diketo-pyrrolopyrrole Red BP Permanent Red 2B Perylene Red Quinacridone Red Violet Dioxazine Violet Quinacridone Violet Phenolic Unsaturated Polyester Polyurethane Silicone X X X X X X X X X X X X X X X X X © 2001 by the Chemical Economics Handbook—SRI International .0007 N PIGMENTS Pigments Page 196 U.May 2001 575.S. 5% for 1999-2004. (B) CEH estimates. The continued replacement of heavy metal pigments by high-performance organic pigments. Includes products for both household and business uses. as is the practice in traditional textile dyeing and printing (see the section on Other for further information on textile printing). the pigment is distributed throughout the fiber. 4 3.0 thousand metric tons. Typical products include detergent bottles and toys.May 2001 575.S. 51 and 52. mainly for carpeting and interior automotive upholstery. pp.S.5 4 2 SOURCE: No growth is foreseen for consumption of organic colorants in the rubber industry. In pigmented fiber. Growth in this market is expected to be about 3. The average annual rate of growth in the volume of organic pigments consumed in the plastics industry is expected to be about 3.0007 O PIGMENTS Pigments Page 197 U. The total 1999 domestic market for organic color pigments in pigmented fibers was as high as 2. Approximately 40% of the total fluorescent organic pigment market is plastics. The major fibers involved are nylon and polypropylene. CEH estimates. (A) “Colorants. Growth in volume for organic pigments by major market is shown in the following table: Average Annual Growth Rates for U. X X X X X X X X Phenolic Unsaturated Polyester Polyurethane Silicone X X Only recommended applications for each pigment type are indicated.5% per year from 1999 to 2004. Consumption of Organic Color Pigments in Plastics—1999-2004 (percent) Automotive Commerciala Packaging Building and Construction a. Consumption of Organic Color Pigments Used in Plasticsa (continued) Thermosets (continued) Epoxy Yellow Diarylide Yellow Disazo Yellow Disazo Condensation Yellow Flavanthrone Hansa Yellow Isoindolinone Nickel-Azo Yellow a. © 2001 by the Chemical Economics Handbook—SRI International . SOURCES: The domestic market for fluorescent pigments for use in vinyl plastisols and molded plastics is valued at roughly $19 million in terms of final sales value. dry weight basis. rather than being printed or dispersed onto the fiber or textile surface.” Plastics Compounding 1988/1989 Redbook. limited applications are not indicated. such as quinacridones and the continued substitution of plastic for metal parts in automobiles will contribute to the healthy growth for organic pigments in automotive plastics. 0%. on a value basis. which are solids containing organic pigment held in a vehicle. In the paper industry. Magruder Color. Major organic pigment suppliers to the textile industry include Bayer. © 2001 by the Chemical Economics Handbook—SRI International .S. Other pigment forms include dry pigment and presscakes. include Ciba. textiles. One possible growth area is in the drug and cosmetic colorants market. Clarient Galaxie Chemical. refer to the CEH marketing research report on Dyes. However. followed by BASF and Ciba Specialty. European Colour and Sun Chemical.S. because these are mostly laked organic dyes. carbazole violet and quinacridone. For more information. PG-7 and 36. 15:1. Textile pigments may be applied as color-concentrate chips. which is covered in the section on Plastics. In terms of sales value. 14. diarylide yellow. which is about a $20 million domestic market in pigment sales value. which is consumed in large amounts in textile printing. 17 and 83. their reported production is included with dyes. The use of fluorescent organic pigments is growing rapidly in textile/apparel printing (a category that includes silk screens). The other markets account for smaller quantities.6 thousand metric tons per year. children’s crayons. providing high brightness. Textile/apparel printing accounts for approximately 40% of the total domestic market value for fluorescent organic pigments. Fastness to dry cleaning is the single most important factor in determining which organic pigments are suitable.) Individual pigments typically used include PB-15. water-insoluble organic pigments are used as aqueous dispersions. with roughly 60% of the total U. and Sun Chemical. However. Total 1999 U.0007 P PIGMENTS Pigments Page 198 The largest of the ten or so U. The domestic market for organic pigments in cosmetics is worth roughly $15 million. high lightfastness and bleed resistance. Other Other markets that consume small quantities of organic color pigments include paper. 15:2. but are also consumed in sizable quantities. Bayer is the largest supplier of organic pigments to the U. and PY-13. watercolors and markers. but with poor fiber affinity. such as a water-soluble acrylic resin. One of the most significant individual pigments is carbazole violet (PV-23). (Textile printing is considered as a separate market from pigmented fibers. pigmented fibers and rubber. PR-23 and 170. consumption of organic pigments in paper is valued at about $20 million. 14 and 16. 15:3 and 15:4. matte board and laminated base paper for countertops.S. HiltonDavis. phthalocyanine blue and green. PV-19 and 23. PO-13. drugs and cosmetics. and food. supply.May 2001 575. producers/importers of organic pigments for pigmented fibers. The most important naphthols used in textile printing do not have assigned Colour Index names. this area consumes a very low volume of organic color pigments and thus would not significantly influence total consumption. paper industry. Domestic growth of organic colorants by volume in these combined markets for 1999-2004 is expected to be 2.5 thousand metric tons per year and textiles consume roughly 1. Paper consumes an estimated 1. Organic pigments used in colored paper are primarily for coatings.S. Organic pigments for textile printing are mainly naphthol red. Ciba’s imported line consists largely of disazo red and yellow chromophthals. Magruder Color. artist’s colors. 34 8. namely the cost of pigment intermediates and crude pigments.64 9. Annual Import Unit Sales Value for Organic Color Pigments (dollars per pound) 1996 Phthalocyanine Blue PB-16 Phthalocyanine Green PG-7 PG-36 Monoazo Orange PO-36 Disazo Red PR-144 Anthraquinine Red PR-177 Perylene Red PR-179 Quinacridone Violeta PV-19 Dioxane Violeta PV-23 Diarylide Yellow PY-12 PY-13 Arylide (Hansa) Yellow PY-74 PY-75 a.38 15.86 5.S.56 18.00 4. Imports. reported prices and unit sales values for selected organic color pigments: U. 1997 1998 1999 na na na na na na na 43. Department of Commerce.66 17.59 4.38 na na 18.62 10.May 2001 575.59 5. while dry dioxane violet (PV-23) pigment was at about $30 per pound in 1999.11 8.S. SOURCE: The price for dry quinacridone violet (PV-19) pigment was in the range of $20-$30 per pound in 1999.26 4.09 8.47 Unit sales vales for dispersions.76 14.49 15.87 5.49 27.32 29.93 8.27 31.26 4. Roughly 65% of the selling price of organic pigments is for raw material costs. followed by powder and then presscakes.0007 Q PIGMENTS Pigments Page 199 Price The following table provides U. U.42 4.52 19.70 na 7.99 14.40 4.S.55 32.03 32.81 16.S.72 5. U.81 13. Some of the raw materials used to produce organic pigments are exclusively foreign-made. Bureau of the Census.82 9. in terms of value per dry pigment weight equivalent.57 19. dispersions and color chips are the most costly forms in which organic pigments are sold.59 4.56 11. © 2001 by the Chemical Economics Handbook—SRI International . Flush colors.08 17.42 3.44 5. presscakes are usually the least expensive forms.19 5.28 4. data were reported as “Color Lakes and Toners” of various specified colors.04 4. 0. Dry weight data for 1989 through 1992 may not be comparable to other years.2 123. (B) CEH estimates based on U. After 1980.0 287.21 13. data were reported in the sources as “Color Lakes and Toners Made from Alizarin and Indigo.8 201.0 Until 1977.78 na 12.9 74.10 7.” From 1978 to 1980.4 36.1 79.5 213.7 177.4 88. as it may be overstated 25% to 40%.64 8.61 8.78 20.90 3.28 11.May 2001 575.8 165.4 197. this factor was used to obtain the data on a dry weight basis. Trade in Organic Color Pigments Importsa Thousands of Metric Tons. Department of Commerce. Dry weight data for 1989 through 1992 may not be comparable to other years.3 15.0 14.07 Millions of Dollars 0.2 171.7 Millions of Dollars 8.06 5.4 144.S.S. Dry Weight 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 a. SOURCES: © 2001 by the Chemical Economics Handbook—SRI International . Bureau of the Census (data for IMPORTS).4 75.86 7.5 328.4 143.7 45. Bureau of the Census (data for EXPORTS).7 178.93 13.4 na 263.9 Exportsb Thousands of Metric Tons. U.8 77.1 245.5 62. b.81 5.84 21.3 106.62 13.69 8.00 21.07 9.53 8.2 274.42 16.41 2.5 80.26 21.S.40 10.26 9.64 2. Reported data for concentrated dispersions from 1980 to 1988 and 1994-1999 are estimated to contain approximately 40% dry pigment by weight.69 6.60 12.1 90.3 25.S.06 25.20 11. (A) U.7 235.6 18.2 92.15 1.8 244.6 184.32 4.S.4 185.29 11.48 11.4 17.21 16.50 9.1 207.0 259. Imports.09 8.39 21.44 10. data were no longer broken down by colors or chemical types.42 16.5 79. as it may be overstated 25% to 40%.0007 R PIGMENTS Pigments Page 200 Trade Historical trade data for U.0 87.0 278.S. Dry Weight 1.75 9. U. Exports.5 120.5 309. Department of Commerce.48 7.8 10. organic color pigments are listed in the following table: U.4 49. 7 13.S. the single largest source of color pigment imports was China with a 28% market share. Imports.S. U. China has become the leading source of blue (PB15:3). Exports of Organic Color Pigments—1999 Country of Destination Belgium Canada United Kingdom Other Total SOURCE: Quantity (thousands of metric tons.S. As recently as 1992. but in 1999 its market share fell to only 7%. some is imported by Ciba Specialty for its U.1 Market Share (percent) 28 18 10 44 100% U. dry weight) 5. followed by Bayer and Ciba. source for organic color pigments.5 17. Bureau of the Census. Department of Commerce. PG-36) and red pigments (PR-57:1). exporter of organic pigments. Hoechst Celanese and Sun Chemical may hold as much as 55% of the total U.3 5. Exports Exports by major country of destination in 1999 were distributed as follows: U. green (PG-7. subsidiaries. Sun Chemical is the largest U.S. A large portion of the imports from Germany is exported by BASF and Clariant (formerly Hoechst).S. an increase of over 50% from its market share in 1996.S. Together.0007 S PIGMENTS Pigments Page 201 Imports Reported imports of organic color pigments by major country of origin in 1999 were as follows: U.S. U. particularly green (PG-7).8 3. Bureau of the Census. Ciba. India has emerged as the third-largest U. dry weight) 3. In 1999.4 1. Department of Commerce.4 3. © 2001 by the Chemical Economics Handbook—SRI International .S. imports value. Imports of Organic Color Pigments—1999 Country of Origin China Germany India Other Total SOURCE: Quantity (thousands of metric tons.S. with a concentration in phthalocyanine pigments. In terms of export value. Bayer. The second-largest source of imports was Germany with 18% of imports. Exports.May 2001 575.S.0 5. BASF.7 Market Share (percent) 31 21 17 31 100% CEH estimates based on U.7 2. Japan. was the largest source of color pigment imports with a 25% market share. 6 31. as is basis) 1997 1998 1999 SOURCE: 12. Ontario plant include Diarylide Yellow PY-12.0007 T PIGMENTS Pigments Page 202 CANADA Producing Companies Dominion Colour Corporaton is Canada’s sole producer of orange.7 © 2001 by the Chemical Economics Handbook—SRI International . Value (millions of Canadian dollars) 30.9 12.3 3. as is basis) 1997 1998 1999 SOURCE: 3. PY-13.May 2001 575. Canada’s organic pigment export data are listed below.8 163. Canadian Exports of Organic Color Pigments Quantity (thousands of metric tons. PY-14 Lithol® Rubine.7 Statistics Canada.9 The majority of Canada’s organic pigment imports come from the United States. the largest-volume organic color pigments produced at its Ajax.7 Statistics Canada.6 11. Calcium Salt PR-57:1 Monoazo Orange PO-36 Trade The following table shows imports for Canada in recent years: Canadian Imports of Organic Color Pigments Quantity (thousands of metric tons. red and yellow organic pigments.9 31. Value (millions of Canadian dollars) 152.6 151.8 3. 49. de C. Nuevo Leónc a. Barium Salt (PR-48:1) Lithol ® Rubine Red (PR-57:1) Diarylide Yellow (PY-12) Diarylide Yellow (PY-13) Arylide Yellow PY-74 Company and Plant Location Bayer de México. 3. 3. Nuevo León Pyosa. 48. 65 PB 15:3. S. X X X X X X X X X X Bayer also produces the following organic pigments in Mexico: Monoazo Yellow Phthalocyanine Blue Monoazo Red Xanthene Red Xanthene Violet Azo Green Triphenylmethane Violet PY 1.V.A. Monterrey. de C.V.A.A. 17. 83 SOURCE: CEH estimates. Clariant also produces the following organic pigments in Mexico: Alkali Blue Pyrazolone Orange Pyrazolone Red PB 56 PO 13 PR 38 c. S. Pyosa also produces the following organic pigments in Mexico: Monoazo Red Monoazo Yellow PR 3. de C.May 2001 575. Monterrey. de C. 53:1. 49:1. Santa Clara. 14.A. Edo. de Méxicob Ftalmex. 48:2. de Méxicoa Clariant (México). 15:4 PR 48:1.0007 U PIGMENTS Pigments Page 203 MEXICO Producing Companies The following table lists the production of organic pigments by Mexico’s two producers: Mexican Producers of Major Organic Color Pigments—March 2001 Phthalocyanine Blue (PB-15) Phthalocyanine Green (PG-7) Permanent Red 2B.V. S. © 2001 by the Chemical Economics Handbook—SRI International . Edo. 57:1 and 112 PR 81 PV 1 PG 8 PV 3 b.V. 53 PY 1. S. Lerma. 56% of Mexico’s organic pigment imports originated in the United States.06 1.55 2. Comercial de México. In 1999. © 2001 by the Chemical Economics Handbook—SRI International . 56% of Mexico’s organic pigment exports went to the United States while the next-largest destination was Germany. Banco Nacional de Comercio (1993-1995). Comercial de México. reflecting a shift of some of Bayer’s pigment production to Mexico.88 1. at nearly 17%. (B) Secretary of Economy. Mexico (1997-1999). In 1999. Banco Nacional de Comercio.18 0.73 0. Mexico’s organic pigment exports have risen eightfold since 1993.02 (A) Sistema de Información.0007 V PIGMENTS Pigments Page 204 Trade Import data are available for Mexican organic color pigments as follows: Mexican Imports of Organic Color Pigments (thousands of metric tons) 1993 1994 1995 1996 1997 1998 1999 SOURCES: 1.24 0. (B) Secretary of Economy. Mexico (1997-1999).55 (A) Sistema de Información.71 na 4.34 na 0.43 4.May 2001 575.58 5. (1993-1995). Export data are available for Mexican organic color pigments as follows: Mexican Exports of Organic Color Pigments (thousands of metric tons) 1993 1994 1995 1996 1997 1998 1999 SOURCES: 0. CEH estimates. São Paulo Venezuela C. The leading Western European suppliers of organic pigments are Clariant. Ciba Specialty Chemicals and BASF. © 2001 by the Chemical Economics Handbook—SRI International . Barueri.R.L. organic pigments are in the hands of only a few producers.to medium-tier pigments. de Pilar. for cost reasons. Unlike inorganic pigments. SOURCE: WESTERN EUROPE In 1999. Western European producers will.0007 W PIGMENTS Pigments Page 205 SOUTH AMERICA The following table lists the producers of organic pigments in South America: South American Producers of Organic Color Pigments—March 2001 Phthalocyanine Blue (PB-15) Phthalocyanine Green (PG-7) Pyrazolone Orange (PO-13) Napthol Red Medium (PR-17) Monoazo Red (PR-245) Diarylide Yellow AAA (PY-12) Company and Plant Location Argentina Anilinas Rieger S. continue to relocate production of their low. Despite volume growth. Western Europe accounted for about 29% of the total world organic pigments production in volume terms and for at least 36% in value terms. Venezolana de Pigmentosa Valencia. The smaller organic pigment producers are Avencia and Bayer. the market value has declined during the last three years because of price erosion.to medium-value pigments to lower-cost producing countries in Asia (particularly China and India) as well as to North and South America (particularly Mexico). Buenos Aires Oscar Carlos Rapp e Hijos S. The volume share is expected to continue to decline as other regions gradually become more self-sufficient in classical pigments and as countries such as India and China increase their exports of low. Western European consumption of organic color pigments was valued at roughly $525 million. In addition. In 1999. all internationally operating companies.A. Pilar. Carabobo a. A. Buenos Aires Brazil Brancotex Indústrias Químicas Ltda. X X X X X X X X X X X Venezolana produces an additional number of azo red and yellow pigments. Mathew-Pdo.May 2001 575. a decline from $600 million in 1996. Western Europe remains the leading region for organic pigments production. Indaiatuba. followed by two foreign producers. Though declining in output. Dainippon Ink (Kemisk Vaerk Køge and INTORSA) and Toyo Ink (Francolor Pigments). São Paulo Cleomar Química Indústria e Comércio Ltda. Azo pigments The following table shows Western European producers of azo pigments.2 39.0 33. 65. manufactures phthalocyanines and a range of other organic pigments at its subsidary in India.2 Producing Companies Western European producers of organic color pigments are shown in the following table. along with the types of pigments they produce: Western European Producers of Organic Color Pigments—2001 Azo Company Avencia BASF Aktiengesellschaft Ciba Specialty Chemicals Clariant European Colour Francolor Pigments Gebroeders Cappelle Intermedios Orgánicos Kemisk Vaerk Køge Société Languedocienne de Micron-Couleurs Tennants Textile Colours SOURCE: CEH estimates. dry weight) Production Imports Exports Consumption SOURCE: CEH estimates. Heubach. Red -X X X X X X X X -X Yellow -X X X X X X X X --Phthalocyanine Blue X X X --X X -X X -Green X X -------X -Other X X X X X X X X ---- In addition to the above-listed companies.0 71.May 2001 575. the German company.0007 X PIGMENTS Pigments Page 206 The following table summarizes the Western European supply/demand situation for organic pigments in 1999: European Union Supply/Demand for Organic Color Pigments—1999 (thousands of metric tons. along with capacities and types of pigments produced: © 2001 by the Chemical Economics Handbook—SRI International . [Japan]) Montcada i Reixac Switzerland Ciba Specialty Chemicals Inc. Ltd. Japan) Rieux Germany BASF Aktiengesellschaft Ludwigshafen Stuttgart-Besingheim Clariant GmbH Frankfurt am Main Italy BASF Italia Spa Cesano Maderno Spain Intermedios Orgánicos... Schweizerhalle Monoazo Disazo Naphthol AS Pigments Red Lakes Other X X X X X X X X X X X X X X X Metal complex X X X Benzimidazolones X X X X X X X Red disazo pigments.May 2001 575. Co. Co..Cromophthal® © 2001 by the Chemical Economics Handbook—SRI International .0007 Y PIGMENTS Pigments Page 207 Western European Producers of Azo Pigments—2001 Red Yellow Company and Plant Location Belgium Gebroeders Cappelle nv Menen Denmark Sun Chemical A/S Køge France Francolor Pigments SA (owned 100% by Toyo Ink Mfg. SA—INTORSA (owned 92.5% by Dainichiseika Color & Chemicals Mfg. Ltd. Phthalocyanine pigments Western European producers of phthalocyanine pigments and the pigments they produce are shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International .0007 Z PIGMENTS Pigments Page 208 Western European Producers of Azo Pigments—2001 (continued) Red Yellow Company and Plant Location United Kingdom Ciba Specialty Chemicals PLC Pigments Paisley European Colour (Pigments) Limited Stockport Monoazo Disazo Naphthol AS Pigments Red Lakes Other X X X X X Classical a 20 pigments (Eljon®. Corfast® and Cortone®) SOURCE: CEH estimates.May 2001 575. 0008 A BASF Italia Spa Cesano Maderno X X © 2001 by the Chemical Economics Handbook—SRI International X X . SARL Halluin Francolor Pigments SA (owned 100% by Toyo Ink Mfg. [Japan]) Villers-Saint-Paul Société Languedociene de Micron-Couleurs SA—SLMC (owned 100% by Total) Narbonne Germany BASF Aktiengesellschaft Fine Chemicals Department Köln Italy (PB-15) (PB-15:1) (PB-15:2) (PB-15:3) (PB-15:4) (PB-15:6) Pigment Green (PG-7) (PG-36) Trade Name X X X X X Isophthal PIGMENTS X X X X X X X X X X X X X X X X X X Helioecht May 2001 575. Co..Pigments Page 209 Western European Producers of Phthalocyanine Pigments—2001 Pigment Blue Company and Plant Location Belgium Gebroeders Cappelle nv Menen Denmark Kemisk Vaerk Køge A/S Køge France Cappelle Frères. Ltd. Pigments Page 210 Western European Producers of Phthalocyanine Pigments—2001 (continued) Pigment Blue Company and Plant Location United Kingdom Avencia Limiteda Grangemouth (PB-15) (PB-15:1) (PB-15:2) (PB-15:3) (PB-15:4) (PB-15:6) Pigment Green (PG-7) (PG-36) Trade Name Ciba Specialty Chemicals PLC Pigments Paisley a. X X X X Irgalith Previously owned by Zeneca Limited (United Kingdom).0008 B © 2001 by the Chemical Economics Handbook—SRI International X Monastral. PG-7 is main pigment PIGMENTS . SOURCE: May 2001 575. CEH estimates. . SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . Ltd. Blue and violet. d. [Japan]) Montcada i Reixac Switzerland Ciba Specialty Chemicals Inc. Montheyd United Kingdom European Colour PLC London a. b.A.5% by Dainichiseika Color & Chemicals Mfg. Also produces standard grades of diketo-pyrrolo-pyrrol-(DPP) and isoindolinone yellow at this location. Huningue Germany BASF Aktiengesellschaft Ludwigshafenb Ciba Spezialitätenchemie Grenzach GmbH Grenzach-Wyhlenc Clariant GmbH Frankfurt am Main Spain Intermedios Orgánicos. Co.May 2001 575.0008 C PIGMENTS Pigments Page 211 Other organic pigments The following table shows Western European producers of other organic pigments along with types of pigments produced: Western European Producers of Other Organic Pigments Company and Plant Location Belgium Gebroeders Cappelle nv Menen France Clariant Huningue S. Also produces specialty grades of diketo-pyrrolo-pyrrol-(DPP) at this location. CEH estimates. Anthraquinonoide Dioxazine Perinone/ Perylene Quinacridone Thioindigo Triphenylmethane Xa X X X X X X X X X X X X X X Also produces quinophthalone at this location. c. SA— INTORSA (owned 92. 0008 D PIGMENTS Pigments Page 212 Production The following tables summarize 1999 Western European production of organic pigments by type and color.May 2001 575. © 2001 by the Chemical Economics Handbook—SRI International . 4 PY-1.7 na 1.3 0.2 -- 4.1 0.5 0.3 --0. flavanthrone. 224 PB-15:1. anthanthrone. indanthrone. PR-260 0. 53:1. 3.9 0.4 0.8 65.4 0. b.1 10.0008 E SOURCE: © 2001 by the Chemical Economics Handbook—SRI International 4. 37 PO-43.0 neg --neg --neg ---0.5 4. 111. anthrapyrimidine.3 0. 242 PY-150. PO-59.0 9.1 4.3 18. May 2001 575.2 2. 4 PO-22.1 -0.5 0. PR-1.3 5.4 0.3 13. 15:4 PG-7.1 ------0. 36 PV-19.7 ----3.1 neg -- -- -- neg 0.5 0.5 0. PR-257 PIGMENTS . CEH estimates.5 ---0. 57:1 PY-180.5 -0. 49:1. 177.2 -----4.2 1. 22.5 12. 166. 15:3. 108. Anthraquinone.6 0.5 0.3 0. dry weight) Brown/ Black Total Volume Produced Yellow Azo Pigments Monoazo Disazo beta-Naphthol Naphthol AS Red Lakes Benzimidazolone Disazo Condensation Metal Complex Isoindoline/one Polycyclic Pigments Anthraquinoideb Diketo-pyrrolo-pyrrole Dioxazine Perinone and Perylene Phthalocyanine Pigments Blues Greens Quinacridone Quinophthalone Thioindigo Triarylmethanes Other Total a. PV-3.7 4.2 -0.0 ---0.5 2. PB-19 PBk-1.0 4 12. PO-16 PO-5. 74.6 0.1 0.2 PY-24.2 15. PV-5:1.4 --0.9 0. 209 PY-138 PR-181 PR-81. 147.6 0. PO-36. 52:1.4 0. 46. 168.5 0.5 21.3 ---13.1 0. 14. PR-149. PR-185 PY-128.6 0.6 0.1 --0. Orange Red Violet Blue Green Major Pigments Produced 0.1 -0. 48:2. PR-122. 83.0 1. 38.4 neg --0. 31 PY-17.8 neg ---0. 255 PV-23. other Color definition according to the Colour Index. PR-144. PR-2.9 0. 68. PB-60 PR-254.1 --- ---neg ----- -------neg ---neg 0. PR-83. PR-48:1.1 0.1 0.3 0. 49:2. PO-51. 69.9 0.0 0.1 0. isoviolanthrone and pyranthrone pigments. 23. 168 PY-12.4 PO-61.5 0. 13. 65.2 -0.0 1.7 ---neg ------0.5 1.9 0.Pigments Page 213 Western European Production of Organic Color Pigments by Type and Color—1999a (thousands of metric tons. Western European production of organic pigments is expected to continue decline over the next few years because of: q Continuing migration of the lower-tier pigment production to lower-cost countries outside of Western Europe Increasing capability for finishing imported crude pigments q Consumption It is estimated that Western Europe consumed some 71 thousand metric tons of organic pigments (dry weight basis) in 1999. © 2001 by the Chemical Economics Handbook—SRI International . it is expected that the printing inks market will be growing fastest during the next five years. granules and highly micronized types) in order to gain a competitive advantage.2 14.2 0. The second-largest segment is paints and coatings with about 30% market share. which accounted for about 45% of total organic color pigments consumption in volume terms in 1999.2 1. the plastics and rubber segment is the third-largest segment. however.0008 F PIGMENTS Pigments Page 214 Western European production of phthalocyanine pigments fell with significant import competition.6 3.2 The largest market segment is printing inks.g. higher value-added grades and forms of phthalocyanine pigments (e. Smaller volumes are consumed in pigmented fibers. dry weight) Azo Pigments Polycyclic Pigments Phthalocyanine Pigments Blues Greens Triarylmethanes Quinacridones Anthraquinones Diketo-Pyrrolo-Pyrroles Perinone/Perylene Thioindigo Dioxazine Other Total SOURCE: CEH estimates.2 0. Most Western European producers have tried to develop new. In volume terms.6 0.. the plastics and rubber segment will be the most promising.4 0. 46. In value terms.May 2001 575.4 3. With about 14% of total consumption.9 0.1 71.4 0. textile printing and in paper coloration. The following table gives an estimate of Western European consumption by pigment type: Western European Consumption of Organic Color Pigments by Pigment Type—1999 (thousands of metric tons. primarily from China followed by India. 0008 G PIGMENTS Pigments Page 215 The following table gives a breakdown of organic pigment applications in Western Europe.8 3. the rest being resins.0 1.5 2.0 20.5 2. but also include high-performance pigments. together with volume growth projections: Western European Consumption of Organic Color Pigments (thousands of metric tons.5 1.9 3.6 16.3 1999 32.1 56.9 The following table gives a consumption breakdown by application for phthalocyanine pigments: Western European Consumption of Phthalocyanine Pigments by Application—1999 (thousands of metric tons) Printing Inks Paints and Coatings Plastics and Rubber Textile Printing Pigmented Fibers Other Total SOURCE: CEH estimates. In 1999.7 1.8 1.3 71. It is estimated that printing inks contain about 15-20% pigments. In Western Europe.9 3.4 0.2 0.2 4.0 18.1% 1993 Printing Inks Paints and Coatings Plastics and Rubber Pigmented Fibers Other Textiles Paper Miscellaneous Total SOURCE: 25. The types of pigments consumed are mostly low-cost pigments.9 0. 7. solvents and additives.8 0 1.5 0. The following table lists production since 1984: © 2001 by the Chemical Economics Handbook—SRI International .0 Printing inks In Western Europe.9 CEH estimates.3 10.0 4.2 1.1 2.5 1. the production of printing inks has significantly increased over the last decade.8 0.8 1. the average organic pigment content in printing ink formulations was about 19%.5 11.2 63.5 2.9 2.8 18.6 8. dry weight) Average Annual Growth Rate. printing inks are the largest application for organic pigments in volume terms.May 2001 575.2 2004 37. 1999-2004 (percent) 3.1 21.5 2.2 0.7 1.6 0.9 7.4 78. 1996 28. as the larger companies began to concentrate more on their core business activities. © 2001 by the Chemical Economics Handbook—SRI International . the cyclicity of advertising spending will amplify growth above or below GDP. have captive demand for printing inks: BASF Aktiengesellschaft Kemisk Vaerk Køge (through Sun Chemical/Danippon Ink and Chemicals) Intermedios Orgánicos—INTORSA (through Dainichiseika Color & Chemicals) Francolor Pigments SA (through Toyo Ink) In spite of the increasing competition and globalization of the printing industry. Also the trend toward downstream integration by pigment producers has come to a halt. The fast expansion of the water-based flexographic ink market for packaging applications in Western Europe also affects the types of pigments used.0008 H PIGMENTS Pigments Page 216 Western European Production of Printing Inks (thousands of metric tons) 1984 1985 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 SOURCE: 460 475 475 478 522 549 576 639 689 690 770 795 810 935 1. the number of printing ink producers has remained relatively constant. resulting in lower ink production costs. Four organic color pigment producers. especially when considering the rapidly increasing export potential to Eastern Europe and Asia. These inks demand that the pigments have special granular characteristics and surface properties to enhance dispersability and compatibility. This. Ink producers are gradually switching to flushed pigments from dry pigments.May 2001 575. coupled with the growing trend toward more color printing in journals and newspapers will generally cause growth in organic pigments consumption. However. Further changes in the printing ink industry have affected pigment production. Overall growth is expected to continue for the next five to ten years.058 CEH estimates based on data from CEPE. Printing Inks and Artists Colour Manufacturers Associations. depending on the growth or shrinkage of advertising budgets. leading to strong consumption growth averaging 4% per year. European Confederation of Paint. as flushed pigments are easier to handle. The development of such pigments is ongoing. The future of the Western European printing ink industry is promising. A wide range of other color pigments are also available for use in printing inks. lake red C and also eosine lakes.May 2001 575.0008 I PIGMENTS Pigments Page 217 Color organic pigments. because of substitution of inorganic pigments such as lead chromate and cadmium. Hansa yellow is used to some extent when extreme lightfastness is required. organic pigments producers are tending toward downstream integration into polyolefin color concentrate (masterbatch) production. Organic pigments are used in practically all types of plastics and rubber. acrylics. It is expected that this substitution trend is maturing. New inorganic pigments. Reds consist of the Lithol ® reds. increasingly used and may limit the penetration of organic pigments. in general. the consumption of organic pigments in paints and coatings has been higher than the growth rate of paints and coatings production. a concentration of the plastic masterbatch producers is in progress.e. as well as cellulosics. The use of organic pigments has grown more or less in line with total plastics consumption. As in to the printing ink industry. Since 1985. the demand for organic pigments has benefited from substitution of toxic inorganic pigments. Paints and coatings Western Europe is the world’s leading region for paints and coatings production. polyolefins. solvent dyes). such as bismuth vanadate and rare earth sulfides. As in other applications. Victoria blue and alkali blues. rhodamine reds. polycarbonate and polyester. By far the largest organic pigment–consuming country for paints and coatings is Germany. toluidines. the use of organic pigments is substantial and increasing. Blues consist of peacock blue (PB-24). Plastics and rubber The third-largest application of organic pigments in volume terms is for plastics and rubber. i. Yellows consist mainly of diarylide yellows and yellow lakes. © 2001 by the Chemical Economics Handbook—SRI International . accounting for about 25% of total world production. nylon. Polyolefin fibers are difficult to color with the currently available textile dyestuffs. Pigmented fibers Basically three different methods give color to fibers and textiles: dyeing (with dyestuffs). are. In addition. para reds. however.. printing (with either dyestuffs or pigments) and spin dyeing (primarily with pigments but also dyestuffs. these organic pigments are being used more and more as replacements for the inorganic chrome yellows. In order to avoid the use of lead compounds. The primary plastics pigmented are PVC. Although the bulk of pigments used are inorganic. accounting for almost 30% of total Western European consumption. polystyrene. phthalocyanine blues. There are only a few exceptions where dyestuffs can be used in coloring polyolefin fibers . such as dyeable nickel-modified polypropylene fibers. have a greater choice of brilliant colors than inorganic pigments. so most polyolefin fibers are pigmented. which in most cases cannot be matched with conventional textile dyestuffs.2 0. 20. During the last few years.7 0. polyester. in decreasing order.8 17. There is. the spin-dyeing technique has considerable advantages over the conventional dyeing technique. The next most-important fibers that are spin dyed are. however. by more than 10% per year between the mid-1980s and mid-1990s. required for the manufacture of outdoor grass-type carpets. CEH estimates.May 2001 575. but it is estimated that polypropylene fibers account for about 70% of all spin-dyed fibers produced in Western Europe. pigments will not be used extensively as dye substitutes given the current product range. primarily because of technological advances in producing esthetic.2 0. From an environmental point of view. Through conventional textile dyeing processes. solvents are used that can be recovered with virtually no loss. Organic pigments are used in practically all chemical fibers. the use of pigments for spin-dyed polyolefin fiber–based carpets and rugs has grown significantly. However. such as polyolefin fibers) and dispersibility of the © 2001 by the Chemical Economics Handbook—SRI International . In the wet and dry spinning process. see the Textile printing section. spin dyeing of chemical fibers has become more popular. One of the major advantages is the availability of pigments with significantly superior light.6 0. A further advantage is the fact that in spin dyeing the color is added to the polymer prior to extrusion without creating wastewater.0008 J PIGMENTS Pigments Page 218 Spin dyeing has certain advantages over the conventional dyeing technique. low-priced polypropylene fiber carpets and rugs. Hence. acrylic. a certain substitution possibility in textile printing. polyamide and polyethylene fibers. together with an estimate of color pigments consumed.1 na 21. Western European Consumption of Spin-Dyed Synthetic Fibers and Color Pigments—1999 (thousands of metric tons) Nondyeable Fibersa Polyolefin Fibers Dyeable Fibers Acrylic Fibers Polyester Fibers Modacrylic Fibers Polyamide Fibers Viscose Fibers Total Inorganic Pigments Organic Pigments a. The selection of the pigments consumed depends largely on the cost of the pigment as well as the heat stability (primarily for those fibers that are melt spun.7 4.and weatherfastness. Shown in the table below are the type of synthetic fibers that are pigmented. In particular. spin dyeing is only possible for chemical fibers and only for a limited number of final fiber applications. For further information.1 SOURCE: Probably one of the most widely used organic pigments in spin dyeing is phthalocyanine green. office products.5 times higher than when dyeing with textile dyestuffs. The major suppliers of organic pigments in Western Europe and their typical brand names are shown in the following table: Western European Suppliers of Organic Color Pigments for Paper—1999 Trade Name Aveinca Monastral Monolite Pigmosol Basoflex Levanyl Heliocet Irgalith Flexonyl Hydroplast CEH estimates. matted boards and laminated base paper for countertops. high lightfastness and bleed resistance.May 2001 575.0008 K PIGMENTS Pigments Page 219 pigment. Some uses include coloring wood. Although the volumes consumed in these applications are small. Although color ink jets are manufactured primarily with dyestuffs. but have poor fiber affinity. They provide improved high brightness. the use of pigments in textile printing has increased. the required unit consumption per ton of fiber spin dyed is about 1. In addition. Hence. the value of some of these specialty markets is appreciable. improved quality and the introduction of environmentally friendlier printing processes. efforts have also been made to use © 2001 by the Chemical Economics Handbook—SRI International . accessories. BASF Bayer Ciba Clariant SOURCE: Other Organic pigments are used in a number of smaller applications. Pigments for paper In Western Europe. A relatively new application of pigments is in the manufacture of digital printing and ink jets. organic pigments are used by the paper industry in the form of aqueous dispersions. artist colors and drawing materials and cosmetics (including soaps). Textile printing Although textile dyestuffs are by far the largest type of colorants used to color textiles. The cost for suitable pigments is generally higher than that for dyestuffs. They are used primarily for coatings. from the cost point of view. inorganic pigments have considerable advantages over organic pigments in this particular application. The textile printing boom in the last twenty years has been characterized by increased productivity. Western Europe consumed about 1.2 thousand metric tons of organic color pigments for textile printing. It is estimated that in 1999. The following table summarizes the European imports of organic pigments for selected years by country of origin: European Community Imports of Organic Colored Pigmentsa (metric tons.609 36. The main disadvantage is that pigments are solid and tend to clog up the jet orifices. prices for organic pigments have differed substantially from country to country.956 2. During this same period Western European organic pigment imports rose by over 25%.971 5. versus (10. Republic of United States Other Total 1988 86 96 59 779 3. The average Western European import value for organic colored pigments and preparations was (8.879 28.945 1992 na 602 243 2. as is) Country of Origin Brazil China Czech Republic India Japan Korea. calculated on a dry pigment weight basis.620 579 2. the European Union imported 63 thousand metric tons of organic pigments and pigment preparations on an as-is basis.408 6.0008 L PIGMENTS Pigments Page 220 pigments. with price declines accelerating from 1997 to 1999. it can be seen from the table below that imports of organic colored pigments into Western Europe have increased nearly eight-fold since 1988.and waterfastness.894 1995 718 1. these volume increases are inflated somewhat because flushed pigments. Price Historically. Imports In 1999. All of the large. The dominant country of origin was the United States.216 62.092 7. Particularly for the large-volume products. followed by China.222 4.176 5. but prices are becoming homogeneous throughout the region because of the growing awareness of international price levels. Imports from the United States have increased significantly. For commodity-type azo pigments prices have decreased substantially since 1992.116 1999 616 8. such as PY-13 and PR-57:1.485 665 3.06 euros per kilogram in 1997. was about 39 thousand metric tons. One of the main reasons for this general price decline is the global overcapacity and the increasing supply from low-cost producers in Asia. Japan and India.May 2001 575. The use of pigments in this application provides the advantage of increased light. global producers source increasing volumes of commodity-type pigments from their overseas subsidiaries.385 19.262 464 7. represent a large portion of the increased volume.396 6.066 903 7. which are not reported on a dry pigment weight basis.21 euros per kilogram in 1999.574 1. prices declined up to 20% during 1992-1996. It is estimated that this volume.670 Import Trends 1999-2004 Moderately increasing Increasing Increasing Increasing Flat Increasing Moderately increasing Increasing © 2001 by the Chemical Economics Handbook—SRI International . however.933 19. In spite of the uncertainties about actual dry weight traded.278 1.287 2. which in 1999 accounted for nearly 17% of total Western European exports in volume terms. Analytical Tables of Foreign Trade: Products-Countries. coupled with the increased competition in the Western European pigment-consuming industries. Exports Until the late 1990s. Statistical Office of the European Community. commodity-type organic pigments imports from China. subsidiaries of the Western European producers.9 26.May 2001 575. have been the prime reasons for growing imports from Asian countries. As a result of the increased competition.S. Western Europe was traditionally a net exporter of organic pigments in value and volume. Statistical Office of the European Community. Exports to outside Western Europe. exports of organic pigments have increased slightly over the last few years. SOURCE: The availability of low-priced organic pigments with acceptable quality. Overall. followed by France and the United Kingdom. Western European exports of organic colored pigments for selected years are shown in the following table: Western European Exports of Organic Colored Pigmentsa (thousands of metric tons. Many of these products are high-value-added pigments. highest-value-added pigments. Data do not include volumes imported by Finland. Now it is a net exporter only in value terms. equivalent to about 33 thousand metric tons on a dry pigment weight basis. the largest export destination by far is the United States. In 1999. Norway and Sweden.17. Western Europe exported approximately 40 thousand metric tons of organic pigments and pigment preparations. NIMEXE. Eurostat. as is) 1988 1992 1995 1999 a.00. Like the developments in dyestuff imports. The pigments exported to the United States are primarily those products that are not manufactured by the U.5 30.0008 M PIGMENTS Pigments Page 221 a. Although pigments are exported throughout the world. The main exporting countries in terms of value are Germany and Switzerland.8 39. Import code # 3204. Includes pigments and pigment mixtures. such as perylenes from BASF (Germany) and diketo-pyrrolo-pyroles from Ciba (Switzerland). 33. Western European producers of organic pigments will increasingly concentrate on the most specialized.5 SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . Eurostat. India and Korea are expected to increase further. (joint venture between Dainichiseika Color & Chemicals [Japan] and Nitrokémia Rt. Azo pigments. Phthalocyanine pigments.May 2001 575.5 thousand metric tons per year.) Füzfögyartelep Poland Wolskie Zaklady Przemyslu Barwnikow “Organika” Wola Krzyszoporska Phthalocyanine pigments. However. Ústí nad Labem Synthesia a. Hungary Nicolor Rt. azo. a. Azo pigments.s. © 2001 by the Chemical Economics Handbook—SRI International .0008 N PIGMENTS Pigments Page 222 EASTERN EUROPE Producing Companies Major producers of organic pigments are listed in the following table: Central and Eastern European Producers of Organic Colored Pigments—2001 Company and Plant Location Czech Republic Spolek pro Chemickou a Hutní Vyrobu. AO Pigment (shareholding company) Tambov Sawolshski Chimsawod Sawolshsk Ukraine Krasitel Rubezhanskoe SOURCE: CEH estimates. Phthalocyanine pigments. in 1991. Phthalocyanine pigments. Pardubice Pigments Produced Azo pigments.and phthalocyanine pigments production was terminated.s. Romania Colorom Codlea Russia Koloros AO Moscow Krata. Various organic pigments. Azo pigments. Capacity will be expanded to 1. Formerly about 95% of the Polish organic pigments production was produced by Organika.2-1. Russia. 3. dry weight basis) 1965 1970 1975 1980 1985 1986 1987 1993 1996 a. Nicolor. Russia and the Ukraine has declined significantly. The plant is reportedly running at high operating rates. SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . Belarus.0 1. in the 1990s.4 9. manufactures phthalocyanine pigments. Turkmenistan. CEH estimates. Commonwealth of Independent States The organic colored pigment industry in the CIS countries is relatively small and highly concentrated and in need of considerable renovation. Georgia. Kazakhstan. Tajikistan.4 7. Organic pigment production in Romania. in Hungary. Moldavia.0008 O PIGMENTS Pigments Page 223 Production Hungary.6 7. Czech Republic VCHZ Synthesia Pardubice is the main organic pigments producer in the Czech-Slovak region. Production of organic pigments started in the 1950s and peaked in 1985. Azerbaijan.4 5. The following table presents historical production data for organic pigments: Former USSR Production of Organic Colored Pigmentsa (thousands of metric tons. Hungary Hungary’s production of pigments was limited to a range of inorganic pigments until the start-up of Nicolor. Kyrgyzstan. which include Armenia. Ukraine and Uzbekistan.0 10.May 2001 575. One of the newer joint ventures.0 Data after 1991 are for the CIS countries only. The majority of the phthalocyanine pigments produced are exported by Dainichiseika to Japan.4 10. with the output destined primarily for export to Japan.8 10. a joint venture of Nitrokémia and Dainichiseika (Japan). Spolek at Usti nad Labem is producing a few organic pigments but total production is small. followed by the Czech Republic are the main organic pigments–producing countries in the region. May 2001 575.0008 P PIGMENTS Pigments Page 224 J APAN Producing Companies The major producers of organic colored pigments are listed in the following table: © 2001 by the Chemical Economics Handbook—SRI International . Dainichiseika Color & Chemicals Mfg. Co. Inc. Anthraquinone. Ltd. Ltd. Ltd.. Most of the companies produce color formulations or inks from the pigments produced. Ltd. CEH estimates based on the Directory of Chemical Producers.. Ltd. Ltd. Anthraquinone Quinacridone..Major Japanese Producers of Selected Organic Colored Pigments—2000 a Pigments Page 225 Insoluble Azo Monoazo (nonlaked) X Disazo Yellow X X X X X X X X X X X X X Toluidine Red Naphthol Red X Permanent (Watching) Red X Soluble Azo Brilliant Carmine 6B X Lake Red (betanaphthol) Phthalocyanine Blue Green Others Company Arimoto Chemicals Co.. Noma Chemical Industry & Co. Sumika Color Co. Ltd. Toyo Ink Mfg. Benzimidazolone Anthraquinone PIGMENTS X X X X X X X X X X X X X X X X X X X X X X X X X Aniline black X X X X X X X X X Dioxazine X X X Anthraquinone May 2001 575. SOURCE: © 2001 by the Chemical Economics Handbook—SRI International . Rhodamine Quinacridone. Fuji Pigment Co.. Ltd. X X X X X X X X X Tartrazine..0008 Q a. Dainippon Ink and Chemicals. Ltd. Kikuchi Color & Chemicals Corp.b Daido Chemical Industry Co.) pigment business was acquired by Clariant (Japan) K. Ltd. Ltd. Sanyo Color Works. Sansui Color Co.K. Co. Ltd. Tokyo Sikizai Industry Co.. Kiwa Chemical Industry Co. Hoechst Japan’s (formerly Hoechst Mitsubishi Kasei Co.. SRI Consulting.. b. Clariant Japan Ltd. on July 1.. 1997.. such as benzimidazolone. consume significant quantities of pigments in ink. DIC.May 2001 575. Fuji Color has its strength in red pigments. The major two coating companies. Kiwa Chemical consumes pigments in fibers and textiles. Dainippon Ink and Chemicals (DIC) and Toyo Ink are the top three organic pigment manufacturers in Japan. in Tianjin. having bought out Tosoh’s quinacridone business unit in 1993. Phthalomex in Mexico. color chip or master batch) each with affiliated companies from outside Japan.A. Kikuchi Color. Bayer and BASF participate in the import market by supplying perylene. Tianjin Toyo Ink Co. Chiba Specialty Chemicals participates in the market by importing specialty pigments. Dainichiseika and Toyo Ink have been importing and exporting pigments.. This plant was expected to have an annual capacity of 1.Ltd. crude. Kansai Paint and Nippon Paint. Toyo Ink also established a joint venture.85 thousand metric tons by the year 2000. which is the leading producer of chrome pigments.. Ltd. Nicolor Co. color concentrates and can coatings. DIC. from plants in Europe. producing phthalocyanine blue crude. Dainichiseika consumes more pigments in plastics and color concentrates than in inks. in Hungary. Sun Chemical in the United States and Denmark. Nippon Pigment has reportedly ceased its production of pigments. The pigment production of Toyo Ink includes phthalocyanine pigment production at Toyo Kasei Kogyo at the plant site of Kawasaki Kasei (Toyo Ink and Kawasaki Kasei each having 50% ownership) where the phthalocyanine crude is produced. and/or surface treated pigment (treated by resin and dispersants. Toyo Ink also has a joint venture. Concerning imports. Sudarsham Chemicals. Toyo Ink and Sakata Inx. Production Historical data on production of organic colored pigments are shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International ... also consume significant quantities of pigments in automobile OEM and other coatings. DIC’s subsidiary. also produce organic pigments. DIC has expanded its share in the automotive basecoat market. Three major ink producers. recently started organic pigments production. Dainichiseika has a pigment production joint venture. DIC has a joint venture in India (29% ownership). with a facility integrated from pigments to printing ink. Those companies have significant quantities of captive consumption to produce downstream products such as inks and colored concentrates. DIC produces phthalocyanine blue crude and pigments at its Kashima plant. Sansui Color has a variety of insoluble azo pigments. such as diketo-pyrrolo-pyrrole (DPP) and anthraqinone (A2B). dimethylquinacridone and isoindolinone. with Pyosa in January 1997 to produce phthalocyanine blue and green.0008 R PIGMENTS Pigments Page 226 Dainichiseika. Clariant (Japan) ceased most pigment production at its Shizuoka site except for a diarylide pigment (PY-83) in Japan and mainly imports of the specialty pigments. Francolor Pigments S. China. DIC and Toyo Ink also consume pigments in plastics. in France is also owned by Toyo Ink and one of its plants at Oissel produces quinacridone pigment. 0% Includes production of high-performance organic pigments such as quinacridones and imidazolones.77 12.04 21.0008 S PIGMENTS Pigments Page 227 Japanese Production of Organic Colored Pigments (thousands of metric tons) Azo Soluble 1975 1980 1985 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 2005 6.41 30.64 0.91 29.37 36 39.31 0.1% 1.24 12.43 0.6% 2.33 15 16. Although the pigment demand in ink is expected to increase 2.13 29.46 12.81 0.32 7.79 0.73 0.76 0.May 2001 575.75 0.86 8.30 0. 1.9% 8.14 13.04 31.07 34.80 0.38 5.25 9.45 31.17 12.32 0.61 0.20 11. resulted from a significant increase of offset ink shipments.56 33.62 0.8 Average Annual Growth Rate (percent) 20002005 a.64 0.07 7.00 5.26 0.63 8.51 5.77 10.63 7.3% annually.78 0.89 13.12 14.08 10.68 27.29 0.84 9.87 8.93 12.95 7.3 Othera 0.51 24.26 8.55 10. production of organic colored pigments is expected to increase 2% through the year 2005.76 0.71 6.34 9.38 7.73 0.5 Lakes 0. (A) Japan Dyestuff & Chemical Industry Association.60 11 12 6. © 2001 by the Chemical Economics Handbook—SRI International .6 0.43 8.23 9.36 13.91 0.61 0.8% 2.4% 4.32 14.30 0.55 31.48 10.54 0.54 9 10 Insoluble Phthalocyanine 7.56 9. SOURCES: Japanese production of organic pigments has been increasing steadily since 1987 and is estimated to reach 36 thousand metric tons in 2000. The average annual growth rate for the 1994-1999 period was approximately 2% and the 5% growth between 1999 and 2000.72 0.52 0.10 27. (B) CEH estimates (estimate for 2005).8 1 Total 15.73 12.31 5.30 25.25 14.65 0.2 0.82 6. as a result of continuing competition with imported products.29 0.25 0.29 7.71 6.83 0.70 33. paint. paint. rubber Insoluble Azo Type 1987 Disazo Yellow (PY 12. plastic Phthalocyanine Greena 2.May 2001 575. production has decreased.88 a.92 1990 4. (A) Japan Dyestuff & Chemical Industry Association. plastic Green color for off-set/gravure ink. But the color quality of the pigment is considered poor.74 Major Application Basic magenta color for off-set ink Advertising in newspaper (inexpensive) Basic magenta color for gravure ink.97 1996 5. excepting Red Lake C and phthalocyanine green.86 1999 7.02 1. probably the result of decreased exports.93 1.06 2.74 1992 4.14 1999 12.78 Major Application Basic yellow color for off-set / gravure ink Phthalocyanine Type 1987 Phthalocyanine Bluea 9.14) 3. Excludes crude cakes.61 1990 4.13.67 1. Red Lake C is used for red color ink in advertising (generally local supermarket advertising) in newspapers.38 Major Application Basic blue color for off-set/gravure ink.73 1996 11. and recently major supermarkets have preferred better color quality in advertising.0008 T PIGMENTS Pigments Page 228 Production by selected organic colored pigments in selected years are broken down as follows: Japanese Production of Major Organic Colored Pigments (thousands of metric tons) Soluble Azo Type 1987 Brilliant Carmine 6B (PR 57:1) Red Lake C (PR 53:1) Permanent Red 2B (PR 48:1.75 1999 6.02 1992 10. such as Brilliant Carmine 6B. 48:2.56 1992 4.38 1990 10. paint. plastic.74 1996 5.45 1. SOURCES: As a result of the continuous increase of ink shipments. production of each organic pigment has shown healthy growth in recent years. (B) CEH estimates. Although the phthalocyanine green consumption in the domestic market is steady.18 1.76 1.22 2.10 2.97 1.79 1.34 1. Consumption Consumption of organic pigments in Japan in selected years is shown in the following table: © 2001 by the Chemical Economics Handbook—SRI International .37 2. 48:3) (Insoluble Azo type) 2.00 1. 2 2.0 0.3 3.3 4.8 1. by replacing dyes. replacing CRT (cathode ray tube) displays and it is believed that Toyo Ink has a strong share of phthalocyanine blue and green pigments.7 0. In these areas.8 4.4 1.3 3. a significant portion of yellow topcoat application for taxis will change to organic pigments and yellow color traffic paint will be replaced by organic (mainly benzimidazolone and possibly DPP or isoindolinone) inorganic (bismuth vanadate) hybrid pigments.2 Quantity 20.9 2. the color in printed pigment materials has 200 years of durable light-stability. SOURCE: In general. State-of-the-art pigment applications. but.2 3.3% per year and this end-use market is expected to be the only driving force for the growth of pigments in Japan. Seiko Epson.4 29. and according to one printer manufacturer. DIC developed microcapsled pigments. offset ink and gravure ink on film substrate (packaging application) will be the major growth area. however. Totals may not equal the sums of the columns because of rounding. the main competition is with dyes.0 0.0 4. CEH estimates. and the key success of pigments are to make particle sizes smaller and increase transparency.0 0. TFT (thin film transistor) displays are the fastest-growing application of color filters for LCD.0 0. crayons. including color filter.3 14. The disadvantage of pigments in this area is that the pigments may clog inkjet nozzles. By 2005.May 2001 575. Chrome pigments will continue to be replaced by organic colored pigments in plastics and surface coating applications.3 33.0 1. Manufacturers are trying to expand into other applications. color toner and other coating applications.3 Includes drawing inks.3 28.3 25. color toner and color filters for LCDs are currently very small quantitively. q q q © 2001 by the Chemical Economics Handbook—SRI International .8 1. moderate growth in demand for organic pigments is expected for the following reasons: q Consumption in printing inks will grow at around 2.6 10 3.9 4. Among the ink shipments.7 2000 Percent 70. For ink jet applications. which has grown drastically in recent years.3 26. which prevents the clogging.8 1998 Quantity 18. 17. b.2 100 2005 Quantity 25. will grow at a high rate.0 1999 Quantity 19. color printer manufacturers recently commercialized pigment type. leather and other uses.0008 U PIGMENTS Pigments Page 229 Japanese Consumption of Organic Colored Pigments 1996 Quantity Printing Inks Paints Plastics Textile Dyeing and Printing Othera Totalb a.0 0.4 2. and Ciba Specialty Chemicals has the biggest share of red pigment (DPP). The growth of special pigments consumption in automobiles is not expected (except yellow taxi topcoats) because of low growth rates for domestic car production over the next five years. such as bubble jet inks.6 1. auto OEM. color filter. SOURCE: Among the specialty pigments. PY-147 PR-254. color filter Chrome pigment replacement. mainly because of chrome yellow replacement. dioxazines and anthraquinones are produced domestically. color toner Auto OEM Isoindoline/one PY-139. trucks).May 2001 575. such as in train cabins and PCM used on vending machines. benzidine-free pigment Pigment resin color in textile. dimethylquinacridones. PY-180 120-150 250-300 Perylene a. Some benzimidazolones.0008 V PIGMENTS Pigments Page 230 Japanese Consumption of Specialty Organic Colored Pigments (metric tons) Major Color Index Generic Name Quinacridone Dimethyl Quinacridone Anthraqinone DPP PV-19 (Mazenda included) PR-122 PR-177. PCM. pigment suppliers are trying to develop markets for quinacridone in other coatings. An increase of some other specialty organic pigments are expected. auto OEM. PCM Auto OEM. industrial coating Chrome pigment replacement. plastic. Coil coating is included in this category in appliances. PCM. b. PCMb Color Toner. quinacridone has a sizable market share. But the recent shift of preferred colors in automobiles by the Japanese resulted in the decrease of red-colored cars and the consumption of quinacridone is believed to have dropped significantly from 1996 to 1999 (possibly a 30-50% drop). PR-179 30-40 40-50 Automobile basecoat at original equipment manufacture. PY-110. The major end-use market for specialty pigments is for automobile basecoats in OEM. auto OEM. ink. PO-69. auto OEM. but now domestic production supplies the majority of demand. but PCM also includes industrial coating in larger structures (such as trains. Precoated metal. coating is processed on metal first and then processed to fabrication. In the past. PR-255 2005 (Expectation) 200 100-120 60-70 40-60 2000 200 60-70 50-60 30-40 Major Application Auto OEMa. PY-173. © 2001 by the Chemical Economics Handbook—SRI International . but many other specialty pigments continue to be imported from European companies. most of the quinacridone pigments were imported. PO-61 70-80 80-90 Dioxazine PV-23 40-50 50-60 Benzimidazolone PY-151. Instead. CEH estimates. plastic Chrome pigment replacement. auto OEM. primarily from Europe. 3 10.1 7.8 121. Estimated prices for selected organic colored pigments in selected years are shown below.4-9.May 2001 575.1 23.140-1.0 130. International Monetary Fund (data for EXCHANGE RATE). International Monetary Fund (information in footnote a). Trade Trade in organic colored pigments since 1981 is shown below.500-2. Japanese Prices for Selected Organic Colored Pigments—2000 Yen per Kilogram Brilliant Carmine 6B (also known as Lithol® Rubine PR-57:1) Disazo Yellow Phthalo Blue Phthalo Green Quinacridone Red Lake C Violet Lake Doller per Kilograma 1.7 a.880 Phthalocyanine 2.191 1.000-8.7-27. reflecting the lower prices for Chinese and/or Indian imports.6-10. © 2001 by the Chemical Economics Handbook—SRI International .700-3.160 2.1-27. (B) International Financial Statistics.500 2.7 (A) Yearbook of Chemical Industries Statistics.8 13.6-74.000 1.400-2.9 113.000 1.000 800-1.000 1. (B) International Financial Statistics .9-23.500-3. Ministry of International Trade and Industry (data for YEN PER KILOGRAM).000 6. SOURCES: (A) CEH estimates.104 2. Market prices of organic pigments have reportedly dropped in recent years.5 15.156 2.160 13.0-18.224 2.012 Exchange Rate (yen per dollar) 94 108.192 2.027 2.8 55. Data are based on an exchange rate of ¥108 per dollar.0008 W PIGMENTS Pigments Page 231 Price Japanese Unit Values for Selected Inorganic Pigments Yen per Kilogram Azo Lakes 1995 1996 1997 1998 1999 SOURCES: 2.920 1. 5 Switzerland 0.03 0. Bayer.11 0.80 0.09 Lakes Exports 0.63 19.11 0.08 0.1 United Kingdom 0.0008 X PIGMENTS Pigments Page 232 Japanese Trade in Organic Colored Pigments (thousands of metric tons) Toners Imports 1981 1985 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCE: 1.42 5. Singapore.66 Exports 9. both phthalocyanine crude and various surface-treated pigments (treated with resin and dispersant) are included in the imports.2 Taiwan 0.09 0. the United Kingdom.70 3. Also.12 Japan Exports & Imports.71 0.64 0. The figures above include exports of phthalocyanine crude.66 4.63 Imports 0. between DIC.09 16. each with affiliated companies from outside Japan.2 United States 0. the Philippines and Indonesia.8 Total 7. There is trading (both imports and exports) of pigments.85 0.08 0.42 0.86 0. specialty pigments are imported by European companies.3 CEH estimates.48 21. Estimated Japanese Trade of Pigments (thousands of metric tons) Import of Pigments by Country of Origin Germany 1999 0. Japan Tariff Association.05 13.98 18.1 Others neg Total 1.9 France 0.22 2.25 3. © 2001 by the Chemical Economics Handbook—SRI International .69 22.40 19.08 0. Dainichiseika and Toyo Ink. such as Ciba Specialty Chemicals. both crude and surface-treated pigments.6 The “other” destinations include Malaysia.10 18.42 0.66 0.70 0. Also.9 Thailand 0. The estimated pure pigment imports and exports in 1999 are listed below.10 0.4 Export of Pigments by Destination Country United States 1999 SOURCE: 1. Clariant and BASF.14 4. Hong Kong/China 1.5 Others 2.84 3.02 0.4 France 0.92 19.66 2.45 3.07 0.05 0.47 0.07 0.90 19. the Republic of Korea.82 20.May 2001 575.63 5.87 5. . Ltd. Ltd. Sigma Pigments Mfg. Yih Chen Chemical Industry Co. Tong Kung Industrial Corp. Songwon Color Co.. Tah Kong Chemical Ind..May 2001 575. Ltd. Dioxazine Pyrazolone. Ltd. Indonesia Monokem Surya PT SOURCE: X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X CEH estimates based on Directory of Chemical Producer. Ltd. Ltd. SRI Consulting © 2001 by the Chemical Economics Handbook—SRI International . New Hsin Jung Enterprise Co.0008 Y PIGMENTS Pigments Page 233 O THER ASIAN COUNTRIES The major producers of organic colored pigments are listed in the following table: Major Asian Producers of Selected Organic Colored Pigments—2000 Insoluble Azo Soluble Azo Lake Red (betaPhthalo naphthol) Blue Company Korea. Fu Tai Chemical Industry Co. Rhodamine Ukseung Chemical Company Ltd. Monoazo Permanent Brilliant (nonDisazo Toluidine Naphthol (Watching) Carmine laked) Yellow Red Red Red 6B Other X X X X X X X Pyrazolone X X X X X X X X Pyrazolone.. Maintop Industrial Co.. Corp.. Janie Color Works Ltd. Nan Tsan Industry Co.. Taiwan Cosmos Colorants Co. Ltd.. Well Chem Products Inc. Republic of Daihan Swiss Chemical Co. Ltd.. Co. Ltd. 0 1.4 1.0008 Z PIGMENTS Pigments Page 234 The table below is the estimation of salient statistics in selected Asian countries: Salient Statistics of Organic Color Pigments in Selected Asian Countries (thousands of metric tons) China Production of Organic Pigments in China Azo Pigments 1997 1998 1999 2.1 0.0 1.1 0.1 Export 0.1 0.4 Export 1.1 8.1 0.7 Production Total 4.4 2.5 5.4 Production Total 7.7 14.1 na Lakes 0.4 Export 3.4 Export 0 0 0 Korea.0 7.9 1.1 0.3 na Other 2 2 na Production Total 7.1 0.0 Pigment Apparent Consumption 11.4 Phthalo Blue 2.4 4 4.6 Pigment Import 1.5 15.4 0.9 10.7 Apparent Consumption 4.May 2001 575. China National Chemical Information Center (China production).4 4.9 Phthalocyanine na 1.4 6.5 0.3 0.2 SOURCES: (A) Korean Dyestuff and Pigments Industrial Association (Republic of Korea production).3 2.8 1.9 1.4 6.1 0. (E) CEH estimates.4 1.5 Taiwan Production of Organic Pigments in Taiwan Diazo 1997 1998 1999 na 1. Republic of Production of Organic Pigments in the Republic of Korea Azo 1997 1998 1999 2.1 Other na 0.2 3.1 0 0. (D) Trade data of each country.3 5.2 Other 1.5 0.2 0. (C) China Chemical Industry Yearbook.6 4.8 Trade Lakes Import 0 0 0.0 Lake 1.7 14.8 na Phthalocyaninies 2.6 Phthalo Green 0.2 Naphthol na 0.7 11.6 2.1 Apparent Consumption 5.1 0.2 Export 0.2 1.3 2.0 Import 11.3 0.4 Trade Lakes Import 0. (B) Taiwan Dyestuff and Pigments Industrial Association (Taiwan production).8 Monoazo na 1.3 1. China The major Chinese producers of organic pigments are listed in the following table: © 2001 by the Chemical Economics Handbook—SRI International .6 1.1 3.4 Export 7.4 1.8 Trade Lakes Import 0.3 Pigment Import 2.2 15.3 1. Ltd. Through joint ventures. Ltd. Nangong Qing-Alpha Chemical Co. © 2001 by the Chemical Economics Handbook—SRI International . 1 Dyestuff Chemical Plant Shanghai Toyo Ink Co. Wenzhou Huanan Chemical Industry Corp. Concerning the specialty pigments. Clariant Chemical has a majority share of its joint venture (ownership of 51%).5 thousand metric tons. Songwon Color.. Changshu Chemical & Medical Industry Bureau Chongqing Dyestuff Factory Clariant Pigments (Tianjin) Ltd. b. Ltd. 2 Dyestuff Chemical Factory Tianjin No. The Republic of Korea’s organic pigment market share is almost evenly divided by three companies (these two joint ventures and Ukseung Chemical). with an azo pigments production capacity of 3..0009 A PIGMENTS Pigments Page 235 Major Chinese Producers of Organic Colored Pigments—2001 Company Anhui Sanquen General Chemical Plant BASF Colorants & Chemicals Co. Ltd. (A) The People’s Republic of China Chemical Industry . 8 Dyestuff Chemical Plant Tianjin Toyo Inc Co. 2 Fertilizer Plant Zhejiang General Chemical Industry Corp.May 2001 575. Ltd. Ltd. which is supplied by Ciba Specialty Chemicals and Clariant Chemical. Zhejiang Xiaoshan Pigment Chemical Plant Zhenjiang City Paint Factory a.7 thousand metric tons capacity and build up new capacity of 2 thousand metric tons) to enhance competitiveness with the latest equipment by 2000.. the consumption of quinacridone is estimated around 50-80 metric tons in 1999.. The Scientific & Technical Information Research Institute of the Ministry of Chemical Industry of the People’s Republic of China. Shenyang General Fertilizer Plant Tianjin No. Ltd. Azo Phthalocyanine X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X Lakes Other SOURCE: Republic of Korea Daihan Swiss Chemical is a joint venture established by Ciba Specialty Chemicals and Daihan Color in 1982. SRI Consulting. (B) 2000-2001 Directory of Chemical Producers—China. Qingdao Chiba Pigmentsb Qingdao Dyestuff Factory Ruian Wanlong Chemical General Manufactory Shanghai Dyestuff Co. Beijing Chemical Industry Group Corp... Xiangtan Chemicals and Pigments Co.b Yancheng County No.. Ningbo Jinbao Group Co. Chiba announced scrap-and build operations (to scrap 1. Ciba Specialty Chemicals joint ventures. Shanghai No. Dainippon Ink and Chemicals Meileda Pigment Industry Co. APPENDIX—SPECIAL EFFECT PIGMENTS Special effect pigments are an increasingly important group of pigments. ultrafine aluminum particle. one of which. Nacreous pigments (pearlescent pigments)—regular reflection takes place mainly on flat and parallel metal pigment particles (e. aluminum flakes).. Ltd. They cause an optical effect by regular reflection or interference. ultrafine bronze particle).6 thousand metric tons in 2003-2004). Special effect pigments can be classified further into several groups: q Metal effect pigments—regular reflection takes place on highly refractive parallel pigment platelets (e. The domestic organic pigment demand is roughly estimated at around 15 thousand metric tons in 1999. constructed 200 metric tons of quinacridone capacity in 2000. India There are over 100 pigment producers in India.. and Tianjin Toyo Ink Co. black or colored pigments and they are either naturally derived (inorganic and organic) or synthetic (inorganic) pigments. Ciba Specialty Chemicals has two joint ventures in China. Hindustan Ink and Resin is a major independent export-oriented producer of finished inks as well as organic pigments such as PY-12. dioxazine pigments (PV-23) and other organic pigments are also exported. including quinacridone. at Hunan province. which produces phthalocyanine pigments and other organic pigments. Among them. China There are numerous pigments producers in China.. Qingdao Chiba Pigments. © 2001 by the Chemical Economics Handbook—SRI International q .g. Sudarshan Chemicals Industries. Production quantities are unknown. The production statistics in 1997/1998 may be understated.. Toyo Ink has two joint ventures in China. has opened in Qingdao with a local company to manufacture azo pigments with 2 thousand metric tons capacity in 1997 (its capacity will be increased to 3 thousand metric tons in the near future).4 thousand metric tons (this capacity will be increased to 5. Another new joint venture.May 2001 575. PR-57:1 and PB 15:3. Special effect pigments are available as white.. China’s exports emphasize phthalocyanine blue (PB-15:3) and green (PG-7).g. TiO2 on mica. These effects can include viewing angle-dependent color (different viewing positions causing color shifting). DIC has a joint venture. Xiangtan Chemicals and Pigments Co.. Ltd.. major pigments producers are Tah Kong Chemical Industrial. Janie Color Works and Cosmos Colorants.0009 B PIGMENTS Pigments Page 236 Taiwan There are several local pigments producers in Taiwan as listed in the table above. India’s exports emphasize phthalocyanine green and blue. Shanghai Toyo Ink Co. Ltd. with a total capacity of 4. thermal and mechanical stability. The type of metal oxide and the thickness and number of metal oxide layers determines the final color of the luster pigment. can be used alone or in combination with titanium dioxide.and metal-color pigments can be produced. q q q q q © 2001 by the Chemical Economics Handbook—SRI International . Semitransparent effect pigments can also be produced using silica flakes coated with titanium dioxide or ferric oxide. From an optical perspective. is the fact that this compound contains lead and is therefore under significant pressure from a toxicological and environmental perspective. Some of the fish scales used are of herring. These types of luster pigments have advanced to the most important group of luster pigments. rapid sedimentation and limited mechanical stability.May 2001 575. More critical today. it is an ideal product but some of its physical characteristics limit its use. in order of importance: q Alumina–metal oxide. iron oxide on mica). other applications are rather limited.g. Depending on the precipitation process. These pigments can create multicolor effects depending on the viewing angle. Micronized titanium dioxide. metal oxide–mica pigments are being used in practically all pigment applications where a special optical effect is required. Because of the smaller size of this pigment. Their main advantages are their favorable optical. Silica flake. production costs are relatively high.. Basic lead carbonate is obtained through the reaction of lead acetate or propionate with carbon dioxide.0009 C q PIGMENTS Pigments Page 237 Interference pigments—the optical effect of colored luster pigments is caused entirely or mainly by the phenomenon of interference (e. Fish silver is used mostly in cosmetic applications (primarily in nail enamels). Fish silver is still commercially produced today. Because of its relatively low lightfastness. iron oxide. Although fish silver (natural fish scales based on guanine and hypoxanthin) was the very first commercially used luster pigment. a pearlescent effect is caused through interference. Because of their good chemical. however. A large number of combination. Bismuth oxychloride luster pigments are used primarily in cosmetic applications. chemical. The yield of pearl essence. From a chemical point of view the commercially available nacreous pigments can be classified into the following type of products. The pigment concentration in fish scale is usually less than 1% and. This compound was one of the very first nontoxic pearlescent pigments produced. basic lead carbonate is used in developing countries for the manufacture of buttons and artificial pearls. It is manufactured through the hydrolysis of the chloride ions available in an acidic bismuth salt solution. as opposed to the opacity caused by standard titanium dioxide pigments. mechanical. in in the mineral form of muscovite. hence. accounting for about 50% of the total world market today. where its physical and chemical sensitivity is not critical. depends largely on the type of fish. Natural pearlescent (natural fish silver). inorganic luster pigments clearly dominate the market today. tin oxide and chromium oxide. a number of pigments with different optical and physical characteristics can be obtained. ukelei and sardines. Effects produced include high chroma sparkle. Still. mica. Basic lead carbonate. toxicological and environmental characteristics. Bismuth oxychloride. obtained through solvent extraction of fish scales. Mica. Basic lead carbonate has poor chemical and thermal stability and its high density leads to a relatively quick sedimentation in the carrier material. United Kingdom X X X X X X X X X Xa SilBerCote® Sparkle Silver® Tufflake® Sudarshan Chemical Industries Ltd. Taiwan X X © 2001 by the Chemical Economics Handbook—SRI International .. United States (subsidiary) Merck Japan Ltd. United States (subsidiary) EM Industries. Germany X X X X X X X X Colorstream™. United Kingdom Dr. Republic of Korea Pearl Essence. India Taica. Iriodin. Germany Other Ecakrt-Werke. Norway Poliperl S.A. Xirallic™ Rona. Republic of Korea Silberline Manufacturing Company.. (subsidiary) Pacific Chemicals. Germany X X X Helicone® liquid crystal Williams. Variocrom® Xab Litho® PHOENIX®. United States Merck KGaA.0009 D PIGMENTS Pigments Page 238 The following table lists some of the major world producers of special effect pigments: Major World Producers of Special Effect Pigments—2001 Natural Pearl Basic Lead Carbonate Bismuth Oxychloride Silica Flake Metal Oxide– Mica X Trade Names Paliocrom®. Jaeger GmbH. United States Semo Ltd. Germany Englehard. United States J. Mearl Division. Sicolux®.May 2001 575. Argentina Presperse Inc. Mearlite Company BASF Aktiengesellschaft. Japan Wacker. Toto Flex® Roto Safe® Mearlin... Germany Kemira Oy. Yang Chemical.. Finland Mallinckrodt. 000 Consumption Trends Increasing Increasing Stable Declining Increasing The main applications of special effect pigments are in printing inks. The total world market size for special effect pigments is estimated at roughly 10 thousand metric tons. 5. Aluminum pigments. Menlo Park. b. Cosmetic Chemicals Printing Inks Specialty Paper Chemicals © 2001 by the Chemical Economics Handbook—SRI International . plastics. CEH estimates. Shown in the following table are estimated world consumption figures for special effect pigments: World Consumption of Special Effect Pigments—1999 Metric Tons Metal Oxide–Mica. Silicon Oxide Natural and Synthetic (titanium dioxide) Pearlescent Bismuth Oxychloride Basic Lead Carbonate Others Total SOURCE: CEH estimate.000 3. SRI Consulting. SOURCE: Englehard (Mearl Division) and Merck are the leading producers. product reviews and industry overview contain additional information that is pertinent to the subject of this marketing research report: Carbon Black Dyes Inorganic Zinc Chemicals Paints and Coatings Industry Overview Specialty Inorganic Fibers Titanium Dioxide Pigments Specialty Chemicals Update Program—The following SCUP reports contain additional information on the subject of this report.000 500 <500 1. wallpaper and decorative laminates.000 10. California 94025. They are also used in adding special-effect coloring to fine paper. Address inquiries concerning this information to Specialty Chemicals Update Program.0009 E PIGMENTS Pigments Page 239 a. Bronze pigments. paints and coatings. textile printing and cosmetics.May 2001 575. BIBLIOGRAPHY Chemical Economics Handbook—The following CEH marketing research reports.