CEH Marketing Reports - Pigments

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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:
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CEH OnlineThe full text retrieval and update database. Updated monthly. CEH CD-ROMThe 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: ZrichTelephone: TokyoTelephone: 650/859-3900 411/283-6333 813/5251-1741 Fax: Fax: Fax: 650/859-2182 411/283-6320 813/5251-1754
2001 by the Chemical Economics HandbookSRI International
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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............................................................................................................................
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
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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........................................................................................................................
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
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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................................................................................................................................
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
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Price ............................................................................................................................................. Trade ............................................................................................................................................ Other Asian Countries ..................................................................................................................... Producing Companies .................................................................................................................. China............................................................................................................................................ Producing Companies .............................................................................................................. Trade ........................................................................................................................................ Republic of Korea........................................................................................................................ Producing Companies .............................................................................................................. Trade ........................................................................................................................................ Taiwan ......................................................................................................................................... Producing Companies .............................................................................................................. Trade ........................................................................................................................................ Organic Color Pigments .......................................................................................................................... Description........................................................................................................................................... Azo Pigments................................................................................................................................... Phthalocyanine Pigments................................................................................................................. Condensation Acid Pigments........................................................................................................... Quinacridone Pigments.................................................................................................................... Perylene Pigments............................................................................................................................ Other Organic Pigments .................................................................................................................. Manufacturing Processes ..................................................................................................................... Azo Pigments................................................................................................................................... Phthalocyanine Pigments................................................................................................................. Quinacridone Pigments.................................................................................................................... Basic Dye Pigments......................................................................................................................... Supply and Demand by Region ........................................................................................................... United States.................................................................................................................................... Producing Companies .................................................................................................................. Salient Statistics........................................................................................................................... Consumption................................................................................................................................ Printing inks............................................................................................................................. Paints and coatings .................................................................................................................. Plastics, pigmented fibers and rubber ...................................................................................... Other ........................................................................................................................................ Price ............................................................................................................................................. Trade ............................................................................................................................................ Imports..................................................................................................................................... Exports..................................................................................................................................... Canada ............................................................................................................................................. Producing Companies .................................................................................................................. Trade ............................................................................................................................................ Mexico ............................................................................................................................................. Producing Companies .................................................................................................................. Trade ............................................................................................................................................ South America ................................................................................................................................. 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
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Western Europe................................................................................................................................ Producing Companies .................................................................................................................. Azo pigments ........................................................................................................................... Phthalocyanine pigments......................................................................................................... Other organic pigments............................................................................................................ Production.................................................................................................................................... Consumption................................................................................................................................ Printing inks............................................................................................................................. Paints and coatings .................................................................................................................. Plastics and rubber ................................................................................................................... Pigmented fibers ...................................................................................................................... Textile printing ........................................................................................................................ Pigments for paper ................................................................................................................... Other ........................................................................................................................................ Price ............................................................................................................................................. Imports..................................................................................................................................... Exports..................................................................................................................................... Eastern Europe................................................................................................................................. Producing Companies .................................................................................................................. Production.................................................................................................................................... Czech Republic........................................................................................................................ Hungary.................................................................................................................................... Commonwealth of Independent States .................................................................................... Japan ................................................................................................................................................ Producing Companies .................................................................................................................. Production.................................................................................................................................... Consumption................................................................................................................................ Price ............................................................................................................................................. Trade ............................................................................................................................................ Other Asian Countries ..................................................................................................................... China............................................................................................................................................ Republic of Korea........................................................................................................................ Taiwan ......................................................................................................................................... China............................................................................................................................................ India ............................................................................................................................................. 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
AppendixSpecial Effect Pigments ....................................................................................................... 236 Bibliography ............................................................................................................................................ 239
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SUMMARY WORLD MARKET SIZE

In 1999, the world market value for colored pigments (inorganic and organic) reached $7.5 billion$2.6 billion for inorganic color pigments and $4.9 billion for organic pigments, of which high-performance organic pigments accounted for $1.1 billion. Between 1996 and 1999 the global color pigments market has been impacted by declines for prices for most pigments classes. 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 Class1999 (total market value = $7.5 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, 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; however, over the same period the U.S. dollar increased in value by 17% relative to the Euro. Therefore, stated in Euro terms, the global pigment market appreciated by 25% between 1996 and 1999, while in dollar terms it grew by only 7%. 2001 by the Chemical Economics HandbookSRI International
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With a 37% market share, Western Europe is the largest colored pigmentsproducing region, followed by North America with 28%, while Asia accounted for 25% of the total market. The following graph shows the world market value in 1999 by region, for the three main organic pigment classesclassical azo pigments, phthalocyanine pigments and organic high-performance pigments:
World Market Value of Organic Pigments by Region and Chemical Class1999
1,600 1,400 1,200 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, Other
Japan
a. Includes all organic pigments.
North America and Europe (i.e., Western and Eastern Europe) are clearly the largest markets for organic pigments. Together with Japan, these regions also account for the dominant share of the most profitable pigments markethigh-performance pigments. Shown below is the world market value by type of organic pigment.
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World Market Value of Organic Pigments by Chemical Class1999

High-Performance Pigments 12%
Phthalocyanine Pigments 29%
Azo/Other 59%
Total Market Value = $4.9 billion
With a 59% world market value share in 1999, azo pigments are the largest group of organic pigments, followed by phthalocyanines (blue and green), with a share of 29%. 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, while the high-performance pigments group typically retains higher margins. This latter group is dominated by the leading organic pigment producers: Clariant, Ciba Specialty and BASF. The following table summarizes the world pigments consumption in value terms in 1999. The data include all major pigment applications, printing inks, paints and coatings and plastics, as well as textile printing, paper and leather, but exclude consumption of special effect (pearlescent/ luster and metallic pigments) and anticorrosion pigments.
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World Market Value of Color Pigments by Region1999 (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 2,551
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,551 Azo/Other Phthalocyanine High-Performance Total Total Colored SOURCE:
641 529 395 1,565 2,260
84 74 31 189 350
557 446 269 1,272 2,138
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
2,114 1,695 1,099 4,907 7,458
CEH estimates.
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WORLD SUPPLY/DEMAND
LEADING PRODUCERS In general, pigment producers specialize either on the manufacture of inorganic pigments or organic pigments. Only a few companies manufacture both pigment groups; Bayer, BASF and Ciba manufacture both, however, for BASF and Ciba, the inorganic pigment business is significantly smaller. This tendency to specialize is attributable to the differences between inorganic and organic pigments in:
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manufacturing processeshaving no chemistry in common volumesorganic pigment market segments typically are smaller market segmentsfew applications in common prices and premiumsinorganic pigments tend to be less expensive, while organic pigments typically have higher prices and higher premiums.
INORGANIC PIGMENTS The largest inorganic pigment is synthetic iron oxide. Worldwide, the top four producers of synthetic iron oxide pigments in 2000 are ranked as follows: Bayer, which holds roughly half of the worlds market; Elementis; Laporte (acquired by Kohlberg, Kravis Roberts); and Toda Kogyo. Their headquarters and manufacturing locations are shown in the following table:
Worlds Largest Synthetic Iron Oxide Pigment Manufacturers Company, Headquarters Bayer, Germany Manufacturing Locations Brazil China (finishing plant) Germany China United Kingdom United States China Germany Italy United Kingdom United States Japan
Elementis, United Kingdom
Rockwood Pigments, United States
Toda Kogyo, Japan SOURCE: CEH estimates.
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O RGANIC PIGMENTS The worlds largest organic pigment manufacturers include four Western European firms, followed by three Japanese companies; headquarters and manufacturing locations are shown in the following table:
Worlds Largest Organic Pigment Manufacturers Company, Headquarters BASF, 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, Inc., Japan China (Suzhou Lintong Dyestuff Chemical Co Ltd.) Japan Denmark (KBK) India (Shudishan) United States (Sun Chemical) Japan France (Francolor) Mexico
Bayer, Germany
Ciba, Switzerland
Clariant, Germany
Dainichiseika Color and Chemicals Mfg. Co., Ltd., Japan
Toyo Ink Mfg. Co., Ltd., Japan
SOURCE:
CEH estimates.
Clariant, followed closely by Ciba Specialty, are the market leaders of organic pigments. At some distance follow BASF and other listed companies. Within the large-volume group of phthalocyanine pigments BASF is the worlds leading producer.
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PRODUCTION Total world production of white, black and colored pigments reached 5.7 million metric tons in 1999. Of this volume approximately 68% was titanium dioxide, 16% iron oxide pigments, about 8% pigment-grade carbon black and only 8% for other colored pigments, including organic pigments. The following graphs show the estimated world production by major pigment group in 1999:
World Production of Pigments1999
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 = 5.7 Million Metric Tons
Synthetic iron oxides represent the largest share of the worldwide colored pigments market and production is dominated by Western Europe. Likewise, of the three major regions covered in this report, Western Europe leads in production of chrome (or chromium) pigments and organic pigments and in the total production of all colored pigments. The United States is a significant producer of organic pigments, accounting for about 25% of total world production. Asia has become an important organic pigments producing region in volume terms. Five countries, including Japan, China, India, the Republic of Korea and Taiwan, account for most Asian production. During the last decade production of and demand for organic pigments in Eastern Europe has declined sharply and is only now gradually stabilizing. The figures below illustrate world production of organic pigments by region and chemical class in 1999, as a percent of the total on a dry weight basis.
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World Production of Organic Pigments1999 (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, phthalocyanine blue and green, accounted for nearly 26% of total organic pigments production in 1999. About 60% of organic pigments have an azo structure in their molecule. Most of the phthalocyanine- and azo-based pigments are considered to be in the lower- to medium-value group of products. The high-performance products are found primarily in the polycyclic pigments. Among the most expensive pigment groups are pigments such as diketo-pyrrolo-pyrrole quinacridone, anthraquinone and perylene. The business of these pigments is, however, in the hands of only a few international companies.
CONSUMPTION The world consumption of white, black and colored pigments reached approximately 5.7 million metric tons in 1999. The following table gives an estimate of the world pigments consumption by region and main pigment class:
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World Consumption of Pigments by Region1999 (metric tons, 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
172,304 282,000 19,709 7,250 9,046 6,600 2,000 362 172
47,640 47,640 4,000 2,000 2,154 2,382 538 300 12
94,671 350,000 13,000 22,500 8,077 6,300 4,000 500 300
17,118 30,000 2,500 1,000 400 1,500 400 400 0
28,181 64,581 3,200 1,400 862 2,692 754 377 0
52,030 48,800 4,700 4,600 4,308 1,800 500 100 50
53,595 95,280 16,600 4,000 3,525 1,200 2,000 350 30
5,496 8,793 1,000 500 108 440 50 0 5
471,034 880,094 64,709 43,250 28,478 22,914 10,242 2,389 569
4 327,144
1 59,027
5 404,682
0 36,200
0 73,866
1 64,859
1 122,986
0 10,895
13 1,099,659
53,000 21,350 10,550 84,900 365,044 1,887,348
6,908 2,978 834 10,719 69,746 309,886
46,000 18,000 7,200 71,200 475,882 1,694,553
3,000 2,700 300 6,000 42,200 200,318
6,677 4,200 754 11,631 85,496 237,177
14,300 7,380 6,520 28,200 93,059 410,189
17,230 15,400 3,769 36,399 159,385 872,980
700 600 200 1,500 12,395 61,491
147,815 72,607 30,127 249,049 1,348,708 5,719,441
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SOURCE:
CEH estimates.
1,338,000 12,000
189,000 3,500
1,112,000 12,000
137,000 4,000
120,000 3,500
261,000 4,100
652,000 8,000
42,600 1,000
3,851,600 48,100
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Titanium dioxide, the most important white pigment, accounted for 68% of total world pigment consumption by weight. From this perspective it is understandable that much of the market attention is focused on this single pigment. Because of this, titanium dioxide and carbon black are each described in detail in separate marketing research reports. The color pigments, which are described in this report, accounted for about 24% of the total pigment consumption in 1999. Within color pigments, iron oxide pigments are the largest in volume terms. Iron oxide pigments accounted for about 65% of the total color pigments consumption in 1999. The United States is the largest color pigmentconsuming country, accounting for about 22% of the total consumption. Western Europe is, however, the largest consuming region, accounting for about 37% of total consumption. Three main applicationsprinting inks, paints and coatings and plasticsaccounted for about 88% of total organic pigments consumption in 1999. The following pie chart gives the world consumption in volume by main application for 1999:
World Consumption of Organic Pigments by Market Value1999
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, is expected to change steadily during the next decade. Some of the most important challenges for pigment producers will be to cope with the rapid globalization of the business, the maturing markets in some applications and regions, the continued oversupply of classical pigments (keeping prices depressed) and the ever increasing environmental pressures. The major business trends are described below.
DEMAND The consumption of pigments is driven primarily by growth in the printing inks, paints and coatings, and plastics industries. Worldwide markets for pigments are expected to grow more or less in line with GDP during the next five years. In Japan, the demand for pigments is expected to grow only slightly, with a slightly stronger growth for Western Europe and stronger growth for the United States. In Asian countries
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other than Japan, primarily China and India, demand for pigments will grow significantly, particularly in surface coating applications but also for printing inks. For the export market, China will require more sophisticated pigments for colored plastic goods, as well as for pigment-printed textiles. 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, averaging 4-8% per year during 1999-2004. Overall it can be expected that during 1999-2004, the market value in Asia (excluding Japan) will grow by 5-6% per year. In South America, the domestic demand for pigments is expected to grow modestly, possibly above the growth rate in North America. Actual value increases, however, will not be spectacular, remaining well below the increase in any of the three major countries/regions. The largest end-use markets for color inorganic pigments are construction, paints and coatings, plastics and ceramics. Color organic pigments are consumed mostly for printing inks, followed by paints and coatings and plastics. Total consumption of iron oxide pigments by volume will grow moderately over 1999-2005, with continued demand from the construction industry, which is the largest market for iron oxides. One of the two major classes of chrome pigments, green chromium oxide, will experience moderate growth. Consumption of the other major class, lead chromates (primarily chrome yellow, chrome orange and molybdate orange), is expected to continue to decline, as will consumption of cadmium pigments. Health and environmental concerns about heavy metalcontaining pigments and increased competition from organic replacements are adversely affecting overall consumption of lead chromate and cadmium pigments. However, in a few regions such as Asia and Oceania, consumption of cadmium pigments, while smaller than in the United States or Western Europe, is still increasing gradually. Worldwide consumption of complex inorganic pigments will experience some growth in volume, aided by their partial absorption of the markets lost by cadmium and chrome pigments. During 1999-2004, color organic pigment consumption in the three major regions combined will grow 2.5 to 3.0% per year by volume. The highest growth rate will be in plastics applications, where the development and use of specialty high-performance organic products continues to increase.
SUPPLY The production of low- to medium-tier products is expected to continue to migrate from Western Europe and the United States to the lower-cost countries, such as China and India (e.g., iron oxide pigments, commodity-type azo pigments and phthalocyanine pigments) and, to a lesser degree, South America (primarily Argentina and Brazil).
MARKET PARTICIPANTS During the last decade, the color pigments industry has passed through a period of significant restructuring, responding to the globalization of pigment markets, competitive factors and the impacts of environmental regulations. A number of smaller producers, unable to compete with larger international firms, closed their plants or were acquired by larger, mainly Western European or Japanese firms. Product lines were realigned toward the more profitable, higher-value pigments. In early 2001, color pigment producers in the United States, Western Europe and Japan were distributed as follows:
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Number of Color Pigment Producers by Major Region2001a Inorganic United States Western Europe Japan Total a. 20 40 14 74 Organic 18 11 16 45 Total 38 51 30 119
Excludes white pigments and carbon black. Because some companies produce both inorganic and organic pigments, each number represents the net number of corporate entities involved in that particular region(s) or pigment category. For this reason, the totals do not equal the sums of the categories. CEH estimates.
SOURCE:
As a result of the anticipated market changes discussed above, the producers of pigments are faced with significant challenges as well as opportunities:
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Prices are becoming uniform between regions as markets become increasingly efficient and global. 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. Large producers are finding their competitive strengths by streamlining their product ranges and shifting production to lower cost countries. Toll manufacturing and swap deals will become even more important. The downstream integration of pigment producers to end-use markets, such as the printing inks, plastics and spin-dyeing markets, will continue as pigment producers secure their shares in the increasingly competitive market. In Asia and particularly in China and India, new opportunities are further developing for international companies. On the demand side, many of the Asian countries have clearly emerged as the most rapidly growing markets for pigments, including high-performance pigments. On the supply side, the sourcing of unfinished (requiring grinding, coating, etc.) large-volume pigments from lower-cost production sites in these countries helps sustain corporate profit margins. A strong local market presence is required in order to capture a sizeable volume of this growing business.
PRODUCT RANGE From a product portfolio perspective, some of the most important challenges to producers will include:
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A continued phase-out of heavy metalcontaining pigments. These pigments will be replaced by organic, as well as novel inorganic pigments (e.g., complex inorganic color pigments, bismuth vanadate and rare earth sulfide pigments). It can be expected that heavy metal pigment substitution will be completed in the United States, Japan and Western Europe within a few years. The other countries will soon have to follow suit, particularly for pigments used in end products
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that are destined for Western markets. In many cases, producers of heavy metalbased color inorganic pigments will be facing critical decisions regarding their viability to remain in the pigments business at all.
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In the surface coating and printing ink markets, producers will have to continue to modify their pigment lines to ensure acceptance in more environmentally acceptable technologies (e.g., waterborne coatings, powder coatings and radiation-curable inks and coatings). Small- to medium-sized producers of pigments, in particular, will have to invest in R&D to be in a position to offer new products and customized service (e.g., customized pigment dispersions, pigments with increased fastness and heat stability).
INTRODUCTION
The worldwide pigments industry produces hundreds of colorant, extender and functional pigments for a wide spectrum of industrial and consumer markets.* The major markets are paints and coatings, plastics (including spin-dyed fibers) and construction materials. Other markets include paper, ceramics, elastomers, inks, textiles, glass, food and cosmetics. This report focuses on pigments classified as colorantsthose that possess opacity and contribute to the color or color-related properties of the vehicles into which they are incorporated. 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. Further information on these pigments (including metal flakes) may be found elsewhere in the Chemical Economics Handbook. The data are segmented first by inorganic color pigments and organic color pigments and then geographically by North America, Western Europe and Japan, which together produce and consume the majority of the worlds pigments. In addition, information is presented for South America, Eastern Europe, China, the Republic of Korea and Taiwan. Further, within each geographic segment, the supply of and demand for each major colorant groupiron oxides, chromes, complex inorganics, cadmiums, other inorganics and organicsare treated separately. White pigments, primarily titanium dioxide and black pigments, primarily carbon black, are only mentioned briefly since titanium dioxide and carbon black are extensively treated in the CEH marketing research reports on those subjects. Pigments can be defined as follows: Color, black, white or fluorescent particulate organic or inorganic solids which usually are insoluble in and essentially physically and chemically unaffected by, the vehicle or substrate in which they are incorporated. They alter appearance by selective absorption and/or by scattering of light. Pigments are usually dispersed in vehicles or substrates for application. Pigments retain a crystal or particulate structure throughout the coloration process. In contrast, dyes are soluble and/or go through an application process which, at least temporarily, destroys any crystal structure of the color substances, according to the Ecological and Toxicological Association of the Dyestuff Manufacturing Industry (ETAD). *
An extender pigment is a pigment used to reduce cost per unit volume by increasing bulk. 2001 by the Chemical Economics HandbookSRI International
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Pigments serve several functions; the two primary ones are as colorants and extenders. Other functional applications include providing corrosion or heat resistance, antifouling capability, rubber acceleration activation and reinforcement. Pigments may be segregated in any one of several different ways. In this report the criteria on which the classification system is based are as follows: (1) colorantblack, white or color, (2) chemical type organic or inorganic, (3) originnatural or synthetic and (4) chemical structure. 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
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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 Guignets Green PG-18 Chromium Phosphate or Arnavdons 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
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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
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Representative Pigments by Chemical Class and Color (continued) Inorganic Pigments (continued) Other Inorganic Pigments Bismuth Vanadate PY-184 Iron Blues or Ferriferrocyanides or Chinese, 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
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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
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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, Metal-Free PB-16
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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 1,4-Diketo-pyrrolo-pyrroles (DPPs) PR-254 PR-255 Flavanthrone Yellow Fluorescent Organic Pigments Indanthrone Blue Isoindolines, 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.
The following table presents the commercially most important organic pigments, arranged by color as well as by chemical constitution. The largest-volume products are boldfaced.
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Commercial Organic Pigments by Color Index and Chemical Classa Yellow Azo Pigments Monoazo Nonlaked Orange Red Violet Blue Green Brown Black
1 , 3, 5, 6, 60, 65, 73, 74, 75, 97, 98, 111, 116 113, 168, 169, 183, 190, 191 120, 151, 154, 180 , 181, 194
Benzimidazolone Disazo Bisacetoacetarylide Diarylide
36, 60, 62
171, 175, 176, 185, 208
32
25
116, 155 12, 13, 14, 17, 55, 63, 81, 83, 87, 114, 121, 126, 127, 136, 152, 170, 171, 174, 176 15, 16
Pyrazolones Disazo Condensation 93, 94, 95, 128
13, 34 31
37, 38, 41, 111 144, 166, 214, 220, 221, 242, 248, 262 257 1, 3, 4, 6 2, 5, 7, 8, 9, 10, 12, 13, 14, 15, 17, 18, 21, 22, 23, 31, 112, 119, 136, 146, 147, 170, 184, 187, 188, 210, 252, 256 25 25 1 8, 10 23, 41
Metal Complex Naphthol Naphthol AS
117, 129, 150, 153, 177, 179
59, 65, 68 2, 5 22, 38
Red Lakes BONA
48:1, 48:2, 48:3, 48:4, 52:1, 52:2, 57:1, 58:4, 63:1, 200 17, 17:1, 46 49:1, 49:2, 53, 53:1, 68 151, 237, 238, 239, 240 110, 139, 173, 185 61, 66, 69 260
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Naphthol Naphthol AS Isoindoline/one
38
Laked
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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, 89, 177 5:1 60 31 51 216, 226 254, 255 23, 37 43 194, Vat Red 74 123, 149, 178, 179 , 190, 224 29 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 68 48, 49 138 88, 181 81:1, 169 1, 2, 3 , 27 1, 2, 9, 10, 14, 19, 59, 61, 62 1, 2, 4 122 , 192, 202, 206, 207, 209 19, 30, 42 7 , 36 26 61 20
Quinacridones Quinophthalone Thioindigo Triarylcarbonium
Other Aniline Black Other a.
1 101, 192 64, 67 90, 251
Boldface numbers indicate the largest-volume pigments, with world production of more than 10 thousand metric tons. Italic numbers denote pigments with significant commercial importance, but with world output of less than 10 thousand metric tons. All other numbers indicate pigments of commercial importance, but with world output of less than one thousand metric tons. CEH estimates; Colour Index.
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SOURCES:
108 147 24
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The standard designation of individual pigments is by their generic name and chemical constitution as assigned by the Colour Index (CI), published by The Society of Dyers and Colourists (of the United Kingdom) and The American Association of Textile Chemists and Colorists. For example, the generic name Pigment Red 101 with Constitution Number 77491 has been assigned to synthetic red iron oxide pigment. Throughout this report, CI names for pigments are abbreviated as shown in the following examples: PBk1 is Pigment Black 1, PB-1 is Pigment Blue 1, PBn-1 is Pigment Brown 1, PG-1 is Pigment Green 1, PO1 is Pigment Orange 1, PR-1 is Pigment Red 1, PV-1 is Pigment Violet 1 and PY-1 is Pigment Yellow 1. Pigments are available in a variety of commercial forms, including the following:
q
Dry colors (usually powders, also granules) Presscakes (water-wet pastes or granules) Flushed colors (thick, 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)
Pigment quality is determined by its properties in the end-use application. According to the Colour Index, the technical value of a pigment is its fastness under the combined effects of the media of incorporation and the external environment, whether the finished product is, for example, a surface coating, ink, cement or plastic. Basic properties include hue, tinctorial strength, hiding power or opacity, dispersibility and fastness to light and heat (which tend to be the most noticeable properties affected by the media). Other properties considered by the end user are gloss, durability, transparency, resistance to chemical attack, bleeding, flocculation and migration, chemical purity, crystal and solvent stability, rheology (fluidity), adhesiveness and abrasiveness.
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ENVIRONMENTAL ISSUES
In general, the pigments with significant markets are practically nontoxic. Carcinogenicity is a concern, however, for some of the inorganic pigments such as lead chromate and cadmium sulfate. The following table shows some relative acute toxicity ratings, 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, 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. b. c. d. OSHA. Total dust. As measured by chromium trioxide equivalent. Cadmium basis. Registry of Toxic Effects of Chemical Substances (RTECS), U.S. National Library of Medicine, Toxicology Data Network (TOXNET), National Institute for Occupational Safety and Health (NIOSH). na Permissible Air Exposure Limitsa (mg/m3 ) 15b
Carcinogenicity No adequate evidence of carcinogenicity in humans Suspected human carcinogen
>12,000 (mouse) >7,080 (rat) na
0.1c
Positive carcinogenicity in rats, anticipated to be a human carcinogen No evidence of carcinogenicity
0.05d
na
na
No adequate evidence of carcinogenicity in humans na
na
>10,800 (rat) >10,000 (rat) >10,800 (rat) >5,000 (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, followed by concerns over the neurological damage that may be caused to children by lead-containing pigments. As a result, the pigments that receive the most regulatory attention contain lead, chromium or cadmium. The following table summarizes the major regional and national environmental and health regulations affecting inorganic and organic pigments and their markets:
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U.S. Environmental and Health Regulations Affecting Pigments Regulatory Agency/Regulation State Lead Paint Bans Affects over 25 states and more than 75% of U.S. highway miles Coalition of Northeastern Governors (CONEG)a State regulations to limit toxic metals in solid waste U.S. 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 childrens toys, consumer paints and paint applied to manufactured goods for consumer use U.S. Environmental Protection Agency (EPA) Resource Conservation and Recovery Act (RCRA) Restrictions on metal concentrations in waste for disposal U.S. Occupational Health and Safety Administration (OSHA) Proposed more stringent permissible exposure level for cadmium in the workplace a. Pigments Affected Lead chromate Markets Affected Highway paint
Lead chromate Cadmium Strontium chromate Zinc chromate
All packaging and packaging components (coatings, inks and labels)
All
Foods and pet foods; paper, plastic and other food and pet foodpackaging materials
All Lead chromate
Cosmetics Artist materials, childrens toys, consumer paints, painted consumer products
Cadmium Lead chromate Strontium chromate Zinc chromate
All markets
Cadmium
All markets
Includes the following states: Connecticut, Iowa, Maine, Minnesota, New Hampshire, New York, Rhode Island, Virginia, Washington and Wisconsin. CEH estimates.
SOURCE:
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WHITE PIGMENTS
White pigments, all of which are inorganic, are characterized by high indexes of refraction, resulting in scattering of light and high opacity. 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. Of the opaque white pigments, titanium dioxide (TiO2) is consumed in the largest volume, because of its low cost per unit of hiding power. The refractive index or hiding power of TiO2 pigments is higher than that of any other commercial white pigment. The United States, Western Europe and Japan combined consumed approximately 2.5 million metric tons of TiO2 in 1997, accounting for as much as 69% of the total world white pigment consumption by volume (excluding use for nonpigmentary applications). In these three regions, the surface coatings market accounts for 50% or more of the total TiO2 consumption. Other major pigment uses include paper and paperboard (where it is also a filler), plastics/elastomers, printing inks, ceramics and building materials. (See the CEH Titanium Dioxide Pigments marketing research report for more in-depth information.) Although ground calcium carbonate pigment is consumed in significant quantities worldwide for paper, paints, plastics and other uses, its main functions are as an extender, filler, bulking agent, 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). Other white pigments of less commercial importance than TiO 2 for pigmentary applications include zinc oxide (see the CEH Inorganic Zinc Chemicals product review), white lead, lithopone, zinc sulfide and antimony trioxide. Because of its outstanding optical properties and good environmental and health attributes, titanium dioxide has totally displaced the older white pigments such as white lead and zinc oxide in most markets. However, zinc oxide, mostly of the lead-free type, continues to find some limited worldwide application as a white pigment in the paint, ceramic and ink industries. In China and Eastern Europe, zinc oxide pigments are still widely used, as the gradual substitution by TiO2 pigments has only recently gained momentum. The most important property that zinc oxides impart to paints is mildew resistance. Zinc oxides also provide hiding power in paints, but they are less than one-seventh as efficient as TiO2 in this capability. Although the primary uses for zinc oxide are nonpigmentary (as a filler and activator in elastomer vulcanization, as a chemical intermediate and as a coating ingredient in photocopying paper), about 9% of the total U.S. zinc oxide consumption is accounted for by paints and ceramics. About 6.5% of total Japanese zinc oxide consumption is for paints and ceramics. Other whites that are of minor commercial importance include lithopone, white lead (basic lead carbonate), zinc sulfide and antimony trioxide. Lithopone (PW-5) is a calcined coprecipitate of zinc sulfide and barium sulfate. It is a white opacifying pigment with hiding power about one-fifth that of titanium dioxide. White lead (PW-1) pigment use still persists to a very minor extent in the surface coatings industry, where its value is primarily as a corrosion inhibitor. 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 childrens use. The white leads consumed in the United States are used almost entirely as heat stabilizers for polyvinyl chloride wire and cable products; less than 5% of total consumption goes into corrosion-resistant paints and coatings. Antimony trioxide (PW-11) is used primarily for its flame-retardant properties and, thus, is outside the scope of this report.
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BLACK PIGMENTS
By far the largest-volume black pigment worldwide is carbon black, which includes a variety of carbonaceous pigments produced by combustion or cracking of hydrocarbon raw materials. Furnace black, from highly aromatic oil feedstock and thermal black, from natural gas, account for more than 95% of the carbon black produced. However, such other types as lampblack, acetylene black and bone black are available. Unlike most pigments, carbon black is often used for functional purposes other than for coloring or opacifying. The major use of carbon black, roughly 90% of annual U.S. consumption, is as a reinforcing agent for rubber products. Pigment applications account for most of the balance of carbon black consumption. The major pigment use for carbon black is in printing inks, including carbon paper, followed by plastics and then paints and coatings. Consumption of carbon black for pigment uses in the United States, Western Europe and Japan combined totaled roughly 222 thousand metric tons in 1997. Detailed information on production and consumption of carbon black is contained in the CEH Carbon Black marketing research report. Other black pigments, most of which are produced in small quantities with limited commercial significance, include magnetite (naturally occurring iron oxide), synthetic black iron oxide, mineral black (powdered, low-grade coal), manganese black (naturally occurring manganese dioxide), complex inorganic pigments, graphite (crystallized carbon, either naturally or synthetically produced) and an organic black pigment aniline black. 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.
INORGANIC COLOR PIGMENTS DESCRIPTION

IRON O XIDE PIGMENTS Excluding titanium dioxide and extender pigments, iron oxides are the largest-volume inorganic pigments. On a worldwide basis, iron oxides have a larger-volume market share than all other color pigments together. Because of their low cost combined with such properties as high opacity, good lightfastness, strong absorption of ultraviolet light, good chemical resistance and heat stability under normal ambient conditions, they are attractive for a variety of commercial applications. Their primary disadvantage is lack of brightness compared with other inorganic pigments. Iron oxides are available in both natural and synthetic forms in a wide range of yellow, red and brown colors as well as black shades. In recent years, synthetic iron oxides, because of their greater color strength, better color uniformity and higher product purity, have replaced natural oxides in many applications. However, some grades of the natural oxides have special properties (for example, siennas have a certain translucency) that, combined with their relatively low price, continue to make them the pigment of choice in certain markets. Recently, manufacturers of natural iron oxide pigments (i.e. Viaton Industries with Rana Gruber) have started to manufacture micronized natural iron oxide red pigment,
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which apparently has a 15% higher color strength than standard synthetic iron oxide pigments. Also, the company claims that these pigments have further advantages, such as an environmental friendly production process, lower oil absorption and so forth. The most important iron oxide pigment, in terms of volume, is red. In weight terms, more than four times more red iron oxide pigments were sold than all red organic pigments in 1995. Some iron oxides are used for nonpigmentary purposes such as foundry sands or industrial chemicals. Since data for some of these applications are incorporated with data for pigment use, the information in this report necessarily includes some nonpigmentary iron oxides. Iron oxides are also used in magnetic media such as audio- and videotapes and computer disks, diskettes and tapes, but information on these applications is not included in this report. The following sections briefly describe the two types of iron oxide pigmentsnatural and synthetic.
Natural Iron Oxide Pigments Natural iron oxide pigments may well have been the first coloring substances known. 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. Today, natural iron oxides are processed from various ores, the principal ones of which are hematite, geothite, limonite, siderite and magnetite. Most of these ores contain considerably less than 100% iron oxide, although magnetite is often 95% Fe3 O4 and calcined siderite is 93-98% Fe2 O3 as used by pigment producers. The balance of the ore components consists of inert substances with little color value. Although these ores are widely distributed, only a few deposits are sufficiently pure and possess the required brightness and color to justify processing into pigment form. 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. Natural red iron oxides are a deep red color because of their high hematite content (typically around 75%). Silica and alumina are normally associated with hematite. Geothites and limonites are ferric oxides in hydrated form (Fe2 O3 xH2O) and are opaque yellow shades. The yellow pigment, sienna, is mined as a limonite ore normally containing roughly 50% Fe 2O3 plus other inorganics, such as silica and alumina, partly combined with the iron oxide. These mixed inorganic compounds (iron silicates and aluminates) are responsible for the unique translucency of sienna pigments. Sienna can be converted by calcination to burnt sienna, which is dark brown. Ochers, the lighter yellow colors, usually contain less Fe2 O3 than siennas, although they may contain as much as 50% Fe2 O3 . Ochers are essentially clay-containing limonite. The brown umber shades are also derived from limonite. Umbers are yellow-brown in the raw state because of the higher manganese dioxide content compared with other natural iron oxide pigments. Like siennas, umbers may be calcined to a deep reddish-brown color (burnt umber), which is the product favored over raw umber in the commercial market. Siderites are basically ferrous carbonate. They are not used as such for pigmentation, but can be calcined to form a brown ferric oxide (metallic brown). If sufficiently pure, siderites may calcine to red. Black natural iron oxide pigment is derived from magnetite (Fe3 O4 ), a magnetic substance used primarily for coal washing. Only a minute quantity of the magnetite mined is consumed in pigment applications.
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Commercially, the natural iron oxides are categorized not in terms of the ores from which they originate but as ochers (yellow), siennas (red-orange-yellow) and umbers (brown). An extensive number of grades of each of these products is available. To meet particular customer specifications, several natural oxides may be physically blended or synthetic oxides added, to produce the required colorant shades. The naturals generally have less color strength and uniformity than synthetic iron oxide pigments. However, even with these disadvantages the natural iron oxide pigments continue to have commercial importance because of their low price. In addition, modern methods of quality control and improved beneficiation methods for natural iron oxides yield constantly improving products of good color value per unit price.
Synthetic Iron Oxide Pigments Synthetic iron oxides, because they are chemically manufactured under controlled conditions, possess a higher degree of consistency from batch to batch than do the natural iron oxides. Synthetics are red, yellow, black and brown. In the United States, the brown products are generally produced by blending black, red and/or yellow oxides. All of the colors are available in a variety of shades, depending on the exact method of manufacture. The chemical formulas of the synthetic products are directly comparable with the natural pigments. Thus, Pigment Red 101, synthetic ferric oxide (Fe2O3 ), is the manufactured version of natural red hematite; 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 ).
CHROME PIGMENTS The chrome pigments discussed in this report include the lead chromate salts (chrome yellow, chrome orange and molybdate orange), chromium oxides (including hydrated chromium oxide) and normal lead silicochromate. The lead chromate salts vary in hue from greenish yellow through orange to pale red, depending upon the chemical composition, crystalline structure, particle size and particle size distribution of the pigment. Chrome yellow (PY-34), for example, ranges from primrose yellow, which has a definite green hue and is composed of lead chromate, lead carbonate and lead sulfate in solid solution, to light yellow. Greater temperature stability and lightfastness are achieved through lower concentrations of lead sulfate. The light yellow does not have lead carbonate and has a different crystalline structure and therefore a different hue. Medium and light red shades are produced by increasing the concentration of lead carbonate. Chrome yellow also includes a medium yellow, which is theoretically pure lead chromate. Chrome orange (PO21) is structurally basic lead chromate (PbCrO 4 PbO). Its variation in color from light orange to redder and deeper shades is associated with particle size differentials. Molybdate orange (PR-104), which varies in hue from light orange to red, is a solid solution of lead chromate, lead molybdate and lead sulfate. Commercial molybdates generally contain 75-85% lead chromate. Chrome yellows and oranges offer more intense colors than iron oxides, good hiding power and satisfactory lightfastness, at a relatively low cost. However, because of their poor alkali and acid resistance, lack of stability at high temperatures and possible discoloration upon long exposure to the
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atmosphere (because of their reaction with sulfide to produce lead sulfide), they are inappropriate for certain applications. To combat these deficiencies, lead chromates may be chemically treated to improve resistance to light, heat, chemicals and other harsh conditions. Pigment particles may be encapsulated with thin layers of metal oxides (e.g., silica, titanium dioxide, antimony oxide or tin oxide) to improve resistance. Typically these coatings may add 3-5% to the weight of the pigment particle. Final properties of the pigment are dependent on the choice of metal oxides and the order in which they are applied. Lead chromates may also be treated by organic agents to improve ease of dispersion, regardless of end-use application. Of the lead chromate salts, molybdate orange has the best hiding power. It possesses brilliant hue and fine particle size, resulting in easy dispersibility for an application such as printing inks. Since molybdate orange is compatible with many inorganic as well as organic pigments, it is often blended with other products to produce desired hues in the commercial marketplace. Manufacturers continue to improve the heat stability and chemical resistance of molybdate orange, thereby extending the areas of possible application to high-temperature plastics and corrosive environments. The chromium oxide greens comprise both the anhydrous oxide (PG-17), which is almost pure chromium sesquioxide and the hydrated oxide (PG-18), often called Guignets green. Chromium oxide is the most stable green of the commercially available green pigments. The hydrated version has a brilliant green hue as opposed to the drab green of the anhydrous oxide. Both chromium oxide greens possess outstanding lightfastness and resistance to attack by acids and alkalies. However, the hydrated oxide is less acid resistant and heat resistant than chromium oxide and loses its water of hydration at high temperatures. Chromium oxide itself, however, can withstand high temperatures and, thus, is appropriate in hightemperature applications such as ceramics. Chrome greens (PG-15) are normally blends of chrome yellows with iron blues. They vary in color from light green, with low iron blue content, to very dark greens, which contain 60-65% iron blue. The chrome greens are commercially available in pure forms and also in forms reduced with extender pigments. Like the lead chromate salts, chrome greens are relatively inexpensive, provide good hiding power and tinting strength and have acceptable heat resistance. However, they are subject to darkening in the presence of sulfur and susceptible to fading in an alkaline environment. Because of these deficiencies and concern about the toxicity of the lead component of this pigment, chrome green has been replaced, to some extent, by the organic pigment, phthalocyanine green. A specialty chrome green product, which is a mixture of high-performance chrome yellow and phthalocyanine blue, is available in the U.S. marketplace. Although this high-performance product is relatively expensive, it is, because of its performance characteristics, being substituted to some extent for phthalo green. Normal lead silicochromate is a pigment with a silica core coated with medium yellow lead chromate. It was introduced to the U.S. market in 1963 as one in a series of coated silica-cored pigments. Since that time it has found use in traffic paints, which are generally applied as thick films. 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.
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COMPLEX INORGANIC PIGMENTS The complex inorganic color pigments (formerly known as mixed-metal oxides) are a small but important group of inorganic pigments. Because of their outstanding heat resistance, chemical inertness, weather resistance and lightfastness, these pigments, which are based on the oxides of two or more metals, are appropriate for a variety of commercial applications. At least fifty different complex inorganic color pigments are available in the United States. Among the most important in the commercial marketplace are the nickel titanates (PY-53), chrome titanates (PBn24), manganese titanates (PY-164) and cobalt chromites (PG-26, sometimes called camouflage green). Nickel and chrome titanates together account for approximately 50% of the total complex inorganic color pigments used. As a group, complex inorganics possess low tinting strength. Thus, higher-than-average pigment loadings are often necessary to produce desired colors. Another disadvantage of this group of pigments is their high price, especially when combined with some organic pigments, which tends to limit their use to applications in which their excellent thermal stability makes them indispensable. Synthetic complex inorganic color pigments are available in a wide range of colors, including violet, blue, green, yellow, red, brown and black, as well as varying shades of these colors. They can be classified in several ways, although usually color, chemical structure or crystal structure is the criterion used in the industry. Although the actual chemical composition of most complex inorganic color pigments is variable, each identifiable oxide does have a basic chemical formula differentiating it from all other oxides. The two most important crystal structures are rutile and spinel, although twelve other crystal classes of the complex inorganic color pigments have been identified. 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. For example, 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. Similarly, a reddish chrome rutile yellow is formed when chromium is substituted for titanium in the crystal structure. Since both nickel and chromium have a lower valence in these compounds than titanium, a higher-valence metal ion, usually antimony, must be added to balance the resultant loss of charge. The two yellow pigments just described are members of the nickel-titanate and chrome-titanate series of complex inorganic color pigments. 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. 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. The complex inorganic color pigment oxides may be used alone, in combination with other inorganics or combined with stable organics. When used with organics, the complex inorganic color pigments provide the opacity and base color while the organic colorant adds color intensity and brightness. A combination of complex inorganic color pigments with organics can be substituted for cadmium pigments in some applications. These combinations were traditionally more prevalent in European countries such as Sweden, Switzerland and Denmark, when bans or proposed bans due to the uncertainty of the safety of cadmium use caused these countries to seek substitute products. While several grades of complex inorganic color pigments are available, the two used most often are ceramic and pigment grades. Both function as colorants. However, the pigment grade is generally of a
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finer and more uniform particle size with a softer texture than the ceramic grade. Some pigment grades are surface-treated to improve their wettability and dispersibility. In general, the zirconium-based complex inorganic color pigments are used for high-temperature ceramic applications, the titanium-based variety are used primarily for plastics and paints, and the cobalt-, chrome-, iron- and zinc-based oxides are used for plastics, paints and ceramics.
ULTRAMARINE PIGMENTS The ultramarine blues (PB-29) and violets (PV-15) are complex sodium aluminum sulfosilicates. The violets contain less sodium than the blues. Ultramarine blue is a brilliantly colored pigment with good heat stability but poor ultraviolet stability. Thus, it is inappropriate for exterior applications. Violet is much weaker in color, but it possesses great permanence. Applications for ultramarine blue include printing inks, textiles, rubber, artists colors, plastics, cosmetics and roofing granules. Ultramarine violet is believed to have fewer applications than blue. Ultramarine pigments are no longer manufactured in the United States.
IRON BLUE PIGMENTS Iron blues (PB-27) are also known as Chinese, Milori or Prussian blues. Demand for iron blues has been declining, due in part to environmental concerns, and the past few years have shown an increasing replacement of iron blues by other pigments. Within the ink category, for example, iron blues can be used for black ink toning, although they have been replaced somewhat by the organic pigment alkali blue (PB19 and PB-61) in this end use. Small quantities of iron blues are consumed in paints and coatings. Other applications for iron blues include carbon paper, certain plastics (e.g., low-density polyethylene), food colorants and paper manufacture. However, iron blues are also being replaced in these applications, primarily by phthalocyanine. Iron blues can also be used in combination with chrome yellow to make chrome green (PG-15). This market has been static and is expected to decline as iron blue is replaced by phthalocyanine blue to make phthalocyanine green, a chrome green replacement. All the U.S. supply of iron blue is now imported.
CADMIUM PIGMENTS All cadmium pigments are based on the compound cadmium sulfide, which itself produces a golden yellow pigment (PY-37) when precipitated, dried and calcined. However, 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. Furthermore, the inert extender barium sulfate is frequently added to the cadmiums to yield lower-cost, yet equally stable, lithopone-type pigments. In fact, in the commercial marketplace, 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. To modify the basic golden yellow color of cadmium sulfide, zinc may be introduced to replace some percentage of the cadmium and to produce greener shades of yellow (lemon and primrose, PY-35 and 37, [(Cd/Zn)S]). To produce redder colors, selenium is substituted for part of the sulfur in the cadmium sulfide crystal lattice. Pigment Orange 20 (Cd[S/Se]) and Pigment Red 108 (Cd[Se/S]) are examples of colorants that result from this reaction. Currently, only Socit Languedocienne de Micron-Couleurs SA (SLMC) in France is still producing mercadium pigments.
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The chemical basis for the range of colors possible with cadmium sulfides and sulfoselenides is as follows: Color Range with Cadmium Pigments
(Cd,Zn)S (cadmium/zinc sulfides) Primrose Lemon CdS (cadmium sulfide) Golden Yellow Orange Cd(S,Se) (cadmium sulfoselenide) Red Maroon
SOURCE: CEH estimates.
As a class, cadmium pigments have two attributes that are primarily responsible for their strong market acceptanceexcellent high-temperature stability and high color saturation for a broad range of colors from primrose yellow to maroon. In addition, these versatile colorants have such other advantageous properties as high resistance to alkali attack, light degradation and color particle migration; excellent hiding power; good dispersion characteristics; and insolubility in organic solvents. Limitations of the cadmium pigments include poor acid resistance and poor weatherability. Their poor weatherability is due to the oxidation of sulfides to sulfates, which are water-soluble. Thus, the selenide-containing cadmium pigments (reds) withstand poor weather better than the sulfides (yellows).
BISMUTH VANADATE PIGMENTS Bismuth vanadate pigments are a relatively new group of high-performance pigments introduced primarily as an alternative to lead chromate pigments. The pigments are brilliant yellow pigments with a green tint. Their main application, with 90% of total consumption, is in paints and coatings; the remaining 10% is in plastics, a growing market. Worldwide there are already a number of producers, located primarily in Western Europe.
RARE EARTH SULFIDE PIGMENTS Although rare earths have been used for color since their discovery, rare earth sulfide pigments are a novel group of pigments introduced by Rhne-Poulenc in France. Currently there are six specific pigments with varying color shadesorange, red, burgundy and yellow. The currently available pigments are all based on the main constituent, cerium sulfide. Variations in color are achieved by the addition of other rare earth sulfides and by modification of the physical form. Rare earth sulfide pigments can be regarded as high-performance pigments as they possess the following characteristics:
q
Excellent heat stability (up to 350C) Very good weather/light stability Acceptable tint strength (70-100% of heavy metal pigments) Excellent opacity
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Good migration resistance (in compliance with European and U.S. regulations regarding food contact) Dimensional stability when incorporated with crystalline polymers Very good ease of dispersion
An important characteristic of these pigments is their overall favorable toxicity status, which passes all current regulations. This prerequisite is the main driver, as rare earth sulfide pigments are aimed directly at replacing heavy metal pigments in plastics (particularly technical plastics such as ABS, polyamides and polycarbonate) and coatings.
MANGANESE VIOLET PIGMENTS Manganese violet (PV-16) is actually a member of the complex inorganic color pigments. However, since it is a precipitated rather than a calcined pigment, the properties of manganese violet are different from those of other inorganic complexes. For example, it is translucent rather than opaque and it is not particularly alkali-resistant. The primary application for manganese violet is in cosmetics. The Shepherd Color Company in Cincinnati, Ohio is the only U.S. manufacturer of this pigment.
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, the methods of processing the ore to produce iron oxide pigments vary considerably. Furthermore, the ultimate commercial application of the pigment determines the degree to which the ore must be treated. Generally, 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, chlorides and sulfates Further grinding or micronizing to produce the finished pigment
Synthetic Iron Oxide Pigments Three principal methods are employed in the manufacture of synthetic iron oxidesprecipitation reactions, thermal decomposition of iron compounds and organic reduction processes utilizing iron as the reducing agent. These processes often utilize spent pickling acid generated by the steel industry as raw materials. Pickling acid removes the oxides of the mill scale during the forming (rolling, drawing, etc.) of hot steel, by conversion to soluble iron compounds in a hydrochloric or sulfuric acid bath. Ferrous
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chloride or ferrous sulfate obtained from spent pickling acid is roasted to drive off water and sulfur oxides, leaving iron oxides behind. The oxides contain 2-10% ferrous chloride, which must be washed prior to pigment use. In the processing, hydrochloric or sulfuric acid can be regenerated and reused in the steel plants. Ferrous sulfate heptahydrate (copperas) by-products from the sulfate process of producing titanium dioxide may also be used. Further, scrap metallic iron may be used as the reducing agent in the organic reduction process of iron oxide production. In this case, the scrap iron is oxidized to iron oxide. In all of these production processes, pigments of high and consistent quality are the goal of the manufacturers. Both color and chemical stability are of major concern since, in subsequent applications, pigments are frequently subjected to extremes of temperature, various chemical environments and ultraviolet light. Thus, test measurements are conducted at each step of the pigment processing to insure that quality standards are met. 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. Synthetic yellow iron oxides are commonly produced by one of two precipitation processes. In both, a ferrous sulfate solution is treated with heat and compressed air, resulting in the conversion of ferrous ions to trivalent insoluble oxides. The difference between the two processes is that in one, ferrous sulfate is the sole source of ferrous ions. In the second, the Penniman-Zoph process, metallic scrap iron is used as an additional component. It not only acts as a neutralizer for the sulfuric acid formed in the process, but also serves as a continuous additional source of ferrous ions. The initial steps of this process involve the preparation of a seed, which is subsequently placed in a tank containing scrap iron and ferrous sulfate solution. The seed is circulated over the scrap iron in the presence of compressed air and iron oxide grows onto the seed. 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, dried, ground and bagged. Another process used to produce synthetic yellow is the aniline process, which employs both organic and inorganic raw materials. 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. The aniline is subsequently removed from the paste, which is then purified, filtered, dried, ground and bagged for sale. 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, usually in the presence of oxygen and metallic iron
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Oxidation of synthetic black iron oxide
The two-stage calcination to copperas (ferrous sulfate heptahydrate, FeSO4 7H2O), a by-product in the sulfate process of manufacture of titanium dioxide pigment, 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, the thermal dehydration of synthetic yellow to ferrite red, yields red oxide particles that are acicular (needle-shaped), rather than spheroidal like copperas red particles. This difference in particle shape results in a yellowish red color. 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. (Under normal conditions yellow, rather than red, oxides are produced.) Black iron oxide, Fe3 O4 or FeO. Fe2 O3 , may be calcined at high temperature to oxidize the FeO and change the color from black to red. The original cubical shape of the black iron oxide particles is maintained during the calcination and an extremely pure red iron oxide results. Synthetic black iron oxide, which is manufactured in both cubical and acicular forms, is produced in the cubical form using methods similar to those used to make yellow oxides, such as the precipitation method, in which a black intermediate is precipitated from an alkaline aqueous ferrous salt solution. The ferrous hydroxide formed is aerated and heated to oxidize the iron precipitate and yield black iron oxide, 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. Because the acicular form is more expensive to produce, it is used primarily in applications that make use of its high magnetic strength (e.g., magnetic ink).
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The acicular form of black iron oxide pigment is manufactured by chemical reduction of synthetic ferrite red. This aniline process, described in the section on yellow iron oxide, is the major process used worldwide to produce synthetic black iron oxide. A variety of black shades may be obtained using any of these production methods. The particle size determines the resultant shade. However, only the cosmetics industry evaluates quality on the basis of shade. All other industries are more concerned with pigment strength.
CHROME PIGMENTS Lead chromate pigments, like many other inorganic pigments, are manufactured by precipitation. Key factors involved in the precipitation process include the purity of raw materials, the concentration and addition sequence of the reactants, the flow rate of the reactants, the temperature during precipitation, the rate of slurry agitation, the presence of particle-size control agents and the time of reaction. Precipitation is followed by drying and grinding without a calcination step. For some lead chromates, 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 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. 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, production of nitric acid and the resultant acidification of the pigment slurry increases the solubility of lead chromate. Redissolving the chromate allows growth of larger pigment particles. However, redissolving is not practiced by the largest producer in the United States. This pigment particle growth is limited by the addition of lead carbonates or phosphates. Proper control of particle size enhances uniformity in hiding power, color intensity and tint of a pigment. Medium yellow, essentially pure chromate, is produced directly in the reactions above. Primrose and light yellow, however, are prepared by coprecipitation of lead chromate with lead sulfate and/or with lead carbonate. The light yellow is precipitated at high temperatures while primrose is processed at lower heats. Chrome oranges are precipitated under alkaline conditions. The degree of alkalinity determines the particle size and, thus, the hue, of the final product. Molybdate orange is manufactured by the addition of a solution of sodium chromate, sodium molybdate and sodium sulfate to a solution of lead nitrate under carefully controlled conditions. The resulting solid solution is a coprecipitate of lead chromate, lead molybdate and a small amount of lead sulfate. Aftertreatments, such as application of a silica coating or addition of aluminum, antimony and/or titanium hydroxides, are used to augment stability, similar to the treatments used in the production of chrome yellow and orange. Chromium oxide greens are calcined pigments prepared by the reduction of sodium bichromate with sulfurous and/or carbonaceous materials. The chemical reactions are as follows:
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(NH4) 2Cr 2O7 + Na2SO4
(NH4) 2Cr2O7
Cr2O3
N2
4 H2O
The product is filtered, washed, dried and pulverized. 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. Chrome greens, blends of chrome yellows and iron blues, are prepared by blending dry pigments, by slurrying together wet yellows and blues or by precipitating lead chromate in the presence of an iron blue suspension. Normal lead silicochromates are prepared by coating a core of silica with medium yellow lead chromate.
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. The mixture is then calcined at high temperature (660-1,400C). The high temperature not only provides the required energy for the reaction, but also stabilizes the final product, making it useful for high-temperature applications. After firing, the pigment is milled to yield a fine powder. 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, although solid-state reactions are the method of choice in the United States.
CADMIUM PIGMENTS Although various pigment manufacturers have developed proprietary methods of producing specific cadmium colorants with particular properties, these methods tend to be variations on a single standard process. 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. An aqueous solution of sodium (or other) alkali sulfide is introduced to precipitate cadmium sulfide in cubic crystallographic form. Cadmium sulfoselenides are produced by mixing cadmium sulfide with an alkaline sulfide-selenide. In either case, after washing and drying, the precipitates are in the form of fine color particles. At this stage of manufacture the particles are too fine to have pigmentary properties. The brilliant colors of the cadmium pigments develop during the following calcination step at 500-700C when the pigment material is converted from the cubic to the more stable hexagonal structure and the particles grow larger. After calcination, the pigments are flushed with weak hydrochloric acid to remove soluble cadmium and then again washed and dried in filter presses. The final filter cake is disaggregated for the marketplace or for further processing. Cadmium lithopones are usually produced by one of two methods. In the first, barium sulfate is mechanically blended with the cadmium pigment after it has been calcined. Because of their similar particle size and specific gravity, the two substances tend to mix well. In the alternative method, barium, in the form of barium sulfide, is added at a much earlier stage of the process to insure efficient mix. It is added to the starting cadmium sulfate (or nitrate) in place of some of the sodium sulfide. Coprecipitation of cadmium sulfide and barium sulfate occurs. The entire coprecipitate, which contains approximately
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62% barium sulfate by weight, is then calcined. The final product is a homogeneous powder, whose opacity and color are determined by the particle size. The calcination step is a particularly important part of cadmium pigment manufacture, for it is at this stage that the crystal structure is changed to yield a pigment of bright color. 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 800-900C.
SUPPLY AND DEMAND BY REGION

UNITED STATES Iron Oxide Pigments Producing companies Iron oxide producers illustrate the diverse nature of pigment producers; they range from major chemical companies to small independent colorant operations and iron ore mining companies. The following table lists natural iron oxideproducing companies, plant locations and specific pigments produced:
U.S. Producers of Finished Natural Iron Oxide PigmentsApril 2001a Umber (brown) Company and Plant Location Arizona Oxides LLC El Mirage, AZ Blue Ridge Talc Co. Inc. Henry, VA Dynamic Color Solutions, Inc. Milwaukee, WI Elementis plc Elementis Pigments Easton, PA East St. Louis, IL Hoover Color Corporation Hiwassee, VA New Riverside Ochre Company, Inc. Cartersville, 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
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U.S. Producers of Finished Natural Iron Oxide PigmentsApril 2001a (continued) Umber (brown) Company and Plant Location Pea Ridge Iron Ore Company Sullivan, MO The Prince Manufacturing Company Bowmanstown, PA Quincy, IL Rockwood Specialties Inc. Rockwood Pigments Inc. Beltsville, MD Davis Colors Los Angeles, CA a. 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
Typically, pigment producers are also resellers, offering for sale a broader pigment line than they produce. CEH estimates.
SOURCE:
Since 1997, the following changes have occurred among U.S. natural iron oxide pigment producers:
q
Soloman Colors sold its natural pigments manufacturing business to The Prince Manufacturing Company in 1999. In 1999, Arizona Oxides merged with Cathay Pigments. Laporte Pigments Corporation was purchased by K-L Holdings in November 2000. Laporte Pigments Corporation was renamed Rockwood Specialties. In early 1997, Arizona Oxides LLC began the production and sales of natural iron oxide pigments from a hematite mine in southwest Arizona. The company also upgrades imported synthetic iron oxide pigments. Harcross Pigments Inc. became Elementis Pigments in 1997.
Four U.S. companies are vertically integrated iron oxide pigment producers, capable of mining the ore used to produce pigments: Arizona Oxides, Hoover Color, New Riverside Ochre and Pea Ridge Iron Ore. Arizona Oxides in Arizona, New Riverside Ochre in Georgia and the Hoover Color in Virginia each mine and produce ocher pigments. New Riverside Ochre receives some of its natural red pigment supply from the Alabama Pigment mine in Dudley, Alabama, which it owns.
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U.S. producers of synthetic iron oxide pigments are listed in the following table:
U.S. Producers of Finished Synthetic Iron Oxide PigmentsApril 2001a Company and Plant Location Bayer Corporation Coatings and Colorants Division New Martinsville, WV Elementis plc Elementis Pigments Inc. Colton, CA Easton, PA East St. Louis, IL BFGoodrich Performance Materialsc Cincinnati, OH Newark, NJ Hoover Color Corporation Hiwassee, VA Rockwood Specialties Inc. Davis Colors Los Angeles, CA Mapico, Inc. St. Louis, MO Mineral Pigments Beltsville, MD The Prince Manufacturing Companyd Quincy, IL Geo. B. Smith Color Corporationd Kirkland, IL Solomon Grind-Chem Service, Inc.d Solomon Colors Division Springfield, IL a. 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
In addition to the companies listed, Hoover Color Corporation manufactures PBn-9, a synthetic product that is a color duplicate of natural Van Dyke brown (an imported product). This is not an iron oxide pigment but rather a ferrite containing zinc oxide or magnesium oxide. Company produces transparent grade only. Some synthetic iron oxide pigments may be resold. CEH estimates.
b. c. d.
SOURCE:
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Since 1997, the following changes have occurred among U.S. synthetic iron oxide pigment producers:
q
In March 1998, the Freedom Chemical Company, (formerly Hilton Davis Company) was acquired by 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.
Salient statistics Iron oxide pigment salient statistics for 1999 are estimated as follows:
U.S. Salient Statistics for Iron Oxide Pigments1999 (thousands of metric tons) Production Natural 84.6 Total SOURCE: 170.1 CEH estimates. Synthetic 85.5 Natural 7.4 85.0 Imports Synthetic 77.6 Exports Natural neg 13.8 Synthetic 13.8 Apparent Consumption Natural 92.0 241.3 Synthetic 149.3
Historical tonnage sales data for finished iron oxide pigments from U.S. producers are presented in the following table:
U.S. Sales of Finished Iron Oxide Pigments from U.S. Producers (thousands of metric tons) Brown Naturalab 1960 1965 1970 1975 1980 1981 1982 1983 1984 1985 1986 1987 1988 1989 8.8 22.7 15.1 14.2 12.2 16.5 13.3 4.3c 4.5c 4.5c 3.0c na na na Synthetic 1.9 3.6 4.3 5.2 9.3 10.2 9.7 12.7 14.8d 16.8d 18.3 22.0d 24.2d 23.6d Natural 16.2 29.6 25.2 26.4 30.6 25.2 19.1 20.7 23.0 24.0 21.0e 22.0 23.5 26.4 Red Synthetic 41.1 27.4 26.6 18.7 29.0 29.4 22.1 27.7 30.3 30.6 32.8 33.4 34.1 32.7
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U.S. Sales of Finished Iron Oxide Pigments from U.S. Producers (continued) (thousands of metric tons) Brown Naturalab 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 na na na na na 2.0c na 2.1 2.3 2.4 Synthetic na 8.0f 8.7f 7.0f 6.1f na 7.8 10.0 9.8 9.4 Natural 26.8 25.6 27.3 28.3 32.0 49.3 49.6 53.6 54.6 55.7 Red Synthetic 32.5 28.3 27.4 na na na na na na na
U.S. Sales of Finished Iron Oxide Pigments from U.S. 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 4.4 4.2 4.8 4.4 5.3 4.8 4.6 15.1i 16.0i 13.4i --j na na na na na na na na na na na na na Synthetic 13.0 18.5 22.8 17.5 19.7 21.7 18.5 21.9 19.5 16.4 22.4f 24.3f 22.7f 21.9f 18.1 16.4 16.7 na na 18.8 23.6 25.7 25.2 25.5 Natural --------------------12.7 15.4 15.4 21.0 Blackg Synthetic 1.9 2.4 5.7 -4.9 5.5 6.1 4.6 4.8 4.9 5.8 5.7 6.4 10.3 25.8ef 15.3 16.2 17.5 17.0 29.6 21.0 20.1 21.0 26.5 Unspecified 2.6 7.0 7.6 8.4 12.6 14.9 11.9 4.5 4.6 4.3 13.0 16.8 15.8 12.7 23.6 23.6 24.9 72.8 83.8 45.3 48.3 49.1 51.7 53.5 Totalbh 89.9 115.4 112.1 94.7 123.6 128.2 105.3 111.4 117.5 115.0 116.4 124.2 126.6 127.6 126.8 117.2 121.3 125.6 138.9 145.0 163.0 176.0 180.0 194.0
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a.
Amounts reported in this column exclude Van Dyke brown, an imported crude pigment processed and sold in the United States. Data for 1960-1963 are not directly comparable with later years due to reclassification of pigments. Sales of brown iron oxide have been withheld by the source to avoid disclosing company proprietary data. Data include reported sales of natural umbers only. Includes data for synthetic black iron oxide. Includes data for natural yellow iron oxides. Includes data for mixtures of natural and synthetic and specialty iron oxides. Data include precipitated magnetic black from 1960 to 1963. Beginning in 1974, data for precipitated magnetic black were combined by the source with data for brown iron oxides. Data include black magnetite in 1960, 1961, 1976-1984 and 1995. From 1962 to 1975, data for black magnetite were combined by the source with data for brown iron oxides. Totals may not equal the sums of the categories because of rounding. Includes data for natural brown iron oxides. Data were combined with natural red iron oxides. (A) Minerals Yearbook, U.S. Department of the Interior, Bureau of Mines (data for 1960; data for SYNTHETIC BROWN, RED, YELLOW, BLACK and UNSPECIFIED for 1965-1984 except NATURAL YELLOW and TOTAL YELLOW for 1984; all data for 1985-1992). (B) Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1992-1993). (C) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 1994-1999).
b.
c.
d. e. f. g.
h. i. j.
SOURCES:
In 1999, the United States sales of finished iron oxide pigments from U.S. producers was 194.0 thousand metric tons (including U.S. production sold domestically and imports for consumption). The following table shows the total U.S. sales of natural and synthetic iron oxide pigments from U.S. producers since 1980:
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U.S. Sales of Finished Iron Oxide Pigments from U.S. 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. b. 53.0 52.1 43.1 44.6 48.3 46.9 42.8 27.8 29.8 49.4 48.6 49.2 52.3 55.8 68.7 76.2 75.0 81.0 84.0 92.0 Synthetic 70.7b 76.1b 62.2b 66.8 69.2 68.1 73.6 96.5 96.8 78.3 76.4 68.1 69.0 69.8 70.2 68.8 88.0 95.0 96.0 102.0 Total 123.6 128.2 105.3 111.4 117.5 115.0 116.4 124.3 126.6 127.7 125.0 117.2 121.3 125.6 138.9 145.0 163.0 176.0 180.0 194.0
Includes some nonpigmentary consumption for all years. Data include mixtures of brown synthetic and natural iron oxides. In 1983-1984, these mixtures are included in the brown synthetic iron oxides data. (A) Minerals Yearbook , U.S. Department of the Interior, Bureau of Mines (data for 1980-1991). (B) Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1992-1993). (C) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 19941999).
SOURCES:
The following table shows historical annual dollar sales values for U.S. producers by type of iron oxide pigment since 1960:
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U.S. Sales Values of Finished Iron Oxide Pigments from U.S. 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 1.21 3.49 3.25 4.07 5.22 6.87 6.26 6.41 3.81c 4.12c 2.99 na na na na na na na na na 2.1 2.8 3.1 3.3 Synthetic 0.60 1.88 1.73 4.49 10.82 12.60 13.48 18.20 22.13d 25.57d 28.10d 34.34d 39.02d 36.05d na 15.07f 15.82f 13.20 11.60 na 14.7 18.9 18.0 17.1 Natural 1.10 1.99 2.16 2.72 3.78 3.79 3.09 4.11 4.91 4.82 3.61e 3.61 4.06 4.71 4.74 5.18 16.56 5.40 6.20 9.60 9.7 11.2 10.9 11.7 Red Synthetic 10.03 8.21 8.51 13.93 34.79 40.01 31.79 38.95 45.40 47.05 49.78 52.90 56.50 50.83 54.24 50.53 49.57 na na na na na na na
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U.S. Sales Values of Finished Iron Oxide Pigments from U.S. 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. b. 0.34 0.40 0.51 0.78 1.25 1.11 1.10 1.70 5.21i 4.72i -- j na na na na na na na na na na na na na Synthetic 3.49 5.53 8.00 14.00 21.42 25.98 24.37 30.08 27.43 24.23 36.29f 36.57f 34.59f 33.63f 29.12 28.18 28.34 na na 32.60 42.4 44.4 43.1 45.4 Natural -------------Blackg Synthetic 0.6 0.9 1.4 -0.6 0.9 1.0 0.8 0.9 0.9 1.1 1.1 1.2 2.1 41.0 23.0 25.5 27.80 27.50 29.60 37.8 34.5 38.0 43.9 Unspecified 0.52 1.12 2.56 6.15 19.09 19.44 26.89 10.18 12.59 11.31 4.52 7.85 8.14 7.22 10.00 10.84 11.28 93.70 97.70 75.20 74.2 54.2 77.0 81.9 Totalbh 17.89 23.53 28.12 46.14 96.97 110.70 107.98 110.43 122.38 122.72 126.39 136.37 143.51 134.57 139.13 132.89 147.08 140.10 143.00 147.00 183.0 169.0 193.0 207.0
------2.1 3.0 2.9 3.7
Values reported in this column exclude the value of imported Van Dyke brown. Data for 1960-1963 are not directly comparable with later years due to reclassification of pigments. Value of brown iron oxide was withheld by the source to avoid disclosing company proprietary data. The source included brown value with natural yellow. Includes data for synthetic black iron oxide. Includes data for natural yellow iron oxide. Includes data for mixtures of natural and synthetic and specialty iron oxides. Data include precipitated magnetic black for 1960. Beginning in 1974, data for precipitated magnetic black were combined by the source with data for brown iron oxides. Data include black magnetite in 1960, 1984 and 1995. From 1965 to 1975, data for black magnetite were combined by the source with data for brown iron oxides. Totals may not equal the sums of the categories because of rounding. Includes data for natural brown iron oxides. Data combined with natural red iron oxides.
c.
d. e. f. g.
h. i. j.
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(A) Minerals Yearbook , U.S. Department of the Interior, Bureau of Mines (all data for 1960 and 1985-1991; data for SYNTHETIC BROWN, RED, YELLOW, BLACK and UNSPECIFIED for 1984). (B) CEH estimates (data for 1963-1984 for NATURAL BROWN, TOTAL BROWN and TOTAL and 1966 datum for BLACK). (C) Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1992-1993). (D) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 1994-1999.
Consumption The reported U.S. consumption of U.S.-produced iron oxide pigments by market segment is shown in the following table and pie charts.
U.S. Reported Consumption of U.S.-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: 27.2 24.4 21.1 29.0 32.9 32.2 33.8 39.8 44.3 44.7 40.0 37.5 41.2 42.7 45.8 43.8 49.4 51.3 59.6 64.0 Plastics, Rubber, Paper, Textiles, Glass, Ceramics 13.6 19.2 14.7 15.6 12.9 13.8 14.0 14.9 21.5 21.7 21.3 18.8 20.6 16.3 16.7 16.7 na na 18.0 17.5 Ferrites and Other Magnetic Applications 11.1 15.4 13.7 na na na na na na na na na na na na na na na na na
Surface Coatings 45.7 42.3 34.7 40.1 41.1 38.0 38.4 36.0 31.7 30.6 30.0 27.0 27.9 23.9 29.2 29.0 36.2 49.5 44.6 45.4
Foundry Sands 6.2 7.7 6.3 6.7 5.9 6.9 5.8 7.5 7.6 6.4 5.0 7.0 7.3 10.0 11.1 13.1 13.0 15.8 12.6 13.5
Animal Feed and Fertilizers 8.7 9.0 8.4 6.7 5.9 6.9 5.8 5.0 5.1 6.4 6.3 7.0 4.9 na na 8.7 na na na na
Industrial Chemicals 8.7 7.7 5.3 5.6 5.9 5.8 7.0 6.2 6.3 6.4 7.5 4.7 3.6 7.5 8.3 na 14.7 7.0 10.8 13.5
Miscellaneous 2.5 2.6 1.1 7.8 12.9 11.5 11.6 14.9 10.1 11.5 15.0 15.2 15.8 25.2 27.8 na na na na na
(A) Minerals Yearbook, U.S. Department of the Interior, Bureau of Mines (data for 1980-1988). (B) Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1989-1993). (C) CEH estimates based on Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (all data for 1994-1999).
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U.S. Market for Synthetic and Natural Iron Oxide Pigments1999

Other 27%
Construction Materials 42% Plastics, Rubber, Paper, Textiles, Glass, Ceramics 7%
Surface Coatings 24%
U.S. Market for Natural Iron Oxide Pigments1999
Other 56%
Construction Materials 22%
Plastics, Rubber, Paper, Textiles, Glass, Ceramics 9%
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The U.S. market for synthetic iron oxide pigments is as follows:

U.S. Market for Synthetic Iron Oxide Pigments1999
Construction Materials 22%
Other 56%
Plastics, Rubber, Paper, Textiles, Glass, Ceramics 9%
Construction materials. Construction material producers use iron oxide pigments to color concrete blocks and roofing tiles, bricks, paving stones, stucco and mortar. Growth in this market segment is influenced by the overall cyclicity of construction activity, the increasing popularity of colored building materials and product innovations. 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. The following table shows reported sales of iron oxide pigments by U.S. producers to the construction materials market since 1980:
U.S. 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 13.6 10.9 9.1 10.9 13.8 14.1 12.0 10.8 13.3 11.2 10.8 9.9 10.9 na na na 14.9 15.4 20.2 19.0 Synthetic 14.5 13.6 12.0 18.1 19.1 18.1 21.8 29.0 31.0 33.5 29.2 27.6 30.3 na na na 34.5 35.9 39.4 45.0 Totalb 28.1 24.5 21.1 29.0 32.9 32.2 33.8 39.8 44.3 44.7 40.0 37.5 41.2 42.7 45.8 43.8 49.4 51.3 59.6 64.0
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a.
Includes sales of imported finished iron oxide pigments, but not imported finished iron oxide pigments sold directly to consumers. Total may not equal the sum of the categories because of rounding. Data may include some mixture of naturals and synthetics. (A) Minerals Yearbook and preprints, U.S. Department of the Interior, Bureau of Mines (data for 1980-1991). (B) Mineral Industry Surveys , U.S. Department of the Interior, Bureau of Mines (data for 1992-1993). (C) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 1994-1999).
b.
SOURCES:
The building materials that consume iron oxides include concrete block, brick, mortar, concrete roofing tiles, roofing granules, paving stones, poured concrete and stucco. Concrete block is the largest construction material application for natural and synthetic iron oxides. U.S. consumption of natural and synthetic iron oxides in roofing tiles and paving stones has been growing strongly, but each holds a smaller market share than colored concrete blocks. Either natural or synthetic iron oxides or pigment blends may be used to color concrete. Most concrete is colored by adding the iron oxide directly to the wet mix prior to pouring. Red and yellow are the most popular colors, followed by brown and black. For black coloration, synthetic iron oxide is used since the tinting strength of natural black is not high enough to achieve satisfactory coloration. Iron oxide pigments are available in both dry and slurry forms. Slurries can be easier to work with, providing advantages in bulk handling and easier mixing and dust elimination. Free-flowing dry forms of iron oxide are available for the construction material market. This product reduces dust problems and is easier to mix. Of all the segments, the U.S. construction industry has shown the strongest growth since 1995 as housing starts rose from 1.35 million units to a rate of 1.67 million units in 1999 and home resales and remodeling remained strong. Despite the expected lower construction activity rate of 1.4-1.5 million units, the growth rate for iron oxide pigments in construction for 1999-2004 should only slow or flatten, as product innovation and more intensive use of pigmented concrete products cause broader use of iron oxide pigments. Surface coatings. 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. The following table shows the consumption of iron oxide pigments (including imports) per segment within the surface coatings market:
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U.S. Consumption of Iron Oxide Pigments for Surface Coatings1999 (percent) Product Finishes, OEMsa Architectural Coatingsb Special-Purpose Coatingsc Total a. 46 37 17 100%
Includes automotive topcoats, primers and underbody components and parts; machinery and equipment; sheet, strip and coil; metal furniture and fixtures. Mainly exterior, water-based flat house paints, stains and trim; interior, water-based flat and semigloss paints. Mainly for maintenance and auto refinishing. CEH estimates.
b.
c.
SOURCE:
The following table reports the sales of iron oxide pigments by U.S. producers to the surface coatings market since 1981:
U.S. Producers 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. 12.7 10.0 10.9 11.8 10.0 8.2 8.2 7.3 8.3 8.2 7.3 8.0 8.4 12.0 17.0 9.7 9.8 10.9 13.8 Synthetic 30.8 24.5 29.0 29.9 26.3 29.9 27.2 24.5 22.3 21.8 19.6 19.9 15.4 17.0 12.0 26.5 39.7 33.7 31.6 Totala 43.5 34.5 39.9 41.7 36.3 38.1 35.4 31.8 30.6 30.0 26.9 27.9 23.8 29.0 29.0 36.2 49.5 44.6 45.4
Totals may not equal the sums of the categories because of rounding.
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(A) Based on Minerals Yearbook and preprints, U.S. Department of the Interior, Bureau of Mines (data for 1981-1991). (B) Based on Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1992-1993). (C) Based on Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 19941999).
Although synthetic iron oxides are the preferred pigment in the paints and coatings industry, there is still a significant market for natural iron oxides in paints, particularly in primers and undercoats, where color consistency is less critical. Primers function not only to promote adhesion but also to provide protection against corrosion. An iron oxide known for its anticorrosive properties is micaceous iron oxide (mined from micaceous hematite); it has protective properties because of the thin, platelike shape of its particles. When a micaceous iron oxide paint is applied to a surface, the thin platelets orient themselves in a plane parallel to the substrate, thus providing a barrier to moisture and corrosive ions. Micaceous iron oxide helps to protect the paint binder from ultraviolet radiation. Although micaceous iron oxide has been used for decades in Europe on bridges and other metallic structures, its use in the United States is relatively recent. Some examples of uses include roof coatings and structural steel coatings on highway bridges. Synthetic iron oxides are among the most useful pigments to formulators of paints and coatings. Since these pigments are manufactured under controlled conditions, the particle size, distribution and shape can be accurately duplicated, resulting in reproducible colors. The easily dispersible synthetic yellow and red iron oxides are the most frequently used iron oxide pigment in paints. Blacks and browns are of less importance. Transparent (low-opacity) synthetic iron oxides are a small-volume, additional specialty product group used in the paints and coatings industry. They are of extremely fine particle size and have low covering power, but are ideal for covering metallized finishes requiring long durability. Most of the transparent oxides find use in OEM automotive topcoat finishes and automotive repair finishes. In the United States, a small percentage is used for wood stains and OEM furniture finishes. The total estimated U.S. market for transparent iron oxides has remained relatively flat for the last decade. The U.S. market for transparent iron oxides is estimated to have been about one thousand metric tons in 1999. Currently, the world market is served by two producers: BASF Aktiengesellschaft in Europe and the Hilton-Davis Company in the United States. Growth in the consumption of natural and synthetic iron oxides depends upon growth in the surface coatings market, the loadings of iron oxide pigments in paints and product innovations. 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. This application has quickly grown to use nearly 10 thousand metric tons per year. It can utilize waste wood and uses primarily low-cost imported pigments. Over the past several decades, surface coatings consumption growth has tended to follow the growth in the overall manufacturing economy, but this parallel to the growth in GDP may become disconnected as the U.S. economy has become increasingly characterized by service industries.
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Plastics, rubber, paper, textiles, glass and ceramics. It is estimated that this segment consumed about 17.5 thousand metric tons of synthetic and natural iron oxide pigments from all sources (including imports) in 1999, in order of rank, by the plastics, glass and ceramics, paper and textiles, and rubber industries. A quantitative consumption breakdown for this group by application is not available. However, reported sales by U.S. producers are as follows:
U.S. Consumption of Iron Oxide Pigments for Plastics, Rubber, Paper, Textiles, 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. 4 7 6 6 5 5 5 5 8 11 10 9 11 7 8 7 na na na 6.3 Synthetic 9 12 9 9 7 8 8 10 13 11 11 10 10 10 8 9 8 na na 11.2 Totala 14 19 15 15 13 14 14 15 21 22 21 19 21 16 17 17 na na 18.0 17.5
Total may not equal the sum of the categories because of rounding. Data may include some mixture of naturals and synthetics. (A) CEH estimates based on Minerals Yearbook and preprints, U.S. Department of the Interior, Bureau of Mines (data for 1980-1991). (B) CEH estimates based on Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1992-1993). (C) CEH estimates based on Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 1994-1999).
SOURCES:
Natural iron oxides (96% Fe2O3 ) are used as rouge in flat glass batches to impart a greenish cast. Synthetic red is often used as a stain to color glass and ceramic bodies or as a component of decorative glazes. The addition of Fe2 O3 to molten glass results in the presence of ferric and ferrous ions in the solution. The ferric ions in conjunction with oxygen result in green coloration, and a preponderance of ferrous ions, in conjunction with oxygen, leads to a yellow-brown colorant.
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Following titanium dioxide, iron oxides are the inorganic pigments used most in plastics. (The ratio of TiO2 use to iron oxide use is about 30:1.) In 1999, the plastics industry was believed to have used as much as 7-8 thousand metric tons of iron oxide pigments. 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. Natural iron oxides are used less often than synthetics in plastics. In addition to their low tinting strength, the presence of higher quantities of impurities can catalyze resin degradation in some plastics. In phenolic resins, however, natural siennas, ochers and umbers can be used. Burnt umber is frequently used to give a brown tint to phenolic resinbased electrical components. Synthetics sometimes are combined in plastics with other, brighter pigments to attain the required color. Synthetic reds are often used because they are the most thermally stable. Yellows tend to change color to red at high temperatures and, thus, must be baked at comparatively lower heats. Yellows can be safely incorporated into polyethylene. Black, too, tends to oxidize to red at high temperatures, although it is also safe in polyethylene. Both yellow and red are strong absorbers of ultraviolet radiation, slowing the breakdown of the polymers and, thus, prolonging the life of the plastic products. Synthetic brown (a blend of red, yellow and black) is frequently used in plastics, particularly for simulated leather or for producing wood grain effects. Overall, resins for which iron oxide coloration is appropriate include the thermoplasticspolyethylene, polypropylene, polystyrene and polyvinyl chloride (PVC)and the thermosets. Polyethylene trash bags are a growing end-use application for iron oxides. Hefty plastic bags, which are green, contain yellow iron oxide and phthalo blue (an organic pigment), while the more recently available red polyethylene bags are colored only with iron oxide. Iron oxide pigments for plastics (or textile) use are generally not sold directly by the producer to either resin manufacturers or plastics fabricators. Instead, the pigments are marketed to independent formulators. They in turn manufacture color systems, which often contain other plastics additives such as modifiers and fillers, to be marketed to plastics fabricators. The colorants may be provided as concentrates (pellets, granules and powders), dry pigments, encapsulates, paste dispersions or liquids. Concentrates, which are concentrated mixtures of colorant in resin, are overwhelmingly the form preferred by fabricators. The consumption of iron oxides in paper, textiles and rubber is believed to be small. Synthetic brown is used in kraft paper and paperboard for food applications (e.g., candy box inserts) and in some other food wrapping materials. Iron oxides are used to some extent in textile applications because of their lightfastness and resistance to heat, solvents and alkalies. However, because of their weak tinctorial strength and drab shades, other pigments (and dyes) are usually preferable. Synthetic reds, browns and yellows are used in rubber, but no quantifiable information is available. The combined average annual growth rate for iron oxides in plastics, rubber, paper, textiles, glass and ceramics is 1.5-2.0% for 1999-2004. At this rate of growth, 2004 consumption would total about 19 thousand metric tons. Other . There are several iron oxide markets, some of which are nonpigmentary, for which little information is available. Foundry sands consumed about 14 thousand metric tons of natural red iron oxides in 1999. These sands are granular materials, primarily silica, that are mixed with binders to make molds for casting metals. At
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least 60% of U.S. foundries are believed to add iron oxides to foundry sands. The average addition of oxide to sand mixture is between 1% and 2%. Although many reasons are given for these additions, the most important is the reduction of veining and gas defects in the final product. About 9 thousand metric tons of iron oxides were consumed in animal feed and fertilizers in 1999. Most of this consumption was natural iron oxides. However, natural oxides can be used only in large-animal feeds, so there is a small market for synthetics as a colorant in small-animal feeds. All fertilizer consumption was of natural oxides. Consumption has been growing slowly in this application for the past decade and is expected to remain fairly flat from 1999 to 2004. Industrial chemicals, particularly catalysts, also consume small quantities of both natural and synthetic oxides. Iron oxide can be used as a dehydrogenation catalyst as well as function as the base material for formulated catalyst products. About 9 thousand metric tons of iron oxides were used in the production of industrial chemicals in 1999, primarily as catalysts in the production of styrene. Iron oxide is also used as a catalyst in the conversion of butenes to butadiene. Among the miscellaneous applications for iron oxide pigments are jewelers rouge, printing ink, including the synthetic black pigments in the ink used for printing all U.S. currency and artists colors. In the artists colors segment, it is believed that use of natural iron oxides greatly exceeds that of synthetics. Synthetic iron oxides have FDA approval for use in food contact and special grades are available for use in cosmetics, food additives and pharmaceuticals. The primary pharmaceutical application is as a colorant for capsules. Iron oxides are also used to color surgical gloves.
Price The following table presents recent U.S. prices for iron oxide pigments:
U.S. Prices for Finished Iron Oxide Pigments (dollars per pound) 1990a Low Black Natural Synthetic Micaceous Red Domestic Primer, Natural, Micronized Pure, Synthetic Spanish Yellow Synthetic Ocher, Domestic a. b. High 1997 1999
-0.6900 -------
0.2700 0.9000 0.6875 0.2875 0.7400b 0.3350c 0.8800b 0.2700d
na 1.08 na na 0.36 na 0.46 na
na 0.60 na na 0.33 na 0.39 na
Bulk truckload shipments, FOB U.S. origin, unless otherwise noted. Carload shipments of bagged material.
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c. d.
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Carload shipments, 50 pound bag, New York warehouse. Prices are for one short ton minimum, bagged material. (A) American Paint & Coatings Journal (data for 1990). (B) U.S. Imports, U.S. Department of Commerce, Bureau of the Census, Unit Import Values (data for 1997 and 1999).
SOURCES:
Trade Imports. In 1999 reported U.S. imports of synthetic iron oxide pigments were over 85 thousand metric tons, the highest annual quantity on record. Reported quantities are thought to be inflated, as some of the imports are thought to be regenerator or magnetic oxides, not exclusively pigments. U.S. import data are shown in the following table:
U.S. 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. 6.2 6.7 7.3 5.3 5.0 6.4 4.4 7.6 7.4 5.8 7.3 8.7 7.7 5.0 2.0 3.3 3.4 4.8 6.4 6.8 9.4 7.8 4.9 7.4 Millions of Dollars 0.3 0.4 0.4 0.7 1.1 2.0 1.3 1.7 1.8 1.6 2.1 2.4 2.1 1.3 1.4 1.6 1.4 1.4 2.1 2.6 3.4 3.0 2.4 3.7 Synthetic Thousands of Metric Tons 6.8 9.2 21.9 19.9 30.2 28.6 18.7 20.3 27.2 30.1 26.1 29.7 31.2 31.7 32.1 31.4 41.6 38.8 45.0 52.5 53.2 60.4 62.6 77.6 Millions of Dollars 1.1 1.7 5.3 8.4 18.7 16.5 11.9 15.0 19.7 21.0 19.4 18.2 25.0 29.2 35.9 37.7 48.5 55.9 59.3 75.0 70.6 72.4 61.8 69..3 Totalb Thousands of Metric Tons 13.0 15.9 29.2 25.1 35.2 35.0 23.0 27.9 34.7 36.1 33.4 38.4 38.9 36.7 34.1 34.7 45.1 43.5 51.4 59.3 62.6 68.2 67.5 85.1 Millions of Dollars 1.4 2.1 5.7 9.1 19.8 18.5 13.2 16.7 21.5 22.6 21.5 20.7 27.1 30.5 37.3 39.4 49.9 57.3 61.4 77.6 74.0 75.4 64.2 73.0
Data exclude Van Dyke brown for 1960-1982.
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b.
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Totals may not equal the sums of the categories because of rounding. (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 19941995). (D) U.S. Imports, U.S. Department of Commerce, Bureau of the Census (data for 1996-1999).
SOURCES:
In 1999, 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. Import data for synthetic iron oxide pigments are reported by category in the following tables:
U.S. 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. 0.46 0.56 0.66 0.94 4.29 5.11 7.55 8.38 9.02 11.87 6.75 9.19 11.00 8.80 9.9 10.2 12.0 Red 4.04 5.16 5.19 6.34 9.90 10.12 11.60 11.13 12.18 17.44 16.90 16.40 21.80 24.20 25.9 26.4 35.0 Yellow 6.93 11.77 13.62 11.89 10.18 10.12 10.68 11.94 8.92 10.30 11.90 15.80 14.70 15.80 19.2 22.8 28.6 Other 8.85 9.74 10.60 6.92 5.27 5.86 1.88 1.14 1.32 2.04 3.25 3.69 4.95 4.40 5.3 3.1 2.0 Totala 20.28 27.23 30.07 26.08 29.64 31.21 31.71 32.14 31.44 41.65 38.80 45.00 52.50 53.20 60.4 62.6 77.6
Totals may not equal the sums of the categories because of rounding. (A) Minerals Yearbook , U.S. Department of the Interior, Bureau of Mines (data for 1983-1988). (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).
SOURCES:
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U.S. 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. 0.26 0.39 0.39 0.60 0.72 1.43 11.44 15.30 18.68 23.23 25.10 26.10 30.70 25.56 23.8 16.7 15.8 Red 2.73 4.63 2.84 2.96 3.58 4.66 4.68 7.12 8.29 11.47 11.90 10.90 20.90 22.22 20.4 19.0 25.7 Yellow 5.12 7.52 5.77 5.52 6.84 7.85 8.59 10.80 8.74 10.10 12.50 16.20 15.90 16.15 19.5 20.4 24.7 Other 6.87 7.17 12.00 10.29 7.10 11.06 4.48 2.69 2.04 3.68 6.50 6.01 7.50 6.67 8.7 5.7 3.1 Totala 14.98 19.72 21.00 19.38 18.24 25.00 29.19 35.92 37.74 48.49 55.90 59.30 75.00 70.60 72.4 61.8 69.3
Totals may not equal the sums of the categories because of rounding. (A) Minerals Yearbook, U.S. Department of the Interior, Bureau of Mines (data for 1983-1988). (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).
SOURCES:
In 1999, imports accounted for about one-third of U.S. iron oxide pigment consumption. Much of the U.S. supply of iron oxide pigments originated in China, followed by Germany. Some of these pigments are further processed by Bayer at its New Martinsville, West Virginia plant, while the balance is sold to end users and resellers. Imports will continue to be an important source of the U.S. supply of iron oxide pigments. Exports. In 1999, U.S. exports of pigment-grade iron oxide were 13.8 thousand metric tons. The major destinations for 1999 iron oxide exports were Mexico and Japan at 7.7 and 1.7 thousand metric tons respectively. Historical export data follow:
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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:
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U.S. Producers of Major Chrome PigmentsApril 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.
Since 1997, the following changes have occurred among U.S. chrome pigment producers:
q
In October 1997, K-L Holdings purchased Laporte Incs 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.
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.
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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:
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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:
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U.S. 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. b. c. 18.1 17.2 16.8 18.1 18.6 15.9 13.6 14.5 12.7 12.0 9.8 9.1 8.5 8.7 8.0 7.5 5.5 5.3 5.0 5.3 Molybdate Orange 4.5 4.5 3.6 4.1 4.2 3.1 3.1 3.2 2.7 3.2 2.8 2.2 2.0 1.8 1.7 1.5 1.5 1.5 1.5 1.6 Chromium Oxidesa 3.2 3.2 3.2 3.6 3.2 3.1 3.0 2.9 2.6 na na na na na na na na na na na Zinc Chromate 4.5 4.5 4.5 3.6 4.1 4.1 4.1 4.1 4.1 3.9 3.8 1.8 2.0 2.0 1.9 1.8 1.8 1.8 1.8 1.8 Otherb 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 2.3 na na na na na na na na na na na Totalc 32.7 31.8 30.4 31.8 32.3 28.4 26.0 26.9 24.4 19.1 16.4 13.1 12.5 12.5 11.5 10.8 8.8 8.6 8.3 8.7
Data for 1984-1988 include about 0.5 thousand short tons annually of specialty-grade chromium oxide green used in camouflage coatings. Includes chrome green (a lead chromate) and normal lead silicochromate as well as corrosion-inhibiting pigments strontium chromate, magnesium chromate, barium chromate and calcium chromate. Totals may not equal the sums of the categories because of rounding. CEH estimates.
SOURCE:
Lead chromatebased pigments are prohibited from use in architectural consumer paints because of regulation by the Consumer Product Safety Act (see ENVIRONMENTAL ISSUES ). Other chrome pigments, chromium oxides for example, are less restricted. The majority of chrome pigments are used in special-purpose coatings and OEM product finishes. The major markets consuming chrome yellows traffic paints, machinery and equipment finishes and OEM transportation vehicle finishesare increasingly switching to nonlead chromate alternatives. The current market for chrome orange, in rustinhibiting paints, is negligible. Although more resistant to alkali attack than chrome yellow, the need for larger particles of chrome and molybdate orange pigments makes over-grinding a problem; over-grinding creates a yellower hue and results in poor hiding power. Because of its brilliance, lightfastness and low cost, molybdate orange has been used in machinery and equipment finishes. In the past it was often blended with organic reds and violets to produce low-cost, durable automotive finishes. Since it weathers well, chromium oxide green has some application in outdoor industrial coatings. A unique feature of chromium oxide green is that it reflects infrared radiation in a manner similar to
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chlorophyll, making it appropriate for use in the formulation of camouflage coatings resembling green foliage. Hydrated chromium oxide green has some limited use in mixtures with other chrome pigments to produce the brilliant lightfast greens of exterior architectural paints. Zinc chromate is used solely as an anticorrosive pigment. Although there are health concerns about zinc chromate, it is less toxic and less expensive than the corrosion-inhibiting strontium and calcium chromate pigments. Nonetheless, consumption of zinc chromate is expected to decline as other less toxic substitutes, such as zinc phosphate, are used. Future consumption of chrome pigments in surface coatings is primarily determined by the regulatory environment, with the use of hexavalent chromium and lead highly restricted. Safety requirements are being addressed with the use of low-dust lead chromates and low-dust, low-solubility Krolor (a registered trademark owned by Dominion Colour) silica-encapsulated lead chromates. They remain in applications where some organic replacements have lacked the performance of lead chromates, particularly in outdoor and harsh environments. Historically, lead chromates largest market segment, traffic paint, has had the greatest impact on lead chromate consumption. Over half of the states of the United States have banned its use on highways, accounting for over 70% of the paved roads of the U.S. (See the ENVIRONMENTAL ISSUES section for more information on lead chromate environmental regulations.) Organic pigment alternatives are more expensive on a per-pound basis and they may not provide equal durability. The consumption of chrome pigments in paints is expected to continue to decrease. Plastics. The second-largest market segment for lead chromate pigments is plastics. In 1999, roughly 3.7 thousand metric tons were consumed in plastics. Estimated consumption of lead chromates by the plastics industry in recent years is reported in the following table:
U.S. 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. 3.6 4.1 3.4 3.9 4.0 4.1 4.5 6.4 7.3 7.0 6.8 6.7 6.6 6.3 5.8 5.6 5.4 4.0 3.7 3.7
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Chromium oxide and chrome greens also find use in this market. Less than one thousand metric tons of chromium oxides were consumed in plastics in 1999. Almost all of this was used in PVC (polyvinyl chloride resin) siding. In plastics the chrome yellows and molybdate oranges, as well as chemically stabilized forms of these pigments, provide high opacity, low cost and bright colors. Furthermore, the excellent blending characteristics of these pigments with colors of adjoining hues considerably extend their utility. The major performance limitation of the chrome yellows and oranges in plastics is in the area of heat stability, since they can be used only up to 180C, although their reactivity with acids, alkalis and sulfides imposes some additional limitations. However, 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. A 15-20%-by-weight coating of silica vastly improves both chemical and heat resistance (up to 320C) as well as the lightfastness of chromate pigments. Consequently, silica-encapsulated lead chromates compete for a portion of the cadmium pigments market in engineering plastics, although organic pigments may be substituted for a greater share of the market. The color shading of chromates is equivalent to that of cadmium pigments and they have a lower price. Generally, conventional chromates are used to color vinyls and low-temperature polyolefin and polystyrene resins. Lead chromates also are recommended for use in various thermosets, including epoxy, phenolics and polyurethane. Chrome greens find some application in the plastics industry, although their sensitivity to alkaline conditions somewhat restricts their performance. They are used in polyesters and low-density polyethylene. Chromium oxide greens, because of their outstanding chemical inertness and heat stability up to 1,000C, are appropriate for plastics use. However, the nonhydrated form is drab in color and low in brightness, which limits its use in applications where a bright green color is preferable. Chromium oxide greens are used in thermoplastics, including ABS resins, cellulosics, polyethylenes and vinyls. Thermoset uses include epoxies, polyesters and urethanes. The hydrated form, a brilliant green hue that dehydrates at 200C, is used only in cellulosics. When a bright green color is desired in other resins, phthalocyanine green, rather than hydrated chromium oxide, is the pigment of choice. As discussed in the Iron Oxide Pigments Consumption section of this report, 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. U.S. consumption of all chrome pigments in plastics for 1999-2004 is likely to continue to decline. It is expected that consumers will continue to substitute organic pigments where possible, 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). Ceramic, glass and construction materials. An estimated 12% of chromium oxide green consumption is in ceramic, glass and construction materials. In 1996, this market represented less than one thousand metric tons. This category includes a number of products ranging from industrial refractories to glass, mortar, whiteware, porcelain enamels, china and tile. Because of its chemical and heat resistance, chromic oxide green is the main ingredient in most green ceramic colorant compositions and is also used to prepare many green-colored glasses. In ceramic appli-
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cations, chromium oxide can be used alone. However, it is frequently combined with other ingredients (e.g., cobalt oxide and aluminum oxide) both to modify its color and to improve its stability. Green glasses can be produced using chromium oxide in solution in a siliceous matrix. This system performs best when antimony trioxide is present in the glass; without it the chromium oxide tends to develop a yellow-orange color. Chromium oxides can also be used in the manufacture of ceramic materials requiring pink coloration. In this case, they are commonly mixed with tin oxide and calcium to form the so-called chrome-tin pinks, which range in hue from pink through crimson to lilac. The majority of these chrome-pink pigments are stable up to 1,350C. 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, it is a component of the vitreous coating applied to the metal surfaces of bathtubs and appliances, such as range tops, washers and dryers. Chromium oxides also find application in industrial refractories. The most common industrial refractories are those composed of single or mixed oxides of chromium, aluminum, calcium, magnesium, silicon and zirconium. Chromium oxide greens are also used to color ceramic glazes, mortar and concrete. Hydrated chromium oxide green is less heat-resistant than chromium oxide and is therefore unsuited for high-temperature ceramic applications, although it can be used for coloring high-baking enamels. The ceramics market for chrome pigments is believed to be relatively stable. No growth is expected during 1999-2004. Roofing granules. Less than one thousand metric tons of chromium oxide green were consumed as a pigment in roofing granules in 1999. Roofing granules are mineral granules, coated with silicates mixed with various pigments. Green chromium oxide is the most commonly used chromium pigment. Because this pigment exhibits outstanding resistance to sunlight and the other severe conditions of exterior exposure, it provides excellent durability in this application. It is expected that substitutions for chromium oxide will increasingly be sought in roofing granules. No growth is anticipated in this market. Printing inks. Historically lead chromates have been used in printing inks as they have good hiding power, ink flow, nonbleeding characteristics and stability. However by the mid-1990s, concerns about health and environmental issues had eliminated lead chromate from inks in nearly all applications in the United States. Because of the deleterious health effects of lead chromate pigments, their use in inks is restricted, especially in inks that could contact food or on articles intended for use by children. 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. Other . Among the various applications that provide small markets for lead chromate pigments are paper, elastomers, pigmented leather finishes and floor coverings.
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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.g., ointments). They have some application in rubber compositions because of their tolerance for any type of cure and also have limited application in textiles and artists colors. No quantitative data on these other markets are available.
Price See the trade section for U.S. average unit import values for chrome pigments.
Trade Imports. U.S. imports and import values since 1964 are shown in the following tables:
U.S. 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 0.1 neg 0.1 0.1 neg neg 0.1 neg neg 0.2 0.1 0.1 0.2 -----------Chrome Yellow 0.7 0.8 4.8 2.2 1.2 1.2 1.3 1.8 2.3 2.9 1.9 3.4 4.0 3.7 3.6 3.5 3.5 3.6 5.1 4.7 7.0 6.8 6.4 6.8 Molybdate Orange neg neg 0.1 0.2 0.5 0.5 0.4 0.7 0.9 1.0 0.8 1.1 1.1 1.0 0.9 0.8 0.9 0.7 0.6 0.7 1.8 1.8 2.0 1.6 Chromium Oxide Green 0.2 0.1 0.9 0.3 3.5 2.2 1.5 1.8 1.8 1.4 2.6 2.4 4.0 -----------Totala 1.0 1.0 6.0 2.9 5.2 4.0 3.2 4.3 5.1 5.4 5.4 6.9 9.3 6.0 5.7 4.9 6.9 5.0 6.4 6.3 9.8 8.6 8.4 8.4
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a.
Totals may not equal the sums of the categories because of rounding. After 1988, total includes zinc yellow and all other pigments and preparations based on chromium compounds. U.S. Imports, U.S. Department of Commerce, Bureau of the Census.
SOURCE:
U.S. Average Import Values for Lead Chromate Pigments (dollars per pound) Chrome Yellow 1997 1998 1999 SOURCE: 1.30 1.30 1.28 Molybdate Orange 1.65 1.75 1.93 Zinc Chrome Yellow na 0.75 0.43
U.S. Imports, U.S. Department of Commerce, Bureau of the Census.
In 1999, 8.4 thousand metric tons of chromium-based pigments were imported to the United States, a decrease from the 9.8 thousand metric tons imported in 1996. Chrome yellow was the major import, accounting for 6.8 thousand metric tons of the total. Canada was the origin for 55% of the chrome yellow imported. Chrome pigment imports from Canada increased beginning in 1996, following the closure of Cookson Pigment, the largest U.S. chromium pigments plant. Exports. U.S. export quantities and values of chrome pigments since 1980 are shown in the following table:
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U.S. 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: 2.7 2.4 2.0 2.3 1.9 1.8 2.3 3.2 3.2 2.3 2.6 2.0 2.7 2.3 1.3 na na 3.8 2.3 1.5 Value (millions of dollars) 9.50 8.62 7.44 8.83 7.21 6.44 7.62 9.53 11.07 7.65 9.25 7.42 11.34 9.40 6.01 na na 13.1 8.2 6.2
(A) U.S. Exports, U.S. Department of Commerce, Bureau of the Census (data for 1980-1992). (B) Mineral Industry Surveys, U.S. Department of the Interior, Bureau of Mines (data for 1993-1994). (C) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for 19951996). (D) U.S. trade (data for 1997-2000).
U.S. lead chromate pigment exports declined after 1996 when over 50% of U.S. production capacity was closed. Canada and Mexico supply most of the export markets formerly served by the United States.
Complex Inorganic Pigments Producing companies U.S. producers of complex inorganic pigments (formerly known as mixed-metal oxides) are listed in the following table. Each producer manufactures other products in addition to those specified in the table.
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U.S. Producers of Major Complex Inorganic PigmentsMarch 1997 a Company and Plant Location Cerdec Corporation Drakenfeld Products Washington, PA Engelhard Corporation Specialty Pigments and Additivesb Elyria, OH Ferro Corporation Coatings, Colors, & Ceramics Group Pigments Division Cleveland, OH Toccoa, GA The Shepherd Color Companyb Cincinnati, OH a. PBk- PBk- 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
Only selected complex inorganic products are shown. All producers listed in the table manufacture both ceramic- and pigment-grade complex inorganic pigments. 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.
Company also produces PG-17. CEH estimates.
SOURCE:
In December 2000, BASF closed its Rensselaer, New York complex inorganic pigments plant.
Production U.S. production data for complex inorganic pigments are not published. For 1999, U.S. production was an estimated 7.9 thousand metric tons.
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Consumption Estimated U.S. consumption of complex inorganic pigments in 1999 was 7.6 thousand metric tons. U.S. consumption for 1996 and 1999 is segmented as follows:
U.S. 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. 4.6 1.8 1.1 0.1 7.6 Market Share (percent) 60 24 15 1 100% Quantity (thousands of metric tons) 4.6 1.8 1.0 0.2 7.6 1999 Market Share (percent) 60 24 13 3 100%
Plastics and rubber. An estimated 4.6 thousand metric tons of complex inorganic pigments were consumed in the plastics and rubber industries in 1999. Although these pigments were used for coloring a variety of thermoplastics, thermosets and high-temperature engineering resins, the leading plastics application was in polyvinyl chloride (PVC) for exterior siding. The leading rubber applications include the coloration of silicon rubber used in high-temperature hoses, spark plug cables and computer cables where color coding is important. The PVC siding market accounts for approximately 75% of total complex inorganics used in the plastics and rubber market segment. The major PVC siding application for complex inorganic pigments, cap stock, uses only an outer layer of pigmentation. Instead of pigmenting the entire piece of siding, a laminate surface of color containing complex inorganics and titanium dioxide is coextruded over a nonpigmented PVC base profile. Coextruded siding not only requires less pigment than traditional PVC siding but also results in a more durable product. PVC siding has traditionally been used for remodeling and for mobile homes, but it has recently gained acceptability in new residential construction. Nickel and chrome titanates are the most frequently used complex inorganics in PVC. Chrome antimony titanium buff rutile (PBn-24) is often the colorant of choice. PG-17, appearing black in higher concentrations is typically used as a substitute for carbon black for siding since it absorbs less energy and, therefore, lowers air-conditioning costs. For overall plastics use, both chrome and nickel titanates have attained prominence as colorants. Nickel titanates in combination with high-performance organic pigments have replaced some lead chromates and cadmium yellows. Their excellent stability at high temperatures can make them a good choice in certain plastics applications. However, their poor tinctorial strength can require a heavy loading, weakening some plastics. Manganese titanates may be used in place of iron-containing pigments, which sometimes compromise the stability of some resins. Imported, rare earthbased pigments from Rhne-Poulenc in France show significant promise in the thermoset plastics market segment. This cerium containing pigment line, known as Neolor, is available
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in orange (PO-75) and red (PR-265). This product is a suitable, albeit expensive alternative to cadmium pigments with a price of $17-18 per pound. Ceramic and glass materials. Complex inorganics were first used in ceramics and glass applications because of their high heat stability. Consumption in 1999 was an estimated 1.8 thousand metric tons. The ceramic and glass materials colorants category includes both colorants used in clay-based products and colorants used in glass manufacture. Since clay-based products are often coated with glazes, the two applications can overlap. Applications for complex inorganics include ceramic bodies, underglaze decoration, colored glazes, overglaze decoration, porcelain enamels, colored glasses, forehearth colors (strongly colored glass added to molten uncolored glass) and on-glass decorations. The processing temperatures required in these applications may be as high as or higher than 1,300C. To withstand these extremely high temperatures, complex inorganics are often the pigments of choice. In particular, complex inorganics of the spinel and zircon families are commonly used. Although these types of pigments possess a wider range of temperature stability than the cadmiums (which are also used to color ceramics), they lack the brilliance and intensity of cadmium colorants. (See the following section on Cadmium Pigments.) 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. Spinels are used extensively in wall tile and in some sanitaryware. Tile and sanitaryware applications differ from one another in the heat required to fuse the glaze to the ware. Tiles are normally heated to about 1,140 C while sanitaryware is fired to about 1,300C. Some spinels fail to withstand the 1,300C temperature. They actually dissolve, destroying the crystal lattice, resulting in disappearance of the color. Thus, for higher-temperature firings, the zircons are employed. Zirconium silicate is an extremely stable oxidic compound with a cubic lattice into which metallic ions may be introduced to generate color. For example, if vanadium is substituted for silicon in the crystal structure, a blue color results. 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. Reductions in the use of cadmium because of environmental regulations continue to create increased demand for complex inorganics over cadmium ; however, the increased imports of ceramics, particularly from Italy, has decreased U.S. ceramic production and the overall demand for pigments in ceramics. Overall, ceramics production has been declining in the U.S. because of manufacturing relocations and rising imports. Porcelain enamel has also been declining as white goods are increasingly manufactured with painted metal. Paints and coatings. Consumption of complex inorganics in paints and coatings in 1999 was estimated at 1.0 thousand metric tons, accounting for about 15% of total consumption. Nickel titanates are probably the most important single group of complex inorganics used in paints. They are consumed in exterior house paints, auto enamels and coil coatings for outdoor applications. To some extent, nickel titanates are used as substitutes for chrome yellows. Cobalt chromite green is the second complex inorganic pigment of significance in the coatings industry. Since this pigment simulates the reflectance properties of chlorophyll, it is valuable as a camouflage coating and has been approved for use in U.S. military applications.
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In practice, camouflage coatings are generally blends of green, brown and black pigments, including cobalt-based complex inorganics. Often the blends include black iron oxide, chromium oxides, zinc ferrites and cobalt chromite green, plus small quantities of organic pigments. Camouflage pigments are used in fabrics for netting, tent materials and truck tarps. However, in coating machinery, camouflage coatings have evolved from alkyds to two-component urethane systems. The urethane finish lasts much longer than the alkyd, reducing the need to refinish as frequently. Coil coatings are believed to consume the largest percentage of the complex inorganics used by the surface coatings industry. These coatings are used primarily on aluminum and steel sidings for residential homes, mobile homes and commercial buildings. The coatings, containing complex inorganic colorants, are liquid resin systems applied at high speeds to continuous sheets, strips and coils of aluminum or steel and baked at high temperatures. The primary complex inorganics used in coil coatings are nickel and chrome titanates, which possess color stability at high temperatures. In the United States, complex inorganic pigments in paints and coatings have nearly completed their growth because of replacement of chrome yellows and cadmium pigments. Other . Limited quantities of complex inorganics are used in adhesives, ceramics, inks (including food contact inks for plastics), roofing granules, concrete swimming pools, cement grouts, artists colors and cosmetics (particularly violet). The size of this market segment was about 200 metric tons in 1999.
Price The following table presents representative list prices for selected complex inorganic pigments:
U.S. 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. Cobalt Surcharge March 1997 Prices Cobalt Surcharge March 2001 Prices Cobalt Surcharge
19.86 na 5.95 16.02 6.68 12.65 36.57 ----
2.06 na none 2.07 none 1.00 1.29 ----
na 18.00 5.00 13.60 6.25 11.60 24.00 ----
na 4.00 none 1.60 none 1.20 5.50 ----
--5.00 13.60 ---3.25 11.60 3.50
--none 0.40 ---none 0.25 none
Prices based on one thousand pound quantities. Cobalt surcharge is included in price and is subject to change without notice, depending on cobalt market conditions. CEH estimates.
SOURCE:
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Trade Trade data for complex inorganic pigments are not reported. It is estimated that just over 450 metric tons were imported by the United States in 1999, primarily from Japan and Germany. Exports are estimated at 675 metric tons in 1999, with destinations primarily in Western Europe, followed by Canada, Asia (China, the Republic of Korea, Taiwan, Malaysia and Singapore) and South America.
Cadmium Pigments Producing companies The following table lists U.S. producers of cadmium pigments, plant locations and specific products manufactured:
U.S. Producers of Cadmium PigmentsMarch 2001a Company and Plant Location Engelhard Corporation Specialty Pigments and Additives Louisville, KY Millennium Inorganic Chemicals, Inc. Baltimore, MD a. 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)
A colon followed by 1 denotes the lithopone form of the pigment. Englehard Corporation is the largest-volume producer. Ferro blends pigments at the Cleveland, Ohio plant that are produced in Celaya, Mexico. SOURCE: CEH estimates.
Salient statistics U.S. salient statistics for cadmium-based pigments are shown in the following table:
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U.S. Supply/Demand for Cadmium Pigments (thousands of metric tons, gross weight basis) Production 1986 1987 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 SOURCES: 0.9 0.8 0.6 0.8 0.5 0.6 0.6 0.7 0.7 0.4 0.4 0.4 0.4 0.4 Imports na na na 0.9 0.8 0.4 0.5 0.3 0.3 0.2 0.2 0.2 0.2 0.2 Exports na na na neg neg 0.1 0.2 0.2 0.4 0.1 0.1 0.2 0.2 0.3 Apparent Consumption na na 2.3 1.7 1.3 0.9 0.9 0.8 0.6 0.5 0.5 0.4 0.4 0.3
(A) U.S. Imports, U.S. Department of Commerce, Bureau of the Census (data for IMPORTS). (B) U.S. Exports, U.S. Department of Commerce, Bureau of the Census (data for EXPORTS). (C) CEH estimates (all other data).
Cadmium pigment consumption and production is expected to fall further as OSHA limits on cadmium exposure in the workplace, CONEG requirements and EPA regulations increasingly restrict the use of cadmium. U.S. consumption of cadmium pigments in 1999 was about 0.3 thousand metric tons, 13% of the amount consumed in 1988. Estimated market shares of cadmium pigments by end use in 1996 and 1999 are presented in the following table:
U.S. Consumption of Cadmium Pigments by End Use 1996 Quantity (metric tons) Plastics Ceramic Materials Paints and Coatings Other Total SOURCE: CEH estimates. 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%
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Plastics. The plastics industry is the largest U.S. market for cadmium pigments. Estimated consumption of cadmium pigments in plastics in recent years is reported in the following table. Much of this consumption is of the lithopone form of cadmium pigments.
U.S. 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. 2.1 2.5 2.0 2.2 2.2 2.2 2.2 2.2 2.1 1.5 1.1 0.8 0.7 0.5 0.4 0.4 0.3 0.2 0.2 0.2
Historically, cadmium pigments have been consumed mainly in the following plastic resins: acrylonitrilebutadiene-styrene terpolymer (ABS), high-density polyethylene (HDPE), low-density polyethylene (LDPE), polypropylene (PP) and polystyrene (PS). Polyvinyl chloride (PVC) and engineering resins such as polycarbonates, polyacetals, nylons, thermoplastic polyesters and polyphenylene oxides have historically accounted for less than 5% of the plastic market for cadmium pigments. In the higher-processing-temperature plastics such as HDPE and the engineering resins, cadmium has been the pigment of choice, although mixtures of complex inorganics and organic pigments may also be used. Bayer Corporation ceased cadmium pigment use in its thermoplastics in 1990. Bayer reformulated its cadmium-containing pigments and substituted organic dyes in its inorganic and organic pigments. Other plastics producers such as General Electric have also replaced cadmium pigments in their products. On a functional basis, cadmium pigments work well in practically all plastics, because of their opacity, resistance to migration, excellent lightfastness, ability to tolerate high temperatures (800-900C), brilliant clear colors and easy dispersibility. They are weak only in their resistance to acidic conditions or moisture. As is true for other pigments, cadmiums are not generally introduced into plastics through direct dispersion of dry pigment into the host resin material. More often, plastics compounders introduce
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pigments in a predispersed form, known as masterbatch pellets, which hold cadmium colorant in a compounded resin, permitting plastics fabricators to add color at the optimum stage of the manufacturing process. Paste dispersions, liquid color and encapsulated pigments have also found wide acceptance among plastics formulators as a means of introducing color to resins. All these pigment vehicles reduce the problem of dusting and provide higher color consistency. Over the next five years, cadmium pigment consumption per volume of plastic produced is expected to decline despite growth in plastics output. Ceramic materials. An estimated 30-40% of the total market for cadmium pigments is in the ceramic materials area. In 1999, this is estimated to have been less than 40 metric tons. Cadmium reds, oranges and yellows have been used extensively (usually in the form of colored frits) in the mass coloration and external decoration of glass, in porcelain enamel coatings for metal and in underglaze and overglaze decorations and glaze stains for ceramic clay objects. Cadmium colorants work well because they are capable of withstanding extremely high ceramic processing temperatures (up to 900C) and because of the bright, varied colors they offer. Currently, the largest portion of cadmium pigments consumed in ceramics is in ceramic tiles and artware, as components of glaze stains and in overglaze and underglaze decorations. Glazes formulated to be compatible with the pigments and to promote color development, pigment stability and chemical durability are used in conjunction with the cadmium colorants. Such glazes are low in alkali content and usually contain cadmium oxide. The presence of the oxide reduces the chemical potential of the cadmium in the molten glaze during firing, thereby enhancing the stability of the pigment in the final glazed product. The largest portion of cadmium pigment consumption for ceramics applications has traditionally been in porcelain enamels for aluminum, sheet steel and cast iron. Such aluminum products as gas barbecue grills may be coated with enamels containing cadmium sulfide or sulfoselenide pigments. There was a market for cadmium pigments in aluminum cookware, but this has declined significantly as imports have replaced domestic products and consumer preference has changed from bright colors to browns. This may also occur with cast iron stove parts, exhaust systems and heater parts. Cadmium yellows and reds are used both in mass coloration of glass (e.g., reds for traffic signals, railway signal glasses and marine navigational lights) and in on-glass decorations (e.g., labels on soda bottles). In these transparent glass applications, the cadmium pigment particles are colloidally dispersed and produce colors by selective absorption and scattering of light. The overall decline in this market is expected to continue. Paints and coatings. In 1999, the consumption of cadmiums in paints and coatings was dominated by primers. Historically, cadmium pigments were used in the manufacture of industrial coatings (particularly coatings used for anticorrosion maintenance) for steam and process chemical pipes, process equipment and general interior plant use, because of their good resistance to chemical attack, particularly from alkalis, as well as resistance to heat. Smaller applications included use in metal coil coatings, some machinery and equipment coatings, auto refinishing and various specialty coatings.
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Other . Altogether, other uses accounted for less than 40 metric tons of cadmium pigments in 1999. Most of the other uses are believed to be in artists paints where cadmium yellows, oranges and reds offer pleasing hue, lightfastness and sulfide stain resistance. Cadmium pigments also have some limited use in rubber products, such as rubber flooring and silicone rubber cable. Cadmiums are stable to the curing conditions of rubber and do not stain or bleed. However, because other less expensive pigments also satisfy rubber requirements, cadmiums are rarely the pigment of choice. Cadmiums were also used to color some printing inks, synthetic fibers, paper laminates and leather finishes. However, use in these applications is believed to be extremely limited and likely to decrease.
Price U.S. year-end prices for cadmium pigments in selected years were as follows:
U.S. Prices for Finished Cadmium Pigments (dollars per pound) 1989 Lithopone Orange, Cadmium-Selenidea Deep Red, Cadmium-Selenideb Light Medium Light Medium Deep Maroon Yellow Pure Red Yellow a. b. 500-pound bags. 400-pound barrels, FOB shipping point, freight allowed east of Rocky Mountains. One-ton lots, FOB shipping point, freight allowed east of Rocky Mountains. (A) American Paint & Coatings Journal (data for 1989 and 1995). (B) Chemical Marketing Reporter (data for 2000). 1995 2000
3.23-3.70 4.15-4.18 4.43-4.46 4.35-4.88 5.31 5.75-5.76 2.34c 8.63-9.64 0.70-0.74
6.65-7.10 4.15-4.18 4.43-4.46 4.35-4.88 5.31 5.75-5.76 5.15c 8.63-9.64 na
6.14b na na na na na na na na
c.
SOURCES:
On a price-per-pound basis, cadmium pigments are generally more expensive than other inorganic pigments (except complex inorganics). Between 1995 and 1996, prices doubled for some lithopone cadmium-selenide reds, while prices for other cadmium pigments remained relatively unchanged, reflecting weak demand. Prices for cadmium pigments are expected to soften as demand continues to decay.
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Trade Trade data for cadmium pigments are reported in the Salient statistics section.
Other Inorganic Pigments See the World Market Value of Color Pigments by Region1999 and World Consumption of Pigments by Region1999 tables for U.S. consumption of minor pigments not produced in the United States, including ultramarines, iron blues, bismuth vanadate and rare earth sulfides. Further information about the manufacture of these pigments and trade can be found in the Western European section. No detailed information is available on the supply and demand for other inorganic pigments.
CANADA Producing Companies Dominion Colour Corporations plant in Ajax, Ontario is the worlds largest lead chromate plant and the only site of lead chromate production in Canada. The company produces chrome yellow (PY-34) and molybdate orange (PR-104). Lead chromates production capacity was expanded by 65% at this plant in 1996. In 1997 the Ajax facility began production of silica-encapsulated lead chromate pigments, using technology purchased from Cookson Pigments.
Consumption Canadian consumption of inorganic color pigments is estimated in the table below.
Canadian Consumption of Inorganic Color Pigments (thousands of metric tons) Iron Oxide 1996 1999 SOURCE: 17.9 21.3 CEH estimates. Lead Chromate 1.6-1.8 1.6-1.8 Cadmium neg neg
Trade Complete data are not available for Canadian trade in inorganic pigments. The majority of Canadas pigment exports are to the United States. According to U.S. trade statistics, Canadian exports of inorganic pigments to the United States are as follows:
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Canadian Exports of Inorganic Pigments to the United States (metric tons) Synthetic Iron Oxide 1993 1994 1995 1996 1997 1998 1999 SOURCE: 394 5,967 6,380 6,260 6,030 4,940 4,064 Chromium 18 na 321 7,056 7,001 5,568 5,209 Cadmium 30 54 34 29 77 47 62
Canadas U.S. chromium exports grew significantly following the closure of half of the U.S. lead chromate production capacity in 1996.
MEXICO Producing Companies Iron oxide pigments De Mateo y Compaa, S.A. de C.V. in Zumpango, Mxico produces synthetic black (PBk-11) and Synthetic Brown (PBn-6).
Chrome pigments The following table lists the chrome pigments producers of Mexico:
Mexican Producers of Chrome PigmentsApril 2001 Lead Chromates Company and Plant Location Pyosa, S.A. de C.V. Monterrey, Nuevo Len SOURCE: CEH estimates. Chrome Yellow (PY-34) Molybdate Orange (PR-104)
BASFs lead chromate pigment plant at Santa Clara closed in 1997, shifting lead chromate supply to imports from BASFs plant in Germany.
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Complex inorganic pigments Only one company is known to produce complex inorganic pigments in Mexico: Ferro Mxicana, S.A. de C.V. in Mexico City. This plant produces black (PBk-28), blue (PB-28, PB-35, PB-71), red (PR-230, PR231, PR-232, PR-233, PR-235, PR-236) and yellow (PY-158, PY-159, PY-160) pigments.
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. 15.6 8.5 12.5 14.8 16.7 17.8
Estimates for consumption of other inorganic pigments are not available.
Consumption Mexican consumption of inorganic pigments is estimated in the table below.

Mexican Consumption of Inorganic Color Pigments (thousands of metric tons) Iron Oxide 1996 1999 SOURCE: 16-17 19-20 CEH estimates. Lead Chromate 2.5 2.5 Cadmium neg neg
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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: 0.3 0.3 0.2 0.2 0.2 0.3 0.3 Cadmium Pigments 0.1 0.1 0.1 0.1 0.1 neg neg Other 1.1 2.9 2.2 2.4 3.1 3.5 5.7 Total 1.5 3.3 2.5 2.7 3.4 3.8 6.0
(A) Sistema de Informacin, Comercial de Mxico, Banco Nacional de Comercio (data for 1993-1995 and TOTAL all years). (B) CEH estimates (all other data).
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: 1.0 1.3 2.2 2.2 2.2 2.2 2.3 Cadmium Pigments neg neg neg neg neg neg neg Other na 2.1 3.1 3.1 3.1 3.2 3.4 Total na 3.4 5.3 5.3 5.3 5.5 5.7
(A) Sistema de Informacin, Comercial de Mxico, Banco Nacional de Comercio (data for 1993-1995 and TOTAL all years). (B) CEH estimates (all other data).
Chromium pigment exports rose rapidly following the pesos devaluation in 1994, while weakening U.S. demand for cadmium pigments led to a decline in cadmium exports. In 1995, 44% of Mexicos chromium pigment exports went to the United States, followed by Canada at 17%. The United States was the sole destination for cadmium pigment exports in 1995. Total inorganic color pigment exports more than doubled between 1996 and 1999 to 6 thousand metric tons.
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SOUTH AMERICA Iron Oxide Pigments The following table lists synthetic iron oxideproducing companies, plant locations and specific pigments produced:
South American Producers of Synthetic Iron Oxide PigmentsMarch 2001a Company and Plant Location Argentina Qumica Sudamericana S.A. Berazategui, Buenos Aires Brazil Bayer S.A. Porto Feliz, So Paulo Chile Pigmentos Marathon S.A. Quinta Normal, Regin Metropolitana de Santiago X ___________________ a. C.A. Venezolana de Pigmentos in Valencia, Carabobo, Venezuela also produces a number of iron oxide pigments. SOURCE: CEH estimates. Black PBK-11 Red PR-101 Brown PBn-6 Yellow PY-42
Chrome Pigments The following table lists the chrome pigment producers in South America:
South American Producers of Lead Chromate PigmentsMarch 2001 Chrome Yellow (PY-34) Molybdate Orange (PR-104) Chromium Oxide Green (PG-17)
Company and Plant Location Argentina ARCOLOR S.A. C.I.I.F.A. Pilar, Buenos Aires Brazil BASF S.A. So Caentano do Sul, So Paulo Cleomar Qumica Indstria e Comrcio Ltda. Indaiatuba, So Paulo Qumica Brasil-Sumar Ltda. Sumar, So Paulo
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South American Producers of Lead Chromate PigmentsMarch 2001 (continued) Chrome Yellow (PY-34) Molybdate Orange (PR-104) Chromium Oxide Green (PG-17)
Company and Plant Location Colombia Pigmentos y Productos Qumicos S.A. Girardota, Antioqua Venezuela C.A. Venezolana de Pigmentos Valencia, Carabobo SOURCE: CEH estimates.
Complex Inorganic Pigments At least two companies produce complex inorganic pigments in South America:
South American Producers of Complex Inorganic PigmentsApril 2001 Company and Plant Location Argentina ARCOLOR S.A. C.I.I.F.A. Pilar, Buenos Aires a Brazil Ferro Enamel do Brazil Industria e Comercio Ltda. Sao Bernardo do Campo Sao Paulob a. b. Black (PBk-28) Blue (PB-28) Blue (PB-35) Brown (PBn-24) Brown (PBn-33) Red (PR-231) Yellow (PY-53) Yellow (PY-160)
Arcolor also produces PB-36. Ferro also produces PR-233, PR-235, PR-236 and PY-159. CEH estimates.
SOURCE:
Cadmium Pigments Cadmium pigments PO-20, PR-108 and PY-37 are produced by ARCOLOR S.A. C.I.I.F.A. at Pilar, Buenos Aires, Argentina.
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Consumption See the World Consumption of Pigments by Region table for South American inorganic color pigment consumption.
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)
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, is carried out by a vast number of companies, yet only a few companies account for the major share of production and Bayer is by far the worlds largest supplier. 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. Whereas companies manufactured only ground pigments in the past, an increasing number of manufacturers are now also offering higher value-added micronized granular grades. 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
In addition, iron oxide pigments are now being produced in a granular form. The advantage of using granular pigments is the low-dust emission and free flowability of the product.
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Natural iron oxide pigments. In Western Europe, natural iron oxide pigments are produced in a number of countries, the most important of which are Spain and Italy for the color iron oxide pigments; Austria is the leading producer of micaceous iron oxide pigments. 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.A. [Belgium]) Chaillac Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Remarks
--
--
--
Barite by-product from feldspar production. Pigment used primarily in the construction industry.
Marius Lamy & Companie SARL Apt Oxymine S.A. (owned by Poortershaven [Netherlands]) Poissy Germany Bruchsaler Farbenfabrik GmbH & Co. KG Bruchsal Dr. Hans Heubach GmbH & Co. KG Langelsheim, Niedersachen Italy Societ Italiana Ossidi Ferro SpA Pozzolo-Formigaro Piemonte
--
--
--
--
--
--
--
--
--
--
Small output only. Produces primarily synthetic iron oxides.
Veneta Mineraria SpA Alagna Valsesia Norway Rana Gruber AS Mo i Rana
--
--
--
By-product from feldspar production.
--
--
Plant started in 1990. Product is byproduct from magnetite and haematite ores. A 4 thousand metric ton-per-year red iron oxide pigment plant came on stream in mid-1994.
Spain Agroqumica del Valls, SA Las Franquesas del Valls
--
--
--
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Western European Producers of Natural Iron Oxide Pigments (continued) Company and Plant Location Spain (continued) Asensi, Termoplsticos Villafranqueza Oxidos del Sur SA Huercal de Almeria Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Remarks
--
--
--
--
A smaller company producing a range of iron oxide pigments.
Oxidos Rojos de Andaluca Ramon Alcade Zorrilla Jan Oxidos Rojos de Mlaga, S.L. (owned by Golden Valley Colours Ltd. [United Kingdom]) Mlaga
--
--
--
Mining and processing plant.
--
--
--
Produces micronized and superfine red pigments.
Productos Minerales para la Industria, S.A.PROMINDSA Sopuerta Tierga
X X
---
-X
X --
Combined capacity for black magnetic iron oxide and yellow pigments. Produces superfine and micronized iron oxide pigments for primarily the paint, glass, ceramic enamels and frits industries.
United Kingdom Elementis UK Ltd. Elementis Pigments Milton Keynes Laminox Ltd. Peterlee Winford Red Oxide Co., Ltd. (100% owned by W. Haley & Son Ltd.) Duffield Winford
--
--
--
--
--
--
---
---
---
X --
Processing plant. Ocher surface mine. Iron oxide content is 40-50%.
a. b.
Micaceous iron oxide. Company is associated with Oxhinsa, SA, Spain. CEH estimates.
SOURCE:
Synthetic iron oxide pigments. The most important producer of synthetic iron oxide pigments in Western Europe and the world is Bayer AG. The company accounts for approximately 50% of total world synthetic iron oxide pigment output.
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Bayer produces a range of more than sixty different varieties of iron oxide pigments, including twenty standard-grade reds, ten yellows, nine browns, five blacks and the micronized grades (Bayferrox), which include ten reds, seven yellows and one black. Recently the company initiated a major upgrade and expansion program for its iron oxide pigment operations at Uerdingen. Through acquisitions and capital investments, K-L Holdings (the acquirer of Laporte) has advanced to the number two position worldwide. The company is manufacturing a wide range of different grades and hues of iron oxide pigments and recently started manufacturing granular pigments. Heubach is a relatively new and aggressive iron oxide pigments producer. Since 1997, the company has operated a 20 thousand metric ton-per-year plant at Langelsheim, Germany. Heubachs iron oxide pigment range includes one yellow, four reds and one black, as well as micronized and encapsulated pigments. BASF is producing a range of transparent iron oxide pigments that are used in higher-value-added products. The range includes four reds, two yellows and one orange. Apart from color pigments, the company is also producing three grades of magnetic pigments. Synthetic iron oxide pigment producers are listed in the following table:
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Western European Producers of Synthetic Iron Oxide Pigments Company and Plant Location Austria Krems Chemie Aktiengesellschaft Krems an der Donau France Cappelle Frres SARL Halluin Germany BASF Aktiengesellschaft Ludwigshafen Black (PBk-11) Brown (PBn-6) Red (PR-101) Yellow (PY-42) Remarks
By-product route.
Transparent pigments.
PIGMENTS
Kln Bayer AG Krefeld
Transparent pigments (Sicotrans). Also orange and magnetic pigments. Mainly for plastics and paint systems. FDA grades (Sicomed for cosmetics and Sicopharm for pharmaceutical applications). Aniline. Penniman-Zoph process. Primarily blending. Heucorox . Start-up in January 1997. Micronized grades.
X X X
X X
Dr. Hans Heubach GmbH & Co. KG Langelsheim
Rockwood Pigments Breckhurs Italy Rockwood Pigments Rockwood Italia SpA Silo Division Torino
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Trade names are Duploxide (red, brown and black iron oxide) and Ferroxide (yellow iron oxide).
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Western European Producers of Synthetic Iron Oxide Pigments (continued) Company and Plant Location Italy (continued) Societ Italiana Ossidi Ferro SpA Pozzolo-Formigaro Black (PBk-11) Brown (PBn-6) Red (PR-101) Yellow (PY-42) Remarks
Spain Cremades y Compaa, S.A. Molina de Segura Oxhinsa, SA Alicante
Purofer.
Scrap iron, precipitation; Spanfer, a synthetic black pigment.
United Kingdom Cookson Matthey Ceramics & Materials Ltd. Materials Division Pigments & Dispersions Stoke on Trent Elementis UK Ltd. Elementis Pigments Milton Keynes
Transparent pigments.
Penniman-Zoph process (Deanox). Black iron oxide pigments are resold from the United States.
Laminox Ltd. (ultimately owned by Plss Stauffer AG) Peterlee SOURCE: CEH estimates.
Micaceous synthetic iron oxide.
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Used mainly in cements and mortars. Also supplies natural iron oxide pigments.
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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 Pigments2001
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. Western European production of iron oxide pigments has reached very high levels, particularly in the traditional areasbuilding materials, paints and coatings and plastics. Below is a summary of 1999 supply/demand for iron oxides in Western Europe.
Western European Supply/Demand for Iron Oxide Pigments1999 (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, Statistical Office of the European Community. (B) Der Aussenhandel sterreichs , Serie 1A, sterreichisches Statistisches Zentralamt. (C) National foreign trade statistics. (D) CEH estimates.
Production During the last five years the overall capacity utilization for iron oxides has improved for most producers, particularly for synthetic pigments. Of the total iron oxide pigment production in Western Europe, Bayer accounted for about 74%. The companys main production plant is located in Krefeld, Germany but the
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group also has plants in the United States and at a joint venture plant in China (Bayer Shanghai Pigments), with a nameplate capacity of 20 thousand metric tons per year. The next-largest market participants are Elementis and K-L Holdings (acquirer of Laporte). Natural iron oxide pigments. In 1999, the Western European production of natural iron oxide pigments accounted for about 15% of global iron oxide pigment production, down from 17% in 1996. 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.g., Rana Gruber, Norway). Particularly, output from Spain has dropped to less than half the output of the early 1990s. Natural iron oxide pigments have some market niches in which they can compete very well with the synthetic grades. Some of these niches are primarily in the building materials industry and in fertilizers. In other applications natural iron oxide pigments, particularly micronized grades, can also compete with synthetic pigments. Synthetic iron oxide pigments. 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. Scrap iron oxide is used almost entirely in applications where quality of the pigment is not overly critical, primarily in the construction industry for the production of bricks and concrete. This large volume of lowgrade iron oxide pigments have been excluded from this report. Because of product consistency, higher tinting strengths and more intense color shades, as well as the considerably lower content of problematic heavy metals (e.g., arsenic, lead, cadmium), synthetic iron oxide pigments have further increased their share over natural iron oxide pigments in most markets. In Western Europe, synthetic iron oxide pigments are produced by a variety of processes and raw materials. For example, Bayer obtains crude iron oxide pigments as a coproduct of aniline production (only a small portion of Bayers aniline production is based on the reduction process with iron scrap). It can be argued, however, that the iron oxide pigment obtained through this process is the main product and not the aniline. Aniline is generally manufactured through different processes, which are more economical. The production of iron oxide pigments from the aniline process is governed by the demand for aniline and the economics of the processes, taking the value of the coproduct iron oxide into account. The following table lists official production data for iron oxide pigments produced in Spain:
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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: 51.6 51.9 na na na na na na na na 40.0 25.0 20.0 22.0 22.0 22.0 Synthetic 1.0 1.2 2.2 2.0 2.0 2.0 2.0 2.0 2.5 3.1 3.2 4.0 4.0 4.0 4.0 4.0
(A) La Industria Qumica en Cifras, Federacin Empresarial de la Industria Qumica Espaola (data for 1970-1996). (B) Mineral Industry Surveys, U.S. Department of the Interior, U.S. Geological Survey (data for NATURAL, 1997-1999). (C) CEH estimates (all other data).
The following table shows Western European production of both natural and synthetic iron oxide pigments by country since 1983:
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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, 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 0.3 0.3 0.3 0.4 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.
The following table shows a breakdown of 1999 production of natural and synthetic iron oxide pigments in Western Europe by country:
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Western European Production of Natural and Synthetic Iron Oxide Pigments1999 (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, U.S. Department of the Interior, U.S. Geological Survey (data for NATURAL). (B) CEH estimates (all other data).
Black iron oxide pigments, particularly PBk-11, are the second-largest group of black pigments (after carbon black) produced and consumed in Western Europe. An estimated 35 thousand metric tons of black iron oxides were produced in Western Europe in 1999.
Consumption It is estimated that Western Europe consumed approximately 350 thousand metric tons of iron oxides in 1999. The largest market segment is construction. Other markets are considerably smaller, 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, because of their low toxicity, have partially replaced heavy metalbased inorganic pigments in certain applications where the low brightness of iron oxide pigments is not a critical issue. (Iron oxide pigments, and in particular iron oxide yellow, are often mixed with organic pigments in order to match the standard shades in the final products.) The volume gained from this substitution process has been small, however, and the process is almost complete, at least in Western Europe. The following table shows the Western European consumption of natural and synthetic iron oxide pigments:
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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. 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 Use1999a 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. b. Natural and synthetic iron oxide pigments. These applications do not depend on the coloring properties of iron oxide pigments. Includes colorants for cosmetics and pharmaceuticals. 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:
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Western European Consumption of Iron Oxide Pigments by End Use1999

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, micronized grades (with a diameter between 0.01 and 0.001 micrometer), which are sold primarily to the paints (e.g., for wood painting) and plastics industry and for specialty applications such as cosmetics, pharmaceuticals or special paper. Total consumption of transparent iron oxide pigments in Western Europe is estimated at less than 4 thousand metric tons in 1999. This volume is included in the above table. The following graph shows the estimated breakdown by market:
Western European Consumption of Transparent Iron Oxide Pigments1999
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. Total consumption of FDA-grade iron oxide pigments, including transparent and nontransparent grades, is estimated at about 4 thousand metric tons in 1999.
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Western European Consumption of FDA-Grade Iron Oxide Pigments1999

Special Paper 12%
Pharmaceuticals 16% Cosmetics 47%
Pet Food 25%
Total = 4 Thousand Metric Tons
Building materials. The building materials industry is one of the largest consumers of pigments, particularly iron oxide pigments. The pigments are used for a wide variety of applications, the most important of which are for colored asphalt and for coloring roof tiles, bricks, cement, mortar, preformed concrete blocks for paving and noise-abatement (sound) walls, and other building materials. In Western Europe, both natural and synthetic iron oxide pigments are used in this application. In many of these end uses intentionally produced synthetic pigments have come under pressure from low-grade pigments, particularly from China. During the 1992-1993 European economic recession, 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. In particular, demand for color building products such as concrete interlocking paving blocks and other products declined. Between 1996 and 1999, consumption increased steadily as the main consuming applications recovered. 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. Paints and coatings. In Western Europe, paints and coatings represent the second-largest segment for iron oxide pigments. It is estimated that in 1999, some 87 thousand metric tons of iron oxide pigments were consumed for the manufacture of paints and coatings. The larger share of iron oxide pigments used in paints and coatings are synthetic pigments, but natural iron oxide pigments are also widely used, particularly in applications with lower-quality requirements (e.g., primers and undercoats). In these coatings, iron oxide pigments often function as an anticorrosion inhibitor rather than as a coloring matter (e.g., micaceous iron oxide). A specialty group of iron oxide pigment used in paints and coatings are the transparent pigments. It is estimated that in 1999, Western European consumption for this application was less than 2 thousand metric tons. The main use of transparent pigments is in the production of metal-effect coatings (i.e., in
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combination with aluminum pigments) and for coloring PET bottles and spin-dyed fibers. Recently there has been substitution pressure from luster pigments, some of which are also based on iron oxide. Plastics. Plastics are the third-largest application for iron oxide pigments in Western Europe. One of the larger applications of iron oxide pigments in this segment is the production of plastic trash bags, which are available in brown, yellow, gray and black colors. It is unlikely that iron oxide pigment consumption in this application will grow more than 2-3% per year in the near future. In the past, the use of certain iron oxide pigments was often problematic because of their relatively low temperature stability during the plastics processing step. Newer, coated pigments have, however, been developed that can be used with practically any plastic. Iron oxide pigments have also been used to replace the toxic chromate pigments wherever possible. However, this substitution is believed to be complete. Magnetic applications (ferrites and other uses). Magnetic iron oxide pigments are used in a wide range of applications, such as the production of ferrites and magnetic information carrier materials. Although the number of carrier material pieces (e.g., discs, magnetic cards) produced has increased significantly, 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, and thinner coatings on, the carrier products Use of other, more effective magnetic materials, such as chrome oxide Migration of media production to lower-cost countries in Asia
It is expected that these trends will continue and future consumption of magnetic iron oxide pigments in Western Europe will eventually stagnate and decline. Paper. In this application iron oxide pigments are used primarily for the production of decorative laminates destined for the furniture industry. Other smaller applications include the production of kraft paper and paper board used by the packaging industry. Also, FDA-grade micronized pigments are used in special papers which are likely to get in contact with lips (e.g., wrapping paper, cigarette paper). The use of pigments in paper has grown, but future growth is difficult to determine. Food colorants/nutritional additive. Iron oxide pigments are among the main coloring pigments in food and feed products. They are used particularly in pet foods, where they serve as a coloring agent as well as a nutritional additive. Understandably, in food products only FDA-grades of iron oxide pigments are acceptable. Because of toxicological concerns, 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. However, the volumes gained are smallparticularly in relation to the changes in consumption in other sectors. It is believed that, because of an increase in the number of pet owners, demand for colored pet foods will increase.
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Cosmetics. Natural and especially synthetic iron oxide pigments are the most important of the color pigments used in cosmetic products in terms of volume consumed. Various grades and types are used to color lipsticks, compact makeup, eyebrow pencils, cover ointments and so forth. In cosmetics, micronized iron oxide pigments are favored over organic pigments because of lower concern about toxicological aspects of their consumption, particularly in relation to mucous membrane exposure. The total Western European consumption of iron oxide pigments in cosmetic products in 1999 is estimated to have been about 400 metric tons. The consumption volume of iron oxide pigments used for cosmetics is unlikely to change significantly, since it is related to the growth of the Western European population. Obviously, fashion trends and the still-decreasing age at which cosmetics use begins will also have some impact on the consumption of iron oxide pigments. Other . Iron oxides have a number of other applications but they are much smaller than the building materials and the markets discussed above.
Price The Western European iron oxide market, although dominated by a few domestic producers, has become very competitive, with increased imports (especially from China) having caused prices for iron oxide pigments to decline considerably during the past ten years. Pressures from consumers, such as the paints and coatings industry, have also had a negative impact on prices. Because of the current business climate and the new capacity that has been built, prices are expected to remain unchanged or decline in inflationadjusted terms for the next few years. 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.
728 740 792
1,072 675 569
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Trade Imports. Western European imports of iron oxide pigments increased significantly in recent years. In 1999, the total volume imported was 85 thousand metric tons, of which 70% came from China. 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 26.3b 3.4 3.6 4.7 Canada -neg neg neg Asia China 1985 1990 1995 1999 a. --c 8.9 52.7 60.2 Japan 0.6 0.7 4.1 2.8 Other 0.3 0.7 6.1 15.8d Australia and Oceania -0.1 0.1 0.1 Total 28.1 16.1 73.1 85.4 Central and South America -0.1 0.1 0.1 Eastern Europe 0.9 2.0 6.0 1.4 Africa -neg 0.1 0.2 Middle East -0.2 0.3 0.1
Includes iron oxides, iron hydroxides and earth colors. Data exclude intraWestern European trade. Actual data are believed to be lower. Included in OTHER. Includes non-EU suppressed imports. (A) U.S. Department of Commerce, Bureau of the Census (data for UNITED STATES). (B) NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community. (C) National foreign trade statistics. (D) CEH estimates.
b. c. d.
SOURCES:
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Bayer started a joint venture pigments project in Shanghai in 1995, with a 20 thousand metric ton-peryear iron oxide pigment grinding and mixing plant. Some production from this plant accounts for part of the exports from China to the European market. Exports. Western Europe is a large net exporter of iron oxide pigments. Total volumes exported in 1999 were reported at 118 thousand metric tons. More than 98% of all iron oxide pigments exported were synthetic pigments. Of this group, the largest single-volume product exported was synthetic iron oxide yellow (PY-42) produced by Bayer AG.
Chrome Pigments Producing companies The following table lists Western European producers of chromium pigments in 2000:
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Western European Producers of Chrome Pigments2001 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. M. Habich AG Leiben Belgium Fabrique de Couleurs Hilaire Grootaert Drongen
Gebroeders Cappelle nv Menen France Cappelle Frres SARL Halluin Socit Nouvelle des Couleurs Zinciques SASNCZ Bouchain Germany BASF Lacke + Farben Aktiengesellschart Besingheim Kln
X X
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Bruchsaler Farbenfabrik GmbH & Co. KG Bruchsal
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Western European Producers of Chrome Pigments2001 (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. Hans Heubach GmbH & Co. KG Langelsheim Italy Kohlberg, Kravis, Roberts (Laporte Italia SpA) Silo Division Torino
Societ Italiana Ossidi Ferro SpA Verona Netherlands Ciba Specialty Chemicals Maastricht B.V. Maastricht A. Vossen Pigment BV Venlo-Blerick Norway Waardals Kjemiske Fabrikker A/S Askoey Portugal
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Western European Producers of Chrome Pigments2001 (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, S.A. Barcelona Intermedios Orgnicos, SAINTORSA Moncada i Reixach Nubiola, S.A. Barcelona
United Kingdom Elementis UK Ltd. Elementis Pigments Milton Keynes Lead Chrome Colours Ltd. Spondon SOURCE: CEH estimates.
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Salient statistics
Western European Supply/Demand for Chrome Pigments1999 (thousands of metric tons) Chromate Pigmentsa Production Imports Exports Apparent Consumption a. 17.3 3.5 7.8 13.0 Chromium Oxides 24.0 0.5 2.0 22.5 Total 41.3 4.0 9.8 35.5
Includes lead chromates but also small volumes of barium, zinc and strontium chromate corrosion-inhibiting pigments. (A) NIMEXE, Analytical Tables of Foreign Trade: ProductsCountries , Eurostat, Statistical Office of the European Community. (B) CEH estimates.
SOURCES:
Total Western European production of lead chromate pigments (including small amounts of the corrosion-inhibiting barium chromate, zinc chromate and strontium chromate), is estimated to have been 17.3 thousand metric tons in 1999. Chromium oxide production is estimated to have been higher, at 24 thousand metric tons. Because of toxicological and environmental considerations, the production and consumption of chrome pigments have decreased and this trend is expecte to continue for some time.
Consumption Chromium-containing pigments are an essential group of pigments with a wide range of applications. While lead represents a clear toxicological and environmental problem, chromium is less of a concern. 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. 17.5 15.0 13.0 Chromium Oxides 23.0 22.5 22.5 Total 40.5 37.5 35.5
Includes lead chromates but also small volumes of barium, zinc and strontium chromate corrosion-inhibiting pigments. CEH estimates.
SOURCE:
Lead chromates. Consumption of chromate pigments has declined in Western Europe by nearly 25% over the volumes in 1993. As legislation regarding the production and use of pigments becomes more severe and as regulations will be increasingly implemented, it can be assumed that the consumption of lead 2001 by the Chemical Economics HandbookSRI International
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containing chrome pigments will gradually decrease. In the Netherlands, for example, the use of leadcontaining pigments were phased out in the year 2000 and it is expected that other, larger consuming countries will follow suit. Major companies that had used chrome pigments in the past are gradually substituting chromates with pigments that do not contain lead, such as bismuth vanadate or in the corrosion-protection pigments segment, with products such as aluminum and zinc phosphates. Iron oxide pigments, mixed with organic pigments to achieve higher brightness, are also used as a substitute in certain applications. As a result of these environmentally driven changes, the Western European consumption of lead chromates has decreased substantially during the last decade. Western European consumption of lead chromate pigments in 1999 is estimated to have been about 13 thousand metric tons, down from about 17.5 thousand metric tons in 1993. These figures include small volumes of the anticorrosion pigments barium, zinc and strontium chromate. 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. 7.9 4.4 0.6 0.1 13.0 Market Share (percent) 61 34 4 1 100%
Includes small volumes of corrosion-inhibiting barium, zinc and strontium chromate pigments. CEH estimates.
SOURCE:
During 1999-2004, it is expected that the consumption of lead chromate pigments, especially in the paints and coatings segment, will decrease further. Even in traffic-grade paints, a segment in which lead chromates have outstanding properties, substitution is still taking place. One of the inorganic substitution pigments is bismuth vanadate, a yellow pigment that has properties similar to chrome yellow. Some of the organic pigments substituting for yellow and orange chrome pigments are based on benzimidazolone yellow and DPP red. These organic pigments all have a drawback of one kind or another, the most important one being that they are clearly more expensive than chrome pigments. Chromium oxide. 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, however, its dull shade. While lead chromate pigments pose environmental and toxicological problems, chromium oxide pigments are unlikely to be influenced much by regulations. Consumption of green chromium oxide pigment in Western Europe in 1999 is believed to have been 22 thousand metric tons. The end-use consumption pattern is shown in the following table:
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Western European Consumption of Green Chromium Oxide Pigments1999 Quantity (thousands of metric tons) Paints and Coatings Building Materials Plastics Enamel and Ceramics Printing Inks Other Total SOURCE: CEH estimates. 11.5 6 2 1.5 neg 1 22.0 Market Share (percent) 52 27 9 7 neg 5 100%
Chromium oxide is also used in technical nonpigment applications. This use of chromium oxide is not discussed here and the data shown are for pigment-grade chromium oxide only. The paint and coating industry is clearly the largest market for chromium oxide pigments. In this application, chromium oxide pigments are used particularly where the fastness properties are required and where its relatively dull shade is acceptable. (This shortcoming is solved in many cases by adding highperformance organic yellow pigments, which change the hue to a brighter green. Often, other pigment combinations are formulated in order to derive the required shade.) A further characteristic of chromium oxide pigments is their high hardness, which can create a problem in some applications because of abrasion. In the building products industry, chromium oxide pigments are used to color cement and chalkbased products. In plastics, chromium oxide pigments are widely used, particularly in technical goods (e.g., machinery parts, communal trash containers, garden furniture, bottle crates). Chromium oxide pigments are being used in practically every possible pigment application; the product has found acceptance even in cosmetics. The generally excellent properties of chromium oxide pigments (fastness, heat stability, etc.) will keep demand growing slowly in Western Europe. There is, however, competition from other green pigments, such as phthalocyanine pigments, which have a brighter color shade and combinations of yellow and blue pigments. Barium, zinc and strontium chromate. Consumption of these anticorrosion pigments has been under environmental pressure and use has started to decline in certain applications. Strontium chromate is, however, still considered an excellent pigment, whose properties are unmatched by any other anticorrsion pigment. It remains the specified anticorrosion pigment for aircraft and military primers. Consequently, demand for this pigment has been quite strong. Nevertheless, in the long term, consumption of strontium chromate will likely decline as new anticorrosion pigments or systems become accepted.
Price The average price of chromium-based pigments imported to Western Europe in 1998 was 3.38 euros per kilogram; in 1999 the average price rose slightly to 3.39 euros per kilogram. Prices are expected to decline as consumption falls.
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Trade Imports. Imports of chromium-containing pigments into Western Europe represent about 13% of consumption. 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 Preparations1995 and 1999a (metric tons) 1995 Canada Hungary Colombia United States China Other Total SOURCE: 1,169 351 na 112 145 119 1,896 1999 1,776 462 215 179 54 1,267 3,953
NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community.
EU imports of chrome-containing pigments have grown since 1995, despite declining consumption. The majority of imports originated from Canada (Dominion Colour Corporation) and were shipped mainly to the United Kingdom. There were also shipments received from Hungary (Holland Colours Hungaria Kft). China has decreased its share since 1995, while the United States has grown, and Colombia has also emerged as an important source. Exports. Exports of chrome pigments from Western Europe totaled about 9.8 thousand metric tons in 1999, up from about 7.4 thousand metric tons in 1995. 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 Preparations1995 and 1999a (metric tons) Destination United States Japan Saudi Arabia Turkey Taiwan Korea, Republic of Other Total a. 1995 588 459 217 456 360 444 4,886 7,410 1999 879 609 590 576 438 388 6,272 9,752
European Union tariff code number is 3206.2000. NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community.
SOURCE:
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Exports are expected to eventually decline as lead chromate paint bans become enforced in developing countries, as in developed countries.
Complex Inorganic Pigments Summary In Western Europe, complex inorganic color pigments (formerly known as mixed-phase or mixed-metal oxide pigments) are a small but increasingly important group of inorganic pigments. Because of the decreasing acceptance of cadmium-based pigments as a result of environmental and toxicological concerns, the use of complex inorganic color pigments, sometimes combined with organic pigments, is in the plastics applications.
Western European Supply/Demand for Complex Inorganic Pigments1999 (thousands of metric tons) Rutile Pigments Capacity Production Imports Exports Apparent Consumption a. na 9.2 0.2 4.5 4.9 Spinel Pigmentsa na 6.1 0.1 3.0 3.2 Total 18.0 15.3 0.3 7.5 8.1
Includes cobalt-based complex inorganic pigments. CEH estimates.
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 Pigments2001 Company and Plant Location Germany BASF Aktiengesellschaft Ludwigshafen BASF Pigment GmbH Kln Bayer AG Leverkusen Cerdec AG, 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
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Western European Producers of Cobalt-Based Complex Inorganic Pigments2001 (continued) Company and Plant Location Germany (continued) Dr. 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. Black (PBk-27) Blue (PB-28) Blue (PB-36) Green (PG-19) Green (PG-26) Green (PG-50)
Western European Producers of Other-Than-Cobalt-Based Complex Inorganic Pigments2001 Spinel-Structured Pigments Company and Plant Location Germany BASF Aktiengesellschaft Ludwigshafen BASF Pigment GmbH Kln Cerdec AG, Keramische Farben (owned 70% by Degussa AG and 30% by Ciba Specialty Chemicals AG) Bonn Dr. Hans Heubach GmbH & Co. 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)
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Western European Producers of Other-Than-Cobalt-Based Complex Inorganic Pigments2001 (continued) Spinel-Structured Pigments Company and Plant Location United Kingdom Johnson Matthey Colour and Coatings Division Ceramics Division Stoke on Trent SOURCE: CEH estimates. Brown (PBn-29) Brown (PBn-31) Yellow (PY-119) Rutile-Structured Pigments Brown (PBn-24) Yellow (PY-53) Yellow (PY-157) Yellow (PY-164)
Production The Western European production of complex inorganic color pigments is estimated at about 15.3 thousand metric tons in 1999. This volume accounts for the rutile and spinel type of pigments, which also includes cobalt pigments. This volume also includes pigments that are sold to the enamels and ceramics industry. The major producer of these pigments is BASF, followed by Cerdec AG (owned 70% by Degussa AG and 30% by Ciba Specialty Chemicals AG). BASF and Cerdec both offer a wide range of complex inorganic color pigments and pigment mixtures. Heubach has recently introduced encapsulated rutilestructured pigments that can withstand even higher temperatures.
Consumption Western European consumption of complex inorganic color pigments was about 8.1 thousand metric tons in 1999. The following table gives an estimate on Western European consumption of complex inorganic pigments by specific pigment:
Western European Consumption of Complex Inorganic Pigments1999 (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.
3.3 1.1 0.5 4.9
1.3 0.9 1.0 3.2 8.1
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The main applications of complex inorganic color pigments in Western Europe are shown and discussed briefly below.
Western European Consumption of Complex Inorganic Pigments by End Use1999 (thousands of metric tons) Rutile Pigments Ceramics and Glass Plastics Paints and Coatings Building Materials Other Total SOURCE: CEH estimates. 0.5 2.3 1.6 0.3 0.2 4.9 Spinel Pigments 2.5 0.5 0.1 -0.1 3.2 Total 3.0 2.8 1.7 0.3 0.3 8.1
Ceramic and glass materials. Because of their heat stability, complex inorganic color pigments are used for coloring glass and ceramic materials. Western Europe (in particular, Italy and Germany, followed by the United Kingdom, Spain and France) is the worlds largest producing region for ceramic goods and consumption of complex inorganic color pigments in this segment is the most important in volume terms. The ceramic goods industry is faced with increasing import penetration, particularly from China and other Asian countries, as well as from Eastern Europe and Brazil. Imports of ceramic goods (and in particular tiles) continue to grow, impacting the Western European growth potential of pigments for ceramic and glass materials. As a result, it is expected that during 1999-2004, production of standard-grade ceramics will stagnate and that a gradual shift towards more premium ceramic products will take place. The consumption of complex inorganic pigments in this segment will grow by only about 2.0% per year. The expected growth rate is slightly higher than the estimated production growth of the ceramic products industry, as there will be some substitution of cadmium pigments. Plastics. Plastics is one of the major industries consuming complex inorganic color pigments in Western Europe. The pigments are used in a variety of commodity and high-performance plastics. The largest volumes are used in PVC and polyethylene. Complex inorganic color pigments are increasingly important in applications where cadmium, chromate and molybdate pigments can no longer be used. In particular, the consumption of Ni-Cr-Ti-based pigments is growing steadily. 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. Paints and coatings. Complex inorganic color pigments are increasingly important in the paints and coatings industry, since they have special characteristics. These pigments show good to excellent performance, particularly in exterior high-grade house paints, auto enamels and coil coatings. Currently, the only application of significance, however, is believed to be for camouflage paints for military applications. During the last few years, because of environmental and toxicological legislation, some of these complex inorganic color pigments have taken a small, but increasing market share from cadmium- and chromatebased pigments. Particularly the various shades of PY-53 have gained in importance.
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Trade No data on Western European trade in complex inorganic pigments are reported. It is estimated, however, that Western Europe was a net exporter of approximately 7.2 thousand metric tons in 1999. There are some imports of complex inorganic pigments from the United States (primarily from Ferro). 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.
Ultramarine Pigments Summary Ultramarine pigments, which can be produced in shades of blue, green, violet or red, have a long history of use in Western Europe. The fairly good performance characteristics of these pigments and their relatively low price led to widespread use. The production process, however, is energy-intensive and time-consumingit can take up to twenty days to produce a batch. The time factor is one of the main reasons many companies have stopped producing these pigments. Holliday Pigments (formerly Reckitts Colors), with works in France and the United Kingdom, is the largest ultramarine pigments producer in the world, with a combined annual production capacity of approximately 14 thousand metric tons. The next biggest producer is Nubiola, which operates two plants, one near Barcelona, Spain and the second in Agualva, Portugal. Between 1996 and 1999 the Western European ultramarine pigments market shifted from being export oriented to being import reliant. This transition coincided with the loss of the detergent market segment that had used low-grade ultramarine pigments; they were replaced by organic optical brightners. 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: 16.5 14.5 0.4 9.7 5.2 1996 16.5 14.1 1.3 10.0 5.4 1999 16.5 3.6 3.0 0.3 6.3
(A) NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community. (B) CEH estimates.
Producing companies The following table lists producers of ultramarine pigments in Western Europe:
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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. M. Habich AG Leiben France Holliday Pigments S.A. Comines Portugal Nubiola - Produtos Qumicos, S.A. Agualva Cacm Spain Nubiola, S.A. Barcelona United Kingdom Holliday Pigments Limited Hull Total SOURCE: CEH estimates.
Blue (PB-29)
Violet (PV-15)
na
na
2.5
8 >16.5
Production It is estimated that in 1999, Western Europe produced about 4 thousand metric tons of ultramarine pigments and preparations, less than a third of total world production, down from about 14 thousand metric tons in 1996. Production is declining in Western Europe because of high production costs. Ultramarine pigments have been produced in two gradesa low grade, used primarily as an optical brightener in laundry detergent and a high grade, used in all other, more durable applications. The production and consumption of the low-grade pigment has decreased because of replacement by more effective organic optical brighteners.
Consumption In 1999, Western Europe consumed an estimated 6.3 thousand metric tons of ultramarine pigments and preparations. Demand for high-grade ultramarine pigments has increased steadily in the last several years because of their safety and versatility.
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Ultramarine pigments are used in practically all types of color applications (e.g., plastics, paints, printing inks, paper and paper coating, detergents, cosmetics and soaps); there are only a few applications for which these pigments are not recommended (e.g., air-drying paints for outdoor use in urban atmospheres). It is expected that Western European consumption of ultramarine pigments will continue to grow during the next few years, possibly at a rate above GDP growth. It is expected that consumption will be driven in part by the continued substitution of ultramarine pigments for pigments with toxic properties. The following pie chart shows Western European consumption of ultramarine pigments (excluding use in detergent) in 1999:
Western European Consumption of Ultramarine Pigments1999
Cosmetics 3% Other Paper 3% 4% Artist Colors 5% Printing Inks 6% Writing Inks 7% Plastics 62%
Paints and Coatings 10%
SOURCE: CEH estimates.
The excellent heat stability of ultramarine blue pigments and the pleasant color shades achieved, are reasons for their wide acceptance in plastic coloration.
Price The average Western European import value for ultramarine pigments in 1999 was 1.34 Euros per kilogram, up from 1.18 euros per kilogram in 1998.
Trade Western European exports of ultramarine pigments have declined since 1996, from 10 thousand metric tons to 297 metric tons in 1999. The drop is attributable to greater production in the Far East. Imports. Imports of ultramarine pigments into Western Europe were negligible in the past. Since the mid1990s, however, imports increased and reached about 3.0 thousand metric tons in 1999. The dominant country of origin was Romania.
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Shown below are the Western European imports of ultramarine pigments and preparations from outside the region.
EU Imports of Ultramarine Pigments by Country of Origina (metric tons) Origin Romania India Colombia Japan United States Other Total a. 1995 754 212 108 148 0 6 1,228 1999 1,345 869 516 213 90 25 3,058
European Union tariff code number is 3206.4100. NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community.
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 2,552 2,690 3,009 3,751 3,025 2,663 3,304 3,176 3,500 3,816 4,259 4,551 4,203 5,209 6,782 6,725 2,936 2,793 3,058
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a.
European Community 1989-1995, European Union 1997-1999. NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community (data for 1985-1995) and European Union (data for 1997-1999).
SOURCE:
Exports. Exports of ultramarine pigments from Western Europe have fallen significantly. In 1999, Western Europe exported 297 metric tons, versus 7,891 metric tons in 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. 6,789 7,286 8,231 8,209 8,455 9,000 8,800 9,700 7,501 7,226 7,891 297
European Community 1989-1995, European Union 1997-1999. After 1989, export data are incomplete, since exports from France are no longer reported. NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community (data for 1985-1995 and European Union (data for 1999).
SOURCE:
Iron Blue Pigments Summary The following table summarizes Western European supply/demand for iron blue pigments:
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Western European Supply/Demand for Iron Blue Pigments (thousands of metric tons) 1996 Capacity Production Imports Exports Apparent Consumption SOURCES: 9.5 6.3 0.6 2.2 4.7 1999 9.5 3.2 1.7 0.9 4.0
(A) NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community. (B) CEH estimates.
Producing companies In Western Europe only two producers of iron ferrocyanide (iron blue) pigments (PB27) remain. Degussa AG, with plants in Germany and the United Kingdom (formerly Manox Ltd.), is the main producer. At its German plant the company has captive potassium ferrocyanide raw material available and in the United Kingdom plant, 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, therefore, reduce the dispersion time required. The Western European producers of iron blue pigments, along with their annual capacities, are listed below.
Western European Producers of Iron Blue Pigments Annual Capacity as of 2001 (thousands of metric tons
Company and Plant Location Germany Degussa-Hls AG Wesseling Spain Intermedios Orgnicos, SAINTORSA Montcada i Reixac United Kingdom Degussa-Hls Limited Manox Division Manchester Total
5.0
0.5
4.0 9.5
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SOURCES:
(A) 1999-2000 Directory of Chemical ProducersEurope, SRI International. (B) CEH estimates.
Production The production of iron blue pigments has declined continually in the past decade. Environmental concerns and reduced demand have forced companies to close their iron blue pigment plants. In 1998, the two remaining producers in Western Europe together produced some 3.2 thousand metric tons of iron blue pigments, down from 3.4 thousand metric tons in 1996.
Consumption Western European consumption of iron blue pigments has eased slightly during the past decade. It is estimated that consumption in 1999 was approximately 4.0 thousand metric tons.
Western European Consumption of Iron Blue Pigments by End Use1999 Quantity (metric tons) Printing Inks Fungicide Coloring Paints and Coatings Paper Chrome Green Manufacture Tinting, Food Colorants Total SOURCE: CEH estimates. 2,600 900 300 120 40 40 4,000 Market Share (percent) 65 22 8 3 1 1 100%
Printing inks. By far the most important use of iron blues is in the printing inks industry, for the manufacture of inexpensive, deep blue colors that have good lightfastness. Iron blues are extensively used in combination with phthalocyanine blues and for toning with black printing inks. 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. Fungicide coloring. Starting in the 1950s, iron blues were used for the coloring of organic fungicides (mainly dithiocarbamate types), used in the treatment of vineyards, particularly in the Mediterranean countries. The use of this coloring pigment permits an easy method for tracking the distribution of the fungicide, which itself is colorless. Apart from this tracking function of the pigment, iron blues, because of their iron content, also have a biological effect on the grapes in that they increase the production of chlorophyll in the leaves. Paints and coatings. Iron blues are well suited for the manufacture of dark blue shades in coatings for the automotive industry. In this application, however, iron blues are considered of minor importance because of the superior quality of organic pigments. Nevertheless, iron blue pigments find limited application in the automotive repair paint segment.
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Paper. Iron blue pigments are used to a small extent in the production of colored paper, as well as for the manufacture of one-time or multiuse carbon paper and copy paper. In these applications iron blues can be used as a single pigment or for toning carbon blacks. They have an advantage over other pigments in that they do not bleed through color bases or olein, particularly in preparations with high volumes of mineral oils. Other. Iron blue pigments find use in a number of other smaller applications. Iron blue pigments are still used in the production of chrome green, a combination pigment consisting of chrome yellow and iron blue. BASF and Cappelle both manufacture chrome green pigments on a campaign basis. Consumption of iron blue pigments for this application is less than 50 metric tons. 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.
Price The average Western European import value for iron blue pigments was 2.01 euros per kilogram in 1999, down from 2.44 euros per kilogram in 1998. 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.
Trade Until 1995, imports of iron blue pigments were small and accounted for 0.6 thousand metric tons or less each year (less than 15% of supply). Up to a third of Western European production was typically exported. Beginning in 1997, imports increased significantly, primarily because of China whose shipments to Western Europe increased ten-fold; while at the same time, Western European production and exports declined. Western Europe is now import dependant, with imports accounting for over onethird of supply. After China, leading countries of origin include Japan (Kyosei Chemical), India and the United States.
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The table below lists import data by country of origin.

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. b. c. --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 1,417 1,467 1,651
Romania. Via Macao. Data included with OTHER. (A) NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community. (B) CEH estimates.
SOURCES:
Western Europes exports of iron blue pigments fell from about 2.2 thousand metric tons in 1996 to about 0.9 thousand metric tons in 1999. The export business is still viable, but declining. The main export destination is the United States, to which the two Western European producers together exported 486 metric tons in 1999, down from 1.5 thousand metric tons in 1996. Exports are expected to continue to decline.
Cadmium Pigments The following table summarizes Western European supply/demand for cadmium pigments in selected years:
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Western European Supply/Demand for Cadmium Pigments (thousands of metric tons) 1988 Capacity Production Imports Exports Apparent Consumption SOURCES: 4.15 2.9 0.05 1.10 1.85 1993 3.1 2.2 neg 0.9 1.3 1996 3.1 2.4 neg 1.4 1.0 1999 3.1 1.1 neg 0.6 0.5
(A) NIMEXE, Analytical Tables of Foreign Trade: ProductsCountries , Eurostat, Statistical Office of the European Community. (B) Jahresstattistik des Aussenhandels der Schweiz, Eidgenoessische Oberzolldirektion. (C) CEH estimates.
Producing companies As cadmium pigment consumption has declined, producers in Western Europe have adjusted with production termination and restructuring. In 1993, BASF terminated the manufacture of cadmium pigments. The remaining cadmium pigment producers in Western Europe are Socit Lanquedocienne de Micron-Couleurs, Johnson Matthey Ceramics & Materials (formerly Cookson Matthey), James M. Brown and General Quimica. 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, particularly in plastics.
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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 Socit Languedocienne de MicronCouleurs SASLMC (owned 100% by Total, France) Narbonne Germany Cerdec AG, Keramische Farben Bonn Spain
1,200
na
General Qumica, S.A.a (owned 100% by Repsol Qumica, S.A.) Comunin-Lantarn United Kingdom Holliday Pigments Limited Stoke on Trent Johnson Matthey Ceramics & Materials Ltd. Materials Division Pigments & Dispersions Stoke on Trent Total a.
150
600
900 >2,850
General Qumica, S.A. is also producing the mercury-containing cadmium pigments PO-113 and PO-113:1. (A) 1999/00 Directory of Chemical ProducersEurope, SRI International. (B) CEH estimates.
SOURCES:
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Production The production of cadmium pigments in Western Europe has declined considerably. It is estimated that Western European production in 1999 was approximately 1.1 thousand metric tons, down from 2.9 thousand metric tons in 1988.
Consumption In 1999, total Western European consumption is estimated to have been 0.5 thousand metric tons. 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. 1,850 1,345 1,015 500
Because of environmental regulations and voluntary substitution by pigment consumers, consumption of cadmium pigments has practically ceased in Denmark, Finland, Ireland, the Netherlands, Norway, Sweden and Switzerland. The consumption pattern in Western Europe is similar to that in the United States and Japan, as shown in the following pie chart and table:
Western European Consumption of Cadmium Pigments by Market Segment1999
Other 5% ABS 30%
LDPE 5% PS 10%
PP 15%
HDPE 20%
Ceramic Materials, Paints and Costings 15%
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Western European Consumption of Cadmium Pigments by Market Segment1999 Market Share (percent) Plastics ABS HDPE PP PS LDPE Other Ceramic Materials, Paints and Coatingsa Total a. Includes artists colors. CEH estimates.
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.g., high-temperature stability, wide range of brilliant colors, nonbleeding characteristics), environmental concern over the use of cadmium in products has led to a series of regulations limiting their use in Western Europe. In a number of countries the use of cadmium compounds has virtually ceased. Faced with the problem of different approaches being taken throughout its member states, the European Union has adopted a directive on the use of cadmium pigments that harmonizes restrictions on their use within the EU member states. The directive does not ban the use of cadmium pigments, but restricts their use where they are not seen to be essential. The following summarizes the regulations laid out in the European Union Directive 91/338 EEC:
q
Beginning December 31, 1992, cadmium pigments may not be used to give color to polymers in which substitution is already demonstrated as feasible. These polymers include: epoxy resins polyurethanes polyvinyl chloride (PVC) cellulose acetate cellulose acetate butyrate low-density polyethylene (LDPE) (except as masterbatch)
Beginning December 31, 1995, 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. The polymers added to the above list are the following: melamine-formaldehyde resins urea-formaldehyde resins polyproplyene cross-linked polyethylene unsaturated polyester resins acrylonitrilemethyl methacrylate polyethylene terephthalate
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polybutylene terephthalate high-impact polystyrene transparent/general-purpose polystyrene Cadmium pigments may, however, be used to give color to all other polymers in which substitution is currently envisaged to be impracticable. Austria, 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. However, the EU Directive 91/338 takes effect only after being implemented in member countries. One use that is unlikely to be affected is glass and ceramics, as there appears to be no alternative for the use of cadmium pigments. Also, the use for artists colors and materials will hardly be affected. Taking these regulations and trends into account, Western European consumption of cadmium pigments is expected to drop to less than 100 metric tons by 2004. It is estimated that the decreased use of cadmium pigments will be substituted for the most part by organic pigments, mainly as mixtures with rutile-structured complex inorganic pigments that augment the hiding power. Some inorganic pigments such as bismuth vanadate and rare earth sulfide pigments are increasingly used as substitutes.
Price Cadmium pigments are relatively expensive specialty high-performance pigments. The price for cadmium pigments depends mostly on the cadmium metal price, which is fixed in U.S. dollars at the London Metal Exchange. 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: 24.83 19.25 Eurostat, Statistical Office of the European Union.
Trade Western Europe has been a net exporter of cadmium pigments for many years. The major exporting countries are the United Kingdom and France. Imports of cadmium pigments and preparations have never been very important. There are small imports from the United States (mainly from Ferro Corporation) and occasionally some material is also imported from Mexico, Canada, India and Ecuador. During 1992-1994 import volumes decreased in line with
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decreasing demand in Western Europe. 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. 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. European Community 1989-1995, European Union 1997-1999. NIMEXE, Analytical Tables of Foreign Trade: ProductsCountries, Eurostat, Statistical Office of the European Union. 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 export business of the Western European producers still holds limited potential for a few years. The main destination for cadmium pigments is the United States. After 1990, volumes exported to the United States have, however, decreased steadily. Because of more stringent regulations, U.S. consumers have reduced the use of cadmium pigments in plastic products. In 1999, cadmium pigment exports to the United States totaled 140 metric tons, down from 308 metric tons in 1990. The following table shows Western European exports of cadmium pigments:
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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. 1,612 1,486 1,072 1,355 1,135 1,660 1,797 1,879 2,547 1,539 1,523 1,391 1,406 1,214 1,365 1,005 787 611 583
European Community tariff code numbers are 3207.76 (until 1987) and 3206.3000 (after 1987). NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community.
SOURCE:
Bismuth Vanadate Pigments Producing companies The following table shows the current producers of bismuth vanadate pigments in Western Europe:
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Western European Producers of Bismuth Vanadate Yellow Pigments2001 BASF Aktiengesellschaft Kln, Germany Bruchsaler Farbenfabrik GmbH & Co. KG Bruchsal, Germany Ciba Specialty Chemicals Maastricht B.V. Maastricht, Netherlands Dr. Hans Heubach GmbH & Co. KG Langelsheim, Germany Gebroeder Cappelle nv Menen, Belgium SOURCE: CEH estimates.
Consumption Bismuth vanadate pigments are a relatively new group of pigments introduced primarily as an alternative to lead chromate pigments. It is estimated that total Western European consumption of bismuth vanadate pigments in 1999 was approximately 300 metric tons. This figure includes the bismuth vanadate/ molybdate mixed pigments. Applications are similar to those of lead chromates, in paints (alkyd, nitrocellulose and stoving paints, as well as in water-based paints) and plastics. It can be expected that consumption of these high-saturation, high color strength alternative pigments will continue to grow. Volume increases will start from low levels and be rather modest due to relatively high prices exceeding DM50 per kilogram.
Rare Earth Sulfide Pigments Rhne-Poulenc, a leading producer of rare earth compounds, has recently commercialized a new group of pigments based on rare earth sulfides. Six pigments, currently based on cerium sulfide, 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, such as nylons. Rare earth sulfide pigments are likely to compete to some extent with complex inorganic pigments.
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Producing companies Rhne-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. At La Rochelle rare earths are separated and sent to Les Roches-Roussilon where sulfurization is carried out; finally, the product is processed to its pigment form at Clamecy. The processing plant, which came on stream in mid-1997, has an annual nameplate capacity of 500 metric tons.
Production Rhne-Poulenc is the sole manufacturer and full nameplate capacity may not have been reached.
Consumption Rare earth sulfide pigments are still in the early stage of their life cycle. In Western Europe, it is likely that less than 200 metric tons of rare earth sulfide pigments were consumed in 1999. The main applications are likely to be in engineering plastics, 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. Also it is envisaged that rare earth sulfide pigments could substitute for certain solvent dyes in outdoor polyurethane products.
Price As of March 2001, rare earth sulfide pigments were sold at about $40 per kilogram, down from about $50 per kilogram in 1997. Market prices will likely continue to decrease with increasing market penetration.
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, 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
--
--
--
--
--
--
0.05
--
--
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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 Wytwrnia Farb i Lakierw Grjec Polifarb Blyzin Blyzin Zaklady Chemiczne Organika-Zachem Bydgoszcz Zaklady Chemiczne Permedia S.A. Lublin Black (PBk-11) Brown (PBn-7) Red (PR-102) Yellow (PY-43) Unspecified Remarks
--
--
--
--
0.5
--
--
--
--
--
3.0
--
--
Total capacity is about 300 metric tons per year.
Russia NIPROINSNauchnoIssledovatelskogo i Proektnogo Chelyabinsk
0.3
--
--
--
--
Also manufactures micronized iron oxide pigments (annual capacity is 200 metric tons).
Yaroslavskoe PO Lakokraska Yaroslavlskaya
--
--
--
2.3
Also manufactures special iron oxide pigments.
Ukraine Krimskoe PO Titan Iskhodnoe
--
--
30.0
--
--
Synthetic iron oxide pigments from titanium dioxide manufacture.
Krivorozhskiy Surikoviy Krivoy Rog
--
--
--
--
Natural iron oxide pigments. Largest production facility in the CIS.
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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
--
--
15.0
2.5
--
Synthetic iron oxide pigments from titanium dioxide manufacture.
Uzbekistan Tashkentskiy Lakokrasochniy Zavod Tashkent SOURCE: CEH estimates.
--
--
--
2.5
--
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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 Hungria 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.
0.3
--
0.3
--
--
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
--
--
--
--
--
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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
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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 Hungria 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
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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 Polands 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 companys 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 regions largest iron oxide pigments producers are located in the Ukraine, Sumskie PO Chimprom and Krimskoe PO Titan, manufacturing about 47% of the regions 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:
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Central and Eastern European Production of Color Inorganic Pigments1999 (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 Pigments1999 (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.
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J APAN Producing Companies The major Japanese producers of inorganic color pigments are listed in the following table:
Major Japanese Producers of Inorganic Color Pigments2000
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
Pearlescent pigments
May 2001 575.0005 Q
Major Japanese Producers of Inorganic Color Pigments2000 (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.
Zinc Chromate/ Zinc Yellow (Unticorrosive pigment)
Iron Blue (Blue 27)
Other
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:
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Iron oxide pigments Although there are a great number of iron oxide producers in Japan, most of the major producers manufacture magnetic iron oxide/ferrites only. Unlike in the United States and Europe, there are no producers of natural iron oxide pigments. Toda Kogyo is the leading supplier of iron oxide for both pigments and magnetic media/ferrite applications. Titan Kogyo and Bayer (import) are the leading suppliers after Toda Kogyo of iron oxides to the pigment sector. 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. Nippon Bengara Kogyo ceased production and is now supplied with iron oxide from Toda Kogyo. Toho Ganryo Kogyo produces heat resistant high-quality yellow and red iron oxide pigments by using purchased iron oxide. Bayer (Japan) imports iron oxide pigments from China, Germany and the United States.
Chrome pigments Kikuchi Color is the worlds leading producer of chrome yellow and also the leading supplier of molybdate chrome orange in Japan. The company has a 100%-owned subsidiary, Dominion Colours (Ontario, Canada), and exports some chrome color pigments back to other Asian countries. In 2000, Kikuchi Color built a chrome color pigments plant, Chongqing Jiangnan Kikuchi, in China with 3.5 thousand metric tons of capacity, which is a joint venture with local company. As other producers (Dainichiseika Color & Chemicals Mfg, Nippon Inorganic Colour & Chemical Company and Toho Ganryo Kogyo) ceased chrome color pigments production in recent years, Kikuchi Color is the only company to expand chrome color pigment capacity worldwide. Nippon Inorganic Colour & Chemical Company withdrew from the pigment business itself by ceasing chrome yellow, molybdate chrome orange and zinc chromate production in 2000, and the company will concentrate on the industrial chemical business. With regard to chromium oxide, which is used as green pigment, Nippon Chemical Industrial and Nippon Denko are the only two producing companies in Japan, and hold similar market share.
Other color inorganic pigments Kyosei Chemical, a joint venture between Dainichiseika and Kuraray, is the sole supplier of iron blue in Japan. Its crude iron blue production is located in Kurarays Nakajo plant site in Niigata prefecture, using Kurarays captive hydrogen cyanide coproduced at methyl methacrylate production (by the acetone cyanohydrin process), and iron blue sales are handled by Dainichiseika. Daiichi Kasei Kogyo is the sole producer of ultramarine blue. Daiichi produces ultramarine pigments at two plant sites, one in Hyogo Prefecture and the other in Shiga Prefecture. Beside ultramarine blue, the company produces ultramarine pink and ultramarine violet. Ferro Enamels (Japan) Ltd. produces a variety of complex inorganic pigments such as PB-28, 36, 72; PBn-24, 29, 33, 118; PG-19, 26, 50; and PY-53. Ishihara Sangyo, one of the leading producers of titanium oxide, also produces titanium yellows, categorized as complex inorganic pigments. Merck Japan Ltd. produces mica-based pearl pigments coated with titanium dioxide, black iron oxide or aluminium oxide, at its Onahama plant site in Iwaki City, Fukushima Prefecture. Reportedly, its capacity was expanded 25% in May, 1999. The flake size of pearl is roughly 20 micrometers in diameter with a 0.4 micrometer thickness and coated with titanium dioxide particles of 0.3 micrometer diameter. Depending on the surface coating type and its thickness, various color pearlescent pigments can be produced. These
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pigments have been consumed mainly in automotive basecoat applications, adding excellent luster appearance. Bismuth vanadate pigments are finding increasing interest in Japan as a substitute to cadmium and chromate pigments. These pigments are produced by Dainichiseika.
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. b. 79.0 127.9 135.8 127.8 138.9 169.5 164.3 173.3 190.8 212.7 225.6 219.2 227.0 211.7 195.2 207.4 222.6 238.9 250.4 216.4 225.4 232.0 Chrome Yellowa 11.5 10.7 10.1 9.7 10.4 9.9 8.5 7.9 7.9 8.2 8.51 8.08 7.93 8.11 7.05 7.07 6.26 5.93 6.41 5.34 3.99 3.60 Chromium Oxideb 1.34 4.20 3.63 3.12 5.16 5.20 5.17 3.84 4.93 6.18 7.06 7.26 6.71 6.50 6.20 6.20 5.10 6.13 5.39 5.78 5.56 5.44 Iron Blue 2.3 3.4 4.0 4.0 5.0 5.0 4.5 3.4 3.4 3.7 3.36 3.43 3.57 3.86 3.97 2.83 3.28 3.50 3.24 2.48 2.35 2.35 Molybdate Chrome Orange 2.39 2.91 2.77 2.74 2.98 2.86 2.57 2.24 2.38 2.47 2.45 2.35 2.51 2.33 1.96 1.97 1.88 2.00 1.94 1.98 1.42 1.24 Ultramarine Blue 0.96 1.02 1.24 1.28 1.42 1.52 1.43 1.47 1.44 1.43 1.58 1.83 1.65 1.58 1.55 1.60 1.49 1.62 1.52 1.29 1.33 1.35
Includes PO-21. Includes PG-15. (A) CEH estimates (data for 2000). (B) Japan Inorganic Chemicals Association (all other data).
SOURCES:
Among the iron oxide produced domestically, pigment use was approximately 27 thousand metric tons, about 12% of total iron oxide production in 1999. The production of chrome pigments is an important application for both sodium bichromate and chromic acid. However, production in Japan is expected to decrease at an average annual rate of 8-9% over the next five years, mainly because of environmental
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issues and their replacement by organic pigments. About 100-120 metric tons of cadmium pigments (yellow, orange, red) were produced in 1999, but most of these (89 metric tons) are for export demand.
Consumption The following table presents production of the major inorganic color pigments:
Japanese Consumption for Inorganic Color Pigments (thousands of metric tons, gross weight) Zinc Molybdate Chromate/ Chrome Chrome Zinc Yellow Orange Yellow 9.0 9.3 7.5 7.4 7.4 7.6 7.0 6.8 6.0 6.0 6.2 5.4 5.1 4.2 3.7 3.3 2.0 2.2 2.4 2.1 2.0 2.0 2.1 2.1 1.9 1.6 1.7 1.5 1.6 1.4 1.2 1.0 0.8 0.5 2.0 1.8 1.3 1.1 1.0 1.2 1.2 1.2 1.0 0.9 0.6 0.7 0.6 0.5 0.3 0.3 0.2 Ultramarine Blue na na na 1.2 1.3 1.4 1.3 1.3 1.2 1.3 1.3 1.5 1.6 1.7 1.8 1.8 1.8 CadZirconium Chrome minium Oxideb Oxideb Pigments na na na na na na na na na na na 0.4 0.4 0.4 0.4 0.4 0.4 na na na na 4.1 4.7 4.8 4.5 5.7 3.3 3.5 3.8 4.0 2.9 2.6 2.4 2.0 na na na na na na na na na 0.2 0.2 0.1 0.1 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 39.7 44.2 45.8 46.4 45.7 48.4 53.4 51.9 50.7 53.2 47.8 48.8 49.0 50.0
Iron Blue na na na 1.6 1.6 1.6 1.3 1.2 1.0 1.0 0.9 0.9 0.8 0.6 0.5 0.4 0.3
Bismuth Vanadate ---------neg neg neg neg neg neg neg 0.1
Total na na na 54.1 62.7 65.4 65.3 63.9 66.0 68.5 66.7 65.7 67.9 59.9 59.5 58.7 57.5
Average Annual Growth Rate (percent) 20002005 a. b.
0.4%
9.5%
9.0%
7.8%
5.6%
0.0%
0.0%
3.6%
na
20.0%
0.4%
The numbers for iron oxide consumption are for pigments only and excludes ferrite applications. Excludes consumption other than pigment use. CEH estimate based on data from the Japan Inorganic Chemicals Association and import data.
SOURCE:
Among the different types of pigment chemicals, the consumption of iron oxide and ultramarine blue has been fairly stable with some fluctuation. Chrome-type pigments and iron blue have been decreasing.
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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. 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, gross weight) Paints 1996 Iron Oxide Chrome Yellow Chromium Oxide Molybdate Chrome Orange Iron Blue Ultramarine Blue Zinc Chromate/ Zinc Yellow Total a. b. 12.9 4.6 1.4 1.4 neg 0.2 0.7 21.1 1999 11.2 2.9 1.4 0.7 neg 0.2 0.3 16.8 Plastics 1996 1.7 0.8 2.4 0.2 neg 0.3 -5.4 1999 1.6 0.5 1.2 0.1 neg 0.3 -3.8 1996 1.4 -neg -0.8 0.2 -2.4 Ink 1999 1.4 -neg -0.5 0.2 -2.1 Other (Pigment) 1996 34.8a 0.1 neg neg neg 0.6 -35.4 1999 Non-Pigment Use 1996 1999 114.2b -1.8 ----116.0 Total 1996 171.5 5.4 5.9 1.6 0.8 1.5 0.7 187.4 1999 163.0 3.7 4.6 1.0 0.5 1.8 0.3 174.9
34.6a 120.7b 0.3 -neg 2.0 0.1 neg 0.6 -35.6 ----122.7
Includes construction materials, ceramics/porcelain, pavement and paper application. Quantity used for ferrite/magnetic applications. CEH estimates.
SOURCE:
The major pigment application of iron oxide is in coloring concrete. Color pigments are used in paint applications for industrial coatings, but poor color-quality pigments of iron oxide are used mainly in anticorrosive coatings. 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. Iron blue is used mainly in newspaper ink for toning of carbon black, but as this application is cost conscious, the use of iron blue has been decreasing. Iron blue is also used as a color component in bluetype pressure-sensitive ink, but some big users have switched from blue ink to black ink in this application. Also, other applications replaced iron blue with organic pigments mixtures for better alkaline resistance, causing a further decrease in iron blue consumption. Meanwhile, the consumption of ultramarine blue has been stable in a wide variety of applications, including inks, coatings, plastics and others. Chrome yellow and molybdate chrome orange, which used to be consumed in screen inks, have not been used in recognizable quantities for ink applications in Japan in recent years because of toxicity concerns. These chrome-containing pigments has been used in industrial paint applications, such as in industrial automobiles (such as forklifts), topcoats on taxis, heavy-duty paint on large metal structures and traffic paint. The decrease of these pigments in paint applications results from two reasons: (a) the decrease of alkyd and oil paint production itself, and (b) paint companies do not formulate these pigments in new coating formulations anymore because of environmental concerns, so that these chrome pigments only continue to use old, existing formulations. Even though yellow is an important color for traffic paint, yellow pigment itself has lately been avoided in new traffic paints, instead being replaced with white traffic paint with double lines. Japanese consumption of chrome yellow is shown in the following table:
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Japanese Consumption of Chrome Yellow (thousands of metric tons, gross weight) Paints 1975 1985 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 a. b. 7.8 6.3 6.2 6.3 6.4 6.0 5.8 5.1 5.1 4.6 4.8 4.4 3.7 3.0 2.8 Plastics 0.9 1.1 1.2 1.1 1.1 1.0 1.0 0.9 0.8 0.8 0.6 0.5 0.5 0.5 0.4 Printing Ink neg neg neg neg -----------Othera 0.3 0.1 neg neg neg neg neg 0.1 0.1 0.1 0.1 0.1 0.1 0.3 0.1 Totalb 9 7.5 7.4 7.3 7.5 7 6.8 6.0 6.0 5.4 5.4 5.0 4.1 3.6 3.3
Includes drawing paints and crayons. Totals may not equal the sums of the categories because of rounding. CEH estimates based on import data and data from the Japan Inorganic Association.
SOURCE:
Japanese consumption of molybdate orange is estimated to have been as follows:

Japanese Consumption of Molybdate Chrome Orange (thousands of metric tons, gross weight) Paints 1975 1980 1985 1988 1989 1990 1991 1992 1993 1994 1995 1996 1997 1998 1999 2000 1.8 2.0 1.8 1.7 1.7 1.8 1.9 1.6 1.4 1.5 1.4 1.4 1.3 1.0 0.7 0.6 Plastics 0.3 0.3 0.3 0.3 0.3 0.3 0.2 0.2 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1 Printing Ink neg neg neg neg neg -----------Othera 0.1 0.1 neg neg neg neg neg neg neg 0.1 neg neg neg neg 0.1 neg Totalb 2.2 2.4 2.1 2.0 2.0 2.1 2.1 1.9 1.6 1.7 1.5 1.6 1.4 1.2 1.0 0.7
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a. b.
Includes drawing paints and crayons. Totals may not equal the sums of the categories because of rounding. CEH estimates based on import data and data from the Japan Inorganic Chemicals Association.
SOURCE:
Zinc chromate pigments, also called zinc yellow, are used primarily in anticorrosive primers. Chrome oxide is excellent in acid, alkali and heat resistance and is used in coatings, porcelain enameled products and special inks. Domestic consumption of cadmium pigments was only around 20 metric tons, which has been decreasing because of environmental concerns. Applications are limited to use in porcelain enameled products, where it is difficult to find a substitution for cadmium pigments. Zirconium oxide is white pigment used for ceramics, but also consumed to produce spinel color pigment (complex).
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. 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 94 108.8 121.0 130.9 113.7
Average unit value including ferrites and pigments. (A) Yearbook of Chemical Industries Statistics, Ministry of International Trade and Industry (data for YEN PER KILOGRAM). (B) International Financial Statistics, International Monetary Fund (data for EXCHANGE RATE).
SOURCES:
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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 700-1,000 700-1,000 Ultramarine Blue 860-980 860-980 Zinc Chromate 550-680 550-680 Exchange Rate (yen per dollar) 109 113.7
Iron Blue 650-750 650-750
SOURCES:
(A) CEH estimates. (B) International Financial Statistics, International Monetary Fund (data for EXCHANGE RATE).
Market prices for inorganic pigments vary within a broader range, by grade and the amount purchased; however, much cheaper prices are available for large-volume consumers. The market price of iron oxide with poor color quality for anticorrosive coating use is much cheaper than the price listed.
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 5.34 10.83 13.49 14.61 13.84 21.56 26.26 26.10 23.19 26.25 23.34 23.34 Exports 15.23 14.48 32.64 38.82 40.10 36.57 39.65 51.35 50.39 52.64 45.79 35.77 Chrome Yellow Imports --0.05 0.04 0.01 0.03 0.01 0.04 0.04 0.06 0.10 0.11 Exports 1.22 0.81 1.34 1.39 1.75 1.35 1.29 1.18 0.96 1.31 1.62 1.04 Molybdate Chrome Orangec Imports --na na na na na na na na na na Exports 0.46 0.44 0.32 0.29 0.35 0.32 0.04 0.23 0.22 0.20 0.61 0.74
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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. --2.65 3.02 2.52 3.88 1.66 2.20 2.39 2.75 1.48 1.24 Exports 0.60 1.17 5.29 4.70 5.08 5.48 3.54 2.17 1.85 2.20 1.74 2.66 Iron Blue Imports neg 0.05 neg neg neg neg neg neg 0.02 0 0 neg Exports 2.00 2.76 1.67 2.19 2.50 2.90 1.84 2.29 2.63 2.52 2.01 1.80 Ultramarine Blue Imports neg 0.08 0.18 0.18 0.17 0.18 0.15 0.21 0.24 0.39 0.39 0.45 Exports 0.34 0.50 0.62 0.56 0.53 0.47 0.50 0.37 0.35 0.32 0.25 0.28
Since 1989, 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 2821.10-010 2841.20-000 na 2819.10-00 3206.43-000 3206.41-010 Exports 2821.10-000 2841.20-000 3206.20-100 na 2819.10-000 3206.43-000 3206-41-000
b.
Data represent all iron oxides including ferrites and pigments. Japan Exports & Imports, Japan Tariff Association.
SOURCE:
In 1999, Japan imported about 23.3 thousand metric tons of iron oxide mainly from China (45.4%), the United States (10.4%) and Germany (19.7%), while the country exported about 35.8 thousand metric tons mainly to the Republic of Korea (31.9%) and the United States (16.6%). Imports are likely to be primarily pigments by Bayer, whereas most of exports are ferrites/magnetic iron oxide. With regard to chrome yellow, Japan exported 1 thousand metric tons to Asian countries and Canada, while imports are very small. Japan exported 1.8 thousand metric tons of iron blue, which is about 76% of its production in 1999, mainly to the United States (31.2%) and Italy (23.6%). Japan exported 86 metric tons of cadmium pigments in 1999, mainly to Taiwan and the Republic of Korea.
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O THER ASIAN COUNTRIES Producing Companies There are a number of producers of inorganic color pigments in Asia:
Major Asian Producers of Inorganic Color Pigments2000
Pigments Page 158
Company Korea, Republic of
Zinc Chromate (anticorrosive pigment)
Iron Blue (Blue 27)
Other
Ukseung Chemical Company Ltd. Taiwan China Steel Corp. X
PIGMENTS
Ching Hua Chemical Co., Ltd. Fu Tai Chemical Industry Co., Ltd. Goodwill Chemical Corp.
Pearlescent pigments X
New Hsin Jung Enterprise Co., Ltd. Poo Nan Chemical Industrial Co., Ltd. Sheng Yu Steel Co., Ltd. Taiwan Colors & Chemicals Co., Ltd. X
May 2001 575.0006 B
Taiwan Itai Enterprises Co., Ltd.
Sambo Fine Chemicals Mfg. Co., Ltd.
Major Asian Producers of Inorganic Color Pigments2000 (continued)
Pigments Page 159
Company Taiwan (continued)
Zinc Chromate (anticorrosive pigment)
Iron Blue (Blue 27)
Other
Yieh Loong Enterprise Co., Ltd. Yih Chen Chemical Industry Co., Ltd. India Number of Companies
15
12
SOURCE:
CEH estimates based on the Directory of Chemical Producers, SRI Consulting.
May 2001 575.0006 C
Yen Kwang Color Co.,Ltd.
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The table below is the estimation of salient statistics in selected Asian countries (imports/exports are listed in the table at each country section).
Salient Statistics of Inorganic Color Pigments in Selected Asian Countries China Production Chromium Yellow 1997 1998 1999 10.1 10.3 na Zinc Chrome 0.1 3.8 na Ultramarine Blue 1.1 0.8 na Iron Oxidea 95.9 103.0 na Molybdate 0.4 0.0 na Red Lead 26.4 18.6 na Total 133.9 136.3 140 Apparent Consumption 27.6 30.2 40.5
Republic of Korea Production Cromium 1997 1998 1999 4.5 4.6 5.1 Zinc 0.9 0.1 0.0 Ultramarine Blue 0.1 0.1 0.1 Taiwan Production Chrome Yellow 1997 1998 1999 a. na 1.7 1.4 Zinc Chrome na 0.2 0.1 Molybdenum na 0.4 0.3 Iron Oxide na 0.5 0.6 Other na 0.7 0.4 Total na 3.4 2.7 Apparent Consumption na 8.5 7.4 Total 5.4 4.7 5.3 Apparent Consumption 19.2 25.9 25.2
Includes 1.7 and 0.4 thousand metric tons of magnetic powder in 1997 and 1998 respectively. (A) Korean Dyestuff and Pigments Industrial Association (Korean production). (B) Taiwan Dyestuff and Pigments Industrial Association (Taiwanese production). (C) China Chemical Industry Yearbook , China National Chemical Information Center (Chinese production). (D) CEH estimates.
SOURCES:
China Producing Companies There are numerous pigment producers in China. Bayer Shanghai Pigment Co. (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. Elementis Shenzhen (majority is owned by Elementis Pigments, formerly known as Harris & Crosfield)
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produces iron oxide pigments at a plant with a 20 thousand metric ton capacity at Shenzhen, Guandong province in 1998. These European joint ventures export significant quantities of iron oxide pigments back to Europe and also export to Japan and other countries. Jinpeng Iron Oxide Co., Ltd. at Guandong province, announced the completion of a plant with a 5 thousand metric ton capacity for iron oxide pigments in 2000. 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. Chinese producers of pigments are listed below.
Chinese Producers of Inorganic Color Pigments2001 Company Bayer Shanghai Pigment Co., Ltd.a Chongqing Jiangnan Chemical Factory Chongqing Xinhua Chemical Plant Guangdong Lingyang Co. Inc. Harbin Paint Plant Harbin Petrochemical Industry Corp. Henan Province Wun County No. 2 Chemical Plant Hunan Three-Ring Pigments Co., Ltd. Linying County Chemical Plant Ningbo Jinbco Group Co., Ltd. Shandong Longkou Chemical Plant Shenyang Paint General Corporation Shenyang Paint Plant Wenzhou Huasu Group Co. Xiangtan Chemical & Pharmaceutical Industrial Co. Yiyang Shangyou Chemical Factory Yunnan Yanglin Chemical Plant Zhengzhou Xinda Chemical Co. Zhenjiang City Plant Factory Zhenjiang General Chemical Factory Zhenjiang General Chemical Industry Corp. a. 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, established to produce high-quality iron oxide pigments. The joint venture started commercial production with an annual capacity of 20 thousand metric tons in the late 1996. 2000-2001 Directory of Chemical ProducersChina, SRI Consulting.
SOURCE:
Trade Export data for selected inorganic pigments in recent years are shown in the table below. Significant quantities of iron oxide have been exported.
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Chinese Trade in Inorganic Color Pigments (thousands of metric tons) Iron Oxide Imports 1997 1998 1999 SOURCE: 20.2 29.5 43.6 Exports 118.4 128.3 136.7 Chrome Yellow Imports 0.8 1.6 2.0 Exports 1.9 2.8 3.7 Red Lead Imports 0.2 0.1 0.1 Exports 1.4 1.0 0.9 Ultramarine Blue Imports 0.2 0.2 0.1 Exports 3.7 4.0 4.0 Iron Blue Imports 0.1 0.0 0.1 Exports 2.5 1.5 0.1
Chinas Customs Statistics, General Administration of Customs of the Peoples Republic of China
Republic of Korea Producing Companies Uk Seung Chemical Company, Ltd. and Sambo Fine Chemicals Mfg. Co., Ltd. (40% owned by Dainichiseika Color & Chemicals Mfg. Co., Ltd, Japan), both located at Pusan, are leading manufacturers of inorganic color pigments in the Republic of Korea. However, their product lines are limited to ultramarine blue, molybdenum orange and chrome yellow.
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. 21.4 24.3 25.9 26.9 41.8 40.3 14.6 23.7 23.4 1.0 1.8 1.4 1.7 1.7 1.5 1.7 3.3 4.6 Chrome Yellow Imports neg neg 0.88a neg neg neg neg neg neg Exports ---neg neg neg neg neg neg Red Lead Imports 0.1 0.1 0.2 0.2 0.1 na neg neg neg Exports 0.1 0.1 na 0.1 neg 0.1 0.1 neg neg Ultramarine Blue Imports 0.7 0.6 0.6 0.8 0.8 0.9 0.8 0.6 0.8 Exports neg neg neg neg neg neg 0.1 neg neg Iron Blue Imports na na 0.1 0.1 0.1 0.1 0.3 0.1 0.1 Molybdate Chrome Orange
Exports Imports Exports na na na neg neg neg neg neg neg neg neg neg neg neg neg 0.2 0.2 0.3 neg neg neg neg neg neg neg neg neg
Chrome pigments. Statistical Yearbook of Foreign Trade, Korea Customs Research Institute.
SOURCE:
Approximately 39% of iron oxide imports came from Japan in 1999. Iron blue pigments also came mainly from Japan (58%). The majority of ultramarine blue pigments originated in the United Kingdom (66%) and Japan (14%) in 1999.
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Taiwan Producing Companies Bayer Taiwan Co., Ltd. is believed to be one of the leading players in iron oxide pigments, and imports pigments from China and Germany to supply the Taiwanese market.
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 27.2 26.9 17.3 17.8 20.6 21.2 9.8 8.5 7.6 0.7 10.4 2.4 4.6 7.4 5.8 3.1 1.8 2.0 Chrome Yellow Imports 0.3 0.4 0.5 0.8 1.0 0.9 neg neg neg Exports 0.5 0.7 0.6 0.5 0.3 0.2 0.2 0.2 0.2 Red Lead Imports 0.9 0.6 0.4 0.3 0.6 0.4 0.2 0.3 0.2 Exports 18.5 1.2 1.3 1.1 2.6 3.8 2.5 2.4 3.0 Ultramarine Blue Imports 0.5 0.6 0.6 0.6 0.7 0.8 0.7 1.0 1.1 Exports neg neg neg neg neg neg neg neg neg Iron Blue Imports 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Molybdate Chrome Orange
Exports Imports Exports neg 0.1 neg neg neg neg 0.0 0.0 0.1 neg neg neg neg neg neg 0.1 0.1 0.1 neg neg neg neg neg neg neg neg neg
SOURCE:
Monthly Statistics of Imports and Monthly Statistics of Exports , The Peoples Republic of ChinaTaiwan District, Statistical Department, Directorate General of Customs, Ministry of Finance.
Taiwans iron oxide imports from Japan decreased from 4.47 thousand metric tons in 1997 to 1.94 thousand metric tons in 1999 (25% of total iron oxide imports). On the other hand, imports from China increased from 1.47 thousand metric tons in 1997 to 2.07 thousand metric tons in 1999 (27%). Ultramarine pigment imports were mainly from the United Kingdom (58%).
ORGANIC COLOR PIGMENTS DESCRIPTION

Organic color pigments can provide certain advantages over inorganic pigments. They generally possess greater brightness and tinctorial strength and can serve as replacements for inorganic pigments. They are usually transparent or semitransparent, in contrast with the more opaque inorganic pigments. However, organic pigments are limited in ways that inorganic pigments are not. For example, they are subject to bleeding in some solvents and degradation after prolonged exposure to light or high temperatures. In addition, they are usually more expensive. However, their aesthetic and performance properties have firmly established them in printing ink, paint, certain plastic and other applications.
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Organic color pigments are classified into two categoriestoners and lakes.
q
A toner is a pure organic pigment that is insoluble in and unaffected by, the vehicle or substrate in which it is incorporated (see the definition of a pigment in the INTRODUCTION of this report). It can be applied as a colorant free of any inorganic carrier and, thus, offers the maximum possible tinting strength for its type. A lake is an organic colorant that has been combined with an inorganic substrate (such as light alumina hydrate) to produce an insoluble pigment. Overall, most organic pigments, both toners and lakes, are consumed as dispersions or presscakes (see the MANUFACTURING PROCESSES section for further description).
Essentially all organic color pigment production is synthetic. 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.
AZO PIGMENTS Azo pigments are either monoazo, with one chromophore (NN) group or disazo, with more than one. As a class, azo pigments are the pigment of choice in many ink, coating and plastics applications. Arylide (Hansa) yellows and oranges include PY-1, 3, 65, 73 and 74. They are monoazo pigments; their nomenclature is derived from the second component of their structure, which is an arylide of acetoacetic acid. Arylides are characterized by intense color, semiopacity and high tinting strength. Lightfastness is good in deep shades, but relatively poor in tints. They show good resistance to chemicals, but have poor bleed resistance and are sensitive to heat. Shades range from deep reddish orange to pale greenish yellow. Diarylide yellows and oranges include PY-12, 13, 14, 17 and 83 and PO-16. The first component of a diarylide is 3,3-dichlorobenzidine, a diaminobiphenyl compound that reacts with two molecules of the second component to yield the diazo pigment. The second component is an arylide, as in the arylide yellows and oranges. 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. Diarylides show good chemical resistance to both acid and alkali environments and generally also have good heat resistance. However, their lightfastness in tints is even poorer than that of the arylides. Bleed resistance varies from low to high, depending upon the functional groups substituted on either the benzidine or arylide portion of the molecule. PY-12 was the largest-volume organic color pigment produced in the United States in 1999. Dinitraniline orange (PO-5) is a monoazo pigment giving a bright orange shade, produced from the coupling of beta-naphthol with 2,4-dinitroaniline. It is a low-cost pigment, of clean color and good to excellent hiding power, having good chemical resistance, excellent dispersibility and good full-strength
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lightfastness. However, lightfastness in tints is poor. It resists bleeding in water, but not in organic solvents. Pyrazolone red (PR-38) and bright orange-red (PO-13 and 34) are disazo pigments whose first component is a dichlorobenzidine derivative, as in the diarylide yellows. The second component is a derivative of pyrazolin-5-one. Pyrazolone pigments are distinguished by high intensity, excellent color and good bleed, bake and chemical resistance. However, these pigments are more expensive than the diarylides and have low hiding power and poor lightfastness in tint formulations. Naphthol reds and browns include PR-2, 5, 7, 9, 17, 22, 23, 31, 112 and 170 and PBn-1, ranging from light yellowish red to deep maroon. They are named for their second component, which is an arylamide of 3-hydroxy-2-naphthoic acid. Their outstanding features are good durability and a high degree of chemical resistance. However, they tend to bleed in certain solvents. Naphthol pigments are used in formulating water-based inks. Their lightfastness is good for interior paint applications, but marginal for exterior use, with the exception of PR-170, which has good lightfastness and excellent bleed resistance in exterior conditions. PR-112, which is less commercially important than PR-170, has excellent lightfastness but no resistance to bleeding in certain solvents. There are also some other recently developed naphthol reds that show greatly improved lightfastness properties. Toluidine red (PR-3) is a monoazo pigment with a second component of beta-naphthol. It possesses good brightness and tinting strength, good hiding power and excellent chemical resistance. PR-3 is bleedresistant in water but not in organic solvents. Toluidine reds are characterized as light, medium and deep and include a range of yellowish red to red shades. Benzimidazolones are monoazo pigments that are variations on the basic benzimidazolone structure. They include PBn-25; PO-36, 60 and 62; PR-171, 175, 176, 185 and 208; PV-32; and PY-120, 151, 154, 156 and 175. Their cyclic carbonamide structure makes this group of pigments much more heat-resistant and light-fast than other less expensive monoazo pigments. The red-orange, brown, yellow and yellow-green pigments are rather dull in color, but the red to red-violet shades (PR-176, 185 and 208 and PV-32) offer good brightness. They are all transparent except for the yellows, which are semiopaque. They are moderately high in price, 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. They are also used in automotive and other industrial finishes, lacquers and certain inks. Although they are less expensive than quinacridones and perylenes, their growth in U.S. highperformance coatings has been limited due to the higher-quality coatings obtained with quinacridones and perylenes. Disazo condensation pigments (including PO-31; PR-144 and 166; PY-93, 95 and 128; and PBn-23) are essentially made up of diazotized aromatic amines and 2-hydroxy-3-naphthoic acid (BON acid), condensed with aromatic diamines. By using a variety of components it is possible to obtain a wide range of colors in the resulting pigments. These high-molecular-weight products were developed in order to obtain colorants with improved physical properties compared with other azo pigments. In general, they offer excellent color intensity and tinting strength; excellent resistance to light, heat, chemicals and solvents; and superior stability and processing capabilities. They outperform the diarylide yellows and soluble azo reds in plastics and pigmented fiber applications. Although they are expensive, their high color strength keeps their overall cost at a more economical level. They have been used in plastics and coatings as replacements for toxic lead-containing inorganic pigments. Available colors range from dull reddish brown (PBn-23) through bluish red (PR-144), orange (PR-166 and PO-31) and yellow (PY-95) to bright greenish yellow (PY-93 and 128). PR-144 and PY-93 are particularly useful in pigmented fiber applications.
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Red lake C (PR-53) is prepared from 2-amino-5-chloro-p-toluenesulfonic acid and beta-naphthol. 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). The latter product was the fifth-largest organic color pigment manufactured in the United States in 1995. It has excellent brightness and tinting strength and fair heat resistance. Weaknesses include poor hiding power and lightfastness and poor alkali and soap resistance. Its color is bright yellowish red. Lithol red (PR-49) is produced by the coupling of 2-naphthylamine-1-sulfonic acid and 2-naphthol. It is commercially produced in the form of four different salts: sodium (PR-49), barium (PR-49:1), calcium (PR-49:2) and strontium (PR-49:3). The barium salt production and use is declining, while calcium salt is growing, particularly in gravure printing. Lithol reds advantages include good color intensity and tinting strength, fairly good bleed resistance, excellent dispersibility and relatively low price. Its drawbacks are poor chemical and bake resistance and no lightfastness. Shades of increasingly darker red are manufactured by preparing metal salts of sodium, barium, calcium and strontium. The sodium salt is the lightest shade; strontium is the darkest. Lithol rubine (PR-57) and red 2G (PR-52) are both prepared by coupling with a second component of BON acid. 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. 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. In 1995, Lithol rubine calcium salt (PR-57:1) was the third-largest volume organic pigment produced in the United States. Red 52:2 can be blended with molybdate orange for use in industrial coatings. Alkali and soap resistance of Lithol rubine and red 2G are poor and heat resistance is only fair; however, solvent bleed resistance is good, as is lightfastness in the full-strength forms. The calcium salts of both pigments provide a clean, intense bluish-red color that is popular in printing ink formulations. Permanent red 2B (PR-48) is prepared by coupling 6-amino-4-chloro-m-toluenesulfonic acid with BON acid. This pigment is available in four salts: barium (PR-48:1), calcium (PR-48:2), strontium (PR-48:3) and manganese (PR-48:4). All the salts have excellent bleed resistance, fair to good heat resistance and lightfastness, but poor alkali and soap resistance. The barium salt is bright yellowish red; the calcium and manganese salts are bluer in tone. Scarlet 3B lake (PR-60) is a monoazo lake pigment that is precipitated onto an alumina hydrate substrate. It is prepared as the barium salt of the coupling of anthranilic acid and 2-naphthol-3,6-sulfonic acid. Its clear, bright red tone, good lightfastness and high bake and bleed resistance, combined with its moderate price, make it competitive with other red pigments for many applications. However, it is limited by inferior acid, alkali and soap resistance and must be specially treated to reduce water solubility.
PHTHALOCYANINE PIGMENTS Phthalocyanine blue and green pigments (including PB-15 and 16 and PG-7 and 36) are based on the phthalocyanine chromophore, which is synthesized from phthalonitrile or from phthalic anhydride and urea. Its large, symmetrical structure, full of conjugated double-bonds, makes it a stable, intensely color compound that is the basis for what has become the leading group of colorants in several applications. In general, all the phthalocyanine pigments exhibit excellent transparency, lightfastness, heat stability, chemical and bleed resistance, processing capabilities and durability. Phthalo prices are generally moderate to high, although the high tinting strength of these pigments makes them economical in terms of
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coloring value. Phthalo blues are the workhorse blue pigment in every major end-use market for organic pigments. Copper phthalocyanine blue, PB-15, is available in two crystalline modifications: the alpha form PB-15, 15:1 and 15:2, which is reddish blue and the beta form PB-15:3 and 15:4, which is more stable and greener in tone. PB-15:3 was the largest-volume organic color pigment produced in the United States in 1999. The alpha form often converts to the beta form in strong solvents and at high temperatures and also has a tendency toward flocculation. 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). The beta form is already stable and noncrystallizing, but it can be treated to be nonflocculating. Thus, the two possible beta forms are PB-15:3 (NC) and PB-15:4 (NCNF). The betas are greener and less intense. They have less bronzing tendency than the alphas, but are equal to them in their other physical properties. Because of their replacement of iron blue in publication gravure ink applications, copper phthalo blues are experiencing high growth rates. Consumption of PB-15:2, which is a red shade, is also increasing at a substantial rate, because of its growth in plastics and automotive coatings applications. One of the newer phthalocyanine pigments is PB-15:6, which is the epsilon modification of copper phthalocyanine. This pigment has the reddest blue shade of all phthalocyanine pigments. Phthalocyanine blue, metal-free (PB-16) is a version of the phthalocyanine molecule in which the central copper atom has been replaced with two hydrogens. The resulting pigment is much greener than the copper modifications. However, its metal-free characteristic is its sole selling point over other less expensive phthalos. The metal-free pigment is available in solvent-unstable (alpha) and solvent-stable (beta) crystalline forms. It is consumed in small quantities, but is growing very quickly as a specialty pigment in certain copier systems requiring metal-free color receptors, because of toxic-metal concerns. PB-16 is supplied only through U.S. imports, mainly by BASF Corp. Phthalocyanine green pigments (PG-7 and 36) are modifications of the copper phthalo blues, with the replacement of hydrogen atoms on the molecule by chlorine atoms (PG-7) or by chlorine and bromine atoms (PG-36). 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, the yellower the color). The physical characteristics of these pigments are like the phthalo blues except that the greens are not subject to crystallization. Phthalo greens are used in coatings, plastics, inks and textiles.
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). The two most important pigments in this family are the alkali blues, PB-19 and 61. In this report, PB-19 and 61 will be treated as a combined pigment and referred to as alkali blue, since in practice they are for the most part used interchangeably. Alkali blue pigments are prepared by sulfonating a phenylated derivative of rosaniline. The product is an acidic internal salt that is insoluble in water. Alkali blues are bright blue to greenish blue in color and exhibit the highest tinctorial strength of any blue pigment. They are transparent, with fair to good bleed and chemical resistance, good dispersibility and fair heat resistance. Their lightfastness is better than that of basic dye pigments but not as good as the phthalocyanine blues. They are suitable for use in inks, alone or as a toner for carbon black pigments. Combined with carbon black, they increase the opacity and
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covering ability of ink. The high tinting strength and low cost of alkali blue pigments make them the most economical of the blue pigments for certain applications.
Q UINACRIDONE PIGMENTS Quinacridone pigments (PV-19 and 42; PR-122, 202, 206, 207 and 209; and PO-48 and 49) are all variations on the basic quinacridone structure, which is Pigment Violet 19. The other quinacridone pigments have substituents, such as methyl groups and chlorines attached to the quinacridone ring, or are combinations of the basic quinacridone with quinacridonequinone, a related structure. The basic chromophore structure of the quinacridones is very symmetrical and stable. Thus, these pigments possess superior color, brightness and tinctorial strength, as well as excellent physical properties. Their lightfastness, heat stability and chemical and bleed resistance make them suitable for many highperformance applications including quality paints, inks and plastics, despite their very high cost. 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, 202 and 206) to violet (PV-19 and 42). They are used mainly in automotive coatings, for both topcoats and refinishes and secondly in plastics. Both quinacridones and perylenes (see description below) are used in conjunction with metals to produce metallic finishes.
PERYLENE PIGMENTS Perylene reds include PR-123, 149, 178, 179, 190 and 224. They are anthraquinone pigments, derivatives of perylene-3,4,9,10-tetracarboxylic diimides. They provide excellent chemical, bleed and bake resistance and generally superior lightfastness, although PR-149 is not light-resistant enough for exterior use. They are available in several transparent and semitransparent shades, with PR-123, 149 and 178 offering brighter colors than the comparatively dull tints PR-179, 190 and 224. Though expensive, they have an important role in the market for high-performance specialty pigments and find considerable use in exterior automotive coatings, particularly the bright red colors. The U.S. supply of perylenes is dominated by Bayer, with the balance coming mainly from BASF.
O THER O RGANIC PIGMENTS Basic dye pigments contain the chromophore triphenylmethane or a similar structure. Permanent basic dye pigments include rhodamine red and violet (PR-81 and PV-1) and methyl and ethyl violets (PV-3 and PB-14). Of these, methyl violet is the most commercially significant. These pigments exhibit excellent color, transparency and tinting strength. Although they are costly, their superior aesthetics and mostly excellent physical properties make them the pigments of choice in specialty ink applications, where their shades are needed to match colors. Fugitive methyl violet (PV-3:3) is exceptionally bright and beautifully colored, but as indicated by the term fugitive, it has poor durability and bleeds in many media. Carbazole violet (PV-23) is made from aminoethylcarbazole and chloranil to produce the conjugated double-bonded ring structure of the dioxazine pigment. Carbazole violet exhibits an exceptionally bright, strong blue-violet color, of excellent heat, chemical and bleed resistance and good lightfastness, although it is very expensive. Carbazole violet is almost always used with other pigments, mostly for pearlescent automotive coatings where it provides a blue color with a red shade (or tint) to the final finish. Diketo-pyrrolo-pyrrole (DPP) pigments, discovered by Ciba-Geigy AG, were introduced to the automotive market in 1986. Today, two pigments are manufactured; the main pigment is PR-254 and of
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minor importance is PR-255. DPP pigments are reportedly synthesized by reacting a succinic ester with a benzonitrile in the presence of sodium methylate in methanol. DPP pigments possess excellent coloristic properties and are used primarily in the demanding automotive market. In 1992, the solid solution pigment of quinacridone and DPP entered the plastics market. Alizarine red and maroon (PR-83 and PV-5:1) are both anthraquinone pigments of very small usage. Alizarine red is a bright bluish-red shade and alizarine maroon is reddish-violet. Tetrachloroisoindolinones (PY-109 and 110, PO-42 and 61 and PR-180) are made by joining two 4,5,6,7tetrachloroisoindolinone residues to a diamine. The nature of the diamine determines the color of the resulting pigment, which can be anything from greenish yellow to bright red. This class of pigments is characterized by excellent brightness, tinting strength, stability and ease of processing. Although they are very costly, 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. Fluorescent organic pigments consist of various dyestuffs (e.g., rhodamines) that have been placed on a resin matrix and are not considered lakes. Resins are based on formaldehyde, polyester or nylon. They are used for apparel/textile printing, fluorescent plastics and some inks. Data on fluorescent brighteners are included in the CEH marketing research report on Dyes. For this reason, fluorescent organic pigments are discussed only briefly in this report and are not included in the data.
MANUFACTURING PROCESSES
Organic pigments are typically produced in two steps: the chemical synthesis of the pigment and its finishing or conditioning, to obtain specific properties. The finishing step enhances and stabilizes the desired pigment characteristics, including its physical form. When synthesis and finishing are complete, the pigment is normally filtered and washed to remove impurities, at which point it is usually referred to as the presscake. As part of their organic pigment product line, most producers sell water-wet presscake or dry color/powder, which is presscake that has been dried and pulverized. However, both presscake and dry powder may undergo various treatments to further tailor the pigments characteristics to meet user needs. Finishing of presscakes for printing ink and similar applications involves two major procedures: (1) drying, grinding and possibly dispersing, and (2) flushing. Pigment dispersion involves thorough mixing of the dried and ground pigment with another material, which is most often liquid, as is done for ink and coating applications. Flushes are produced when the water content of a presscake is replaced or flushed away, by an oil-based liquid. In this case, the oil base that is used is specific to the intended use.
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. In general, the following steps are taken in the production of azo pigments. The first component, a primary aromatic amine (or a diamine, in the case of diazo pigments), is dissolved or suspended in an acidic solution. Sodium nitrite is added, which forms nitrous acid in the solution and
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diazotizes the amine. The temperature is usually held below room temperature during this step of the manufacturing procedure. The unisolated diazonium salt can then be coupled under basic conditions with the second component, which is a phenol, naphthol, aromatic, amine or methylene group. Typical examples of the second component are 2-naphthol, 3-hydroxy-2-naphthoic acid, an arylide or arylamide of acetoacetic acid or a pyrazolone derivative. After the coupling process is complete, if the pigment is insoluble, it will precipitate from the solution. Examples of this type are arylide (Hansa) yellows and oranges, diarylide yellows, orthonitraniline and dinitraniline oranges, pyrazolone oranges and reds, naphthol reds and browns, toluidine red, para red, parachlor red and chlorinated para red. If the pigment is soluble, the addition of a metal salt is required to precipitate the toner. Soluble azos contain anionic groups, such as sulfonic or carboxylic acid; examples include Lithol red and Lithol rubine, red lake C, red 2G, permanent red 2B and scarlet 3B lake. Finally, the product is filtered and either washed and dried or prepared as a flush color. Production factors affecting the intensity, shade and physical properties of the finished pigment include the method and rate of coupling, the pH and temperature of the reaction solution, the concentrations of the reactants, the mixing efficiency and the drying method and temperature. These factors all affect the ultimate size, shape and surface area of the pigment particles, which in turn influence color, brightness and such properties as dispersibility and flow of the final product.
PHTHALOCYANINE PIGMENTS There is more than one commonly used method of preparing phthalocyanine pigments. In one process, phthalic anhydride is combined with urea, a copper salt (usually copper-I chloride, but copper-II chloride may also be used) and a catalyst, 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
N C N C
+ 8 H 2O + 4 CO2
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The catalyst may be a molybdate or molybdic acid derivative. The reactants can be dissolved in an organic solvent or heated to 180-200C to complete the reaction. Then the product is washed with hot water or hot dilute acid to remove any urea by-products formed during the reaction. A second method uses phthalonitrile and a copper salt for starting materials, as follows:
N CN C
2+
C N Cu N C
N C N C
4
CN
Cu
+ 2e
C N
The reaction conditions are the same as for the first method, requiring an organic solvent or heating. However, no washing is needed after completion. The product of both of the above methods is not a finished pigment but is the basic blue copper phthalocyanine structure. Different methods of finishing are applied, depending on the pigment form ultimately desired. To obtain the alpha forms PB-15 and 15:1, the base product is acid-pasted (mixed with concentrated sulfuric acid followed by rapid dilution with water). PB-15:2 can be obtained from the acid-paste method, but is more commonly obtained from the salt-ground monochlor. The beta form (PB-15:3, 15:4) is made by grinding the phthalocyanine base in the presence of a polar solvent. Other surface treatments can be applied at this point, to either the alpha or the beta form pigment, to yield a product of upgraded physical properties, such as a noncrystallizing or nonflocculating pigment. The metal-free pigment (PB-16) is usually made by following the phthalonitrile method to produce not a copper salt but a sodium, calcium or magnesium salt. This is followed by treatment with dilute acid to remove the metal ion. Acid pasting is then used to obtain the finished pigment. In the synthesis of phthalo green (PG-7), the phthalocyanine base is dissolved in a strong chlorinated solvent (such as chlorosulfonic acid, sulfonyl chloride or aluminum chloridesodium chloride eutectic mixture) to replace from thirteen to fifteen hydrogens with chlorines on each molecule. PG-36 is made by first applying brominated solvent until a desired number of bromines have been substituted for hydrogen, followed by application of chlorinated solvent to attach chlorines on some of the remaining sites. Usually eleven to fourteen hydrogens are replaced, with four to nine bromines and two to ten chlorines. After the halogenation step is completed, the solvent-pigment mixture is poured into water to separate the pigment from the solvent. The product may then be acid pasted or ground to produce the finished pigment.
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Q UINACRIDONE PIGMENTS Quinacridone pigments are usually prepared by one of the following methods:
q
Cyclization of 2,5-diarylamino terephthalic acid or one of its derivatives:

H N
COOH H N O C
HOOC
H
polyphosphoric
acid C O N H quinacridone
2,5di(phenylamino) terephthalic acid
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
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 pigments physical properties.
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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 PigmentsMarch 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
Xc
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U.S. Producers of Organic Color PigmentsMarch 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
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.)
May 2001 575.0006 S

b. c.
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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.
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 CDRs 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:
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Market Positions of U.S. Producers/Suppliers of Organic Color Pigments2000a 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 EuropeanCiba, Clariant, Bayer and BASFand 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 Chemicals 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 Chemicals 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. CDRs acquisition of BASFs Holland, Michigan organic pigment plant in 1996 gave CDR a more efficient plant and significantly increased its ink market share. CDRs 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. Clariants 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 Clariants U.S. organic pigment sales are derived from imports.
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BASF is the worlds largest producer of alkali blue and is the largest U.S. supplier of that pigment, holding roughly 75% of the U.S. market. BASFs alkali blue is made at the Huntington, West Virginia plant. BASF is the second-largest U.S. supplier of perylenes. Imports by BASF account for the majority its total value of U.S. organic pigment sales; exports also account for a significant share. Value-added organic pigment products (i.e., flushes and dispersions) represent up to 30% of its total organic pigment sales. In sales value, BASFs most important individual organic pigments are its phthalocyanines, followed by its perylenes, PR-178 and 179 (all of which are imported). Its PR-178 is used largely in the U.S. automobile industry. Bayer is the largest perylene producer and has the largest share of U.S. perylene supply. Bayers largest U.S. organic pigments market segment is high performance pigments for coatings, particularly automotive finishes; these constitute 70-80% of its total U.S. organic pigment sales. Like Ciba, Bayer supplies low-volume, high-value organic pigments, particularly perylenes, phthalocyanines and quinacridones as well as specialty yellows. Bayers second-largest organic pigments market segment is plastics. All of Bayers perylenes are domestically produced and significant amounts are exported. Magruder Color is the second-largest domestically owned U.S. supplier of organic pigments; its specialty is flush colors for inks; Magruders major business is organic pigments for inks. A significant quantity of its organic pigment sales are from flushes made from purchased pigments. Magruders November 2000 purchase of Uhlich Color gave it a broader customer list as well as additional pigment production technology. Apollo Colors is the third-largest domestically owned U.S. organic pigment producer and the fourthlargest flush color manufacturer for the ink market in the United States. Apollos product line includes red and yellow azos and phthalocyanine blue and green, specialty pigment dispersions from purchased pigments and phthalocyanine pigment press cakes. Apollos November 2000 purchase of Allegheny Chemical Corp. 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. 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):
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U.S. Producers of Largest-Volume Organic Color PigmentsMarch 2001 Diarylide Yellow AAA (PY-12) Phthalocyanine Blue (beta) (PB-15:3) Lithol Rubine, Calcium Salta (PR-57:1) Alkali Blue (PB-19 and PB-61) Diarylide Yellow AAOT (PY-14) Red Lithol Red, Lake C, Barium Barium Salt Salt (PR-49:1) (PR-53:1) Permanent Red 2B, Barium Salt (PR-48:1) Phthalocyanine Green (PG-7) Quinacridone Violet (PV-19)
Company and Plant Location Apollo Colors Rockdale, IL Allegheny Chemical Corp. 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 Daicolor-Pope, Inc. Paterson, NJ Engelhard Corporation Specialty Pigments and Additives Louisville, KY Euoropean Colour. Fall River, MA
PIGMENTS
X X
X X X
X X X
X X
X X X
X X X
X X X
May 2001 575.0006 V
Pigments Page 179
U.S. Producers of Largest-Volume Organic Color PigmentsMarch 2001 (continued) Diarylide Yellow AAA (PY-12) Phthalocyanine Blue (beta) (PB-15:3) Lithol Rubine, Calcium Salta (PR-57:1) Alkali Blue (PB-19 and PB-61) Diarylide Yellow AAOT (PY-14) Red Lithol Red, Lake C, Barium Barium Salt Salt (PR-49:1) (PR-53:1) Permanent Red 2B, Barium Salt (PR-48:1) Phthalocyanine Green (PG-7) Quinacridone Violet (PV-19)
Company and Plant Location Galaxie Chemical Corp. Paterson, NJ BFGoodrich Performance Materials Cincinnati, OH Industrial Color Inc. Joliet, IL Magruder Color Company, Inc. Elizabeth, NJ Indol Division Carteret, NJ Max Marx Color Corp. Irvington, NJ Nichem Corp. Chicago, IL PMC Inc Chicago, IL Sun Chemical Corporation Colors Group Pigments Division Cincinnati, OH Muskegon, MI Newark, NJ Rosebank, NY
X X
X X
X X
X X X
X X
X X
May 2001 575.0006 W
a.
Although PR-57:1 is commonly referred to as Lithol rubine, calcium salt, Lithol for this pigment is a registered trademark of BASF Corporation. CEH estimates.
SOURCE:
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Salient Statistics Time series data on the U.S. production of organic color pigments by chemical type are presented in the following table:
U.S. 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. 8.76 10.69 12.75 12.99 18.80 20.68 19.82 22.57 23.45 11.67 12.82 13.80 13.57 14.31 16.91 15.96 19.23 11.55 13.95 13.49 13.5 13.0 14.3 15.0 Yellowd ---------9.63 10.33 10.90 12.49 13.06 14.10 14.55 14.69 13.51 14.84 14.92 15.0 15.1 16.6 18.2 Other ---------1.01 1.25 1.21 1.12 1.22 1.25 1-1.5 1-1.5 1-1.5 1-1.5 1-1.5 1.3 1.3 1.4 1.7 Phthalocyaninee 2.93 5.00 5.05 4.30 5.51 6.57 5.12 6.44 6.07 5.42 8.34 8.18 10.34 10.65 11.53 10-12 10-12 10.94 13.49 14.57 14.6 14.5 15.6 17.0 Condensation Acidf 2.71 2.90 3.00 1.03 3.48 3.59 3.29 3.08 3.65 3.92 3.91 4.64 3.91 5.08 5.96 5-6 5.5-6.5 5.5-6.5 5.5-6.5 5.5-6.5 6.0 6.0 6.0 6.0
Dyeg 0.77 0.88 1.42 1.22 0.67 0.66 0.54 0.65 0.73 1.45 0.58 0.63 0.64 0.68 1.05 0.8-1 0.8-1 1.0-1.2 1.0-1.2 1.0-1.2 1.1 1.1 1.2 1.3
Otherh 0.20 0.20 0.23 0.14 0.58 0.63 0.64 0.73 1.22 0.19 1.00 1.24 1.36l 2.11 0.93 1-2 1.5-2.5 2.0-3.0 2.0-3.0 2.5-3.5 3.0 3.0 3.3 3.6
Unspecifiedi 1.28 1.96 3.08 2.85 2.37 2.26 2.90 2.16 3.75 3.39 1.91 2.01 2.42m 3.25 1.72 na na na na 4.5-7.2 5.8 8.5 9.2 8.7
Totalj 16.66 21.63 25.54 22.53 31.41 34.38 32.32 35.64 38.85 36.68 40.15 42.60 45.85lm 50.36 53.45 51.31 56.94 59.60 61.0 60.2 60.3 62.5 67.6 71.5
The net weight of synthetic organic color pigments includes lakes, toners and active toner content of extended toners. The toner content of extended toners and flush colors represents the active coloring portion of the pigment; the remainder consists of inert materials added to improve certain physical properties of the pigment, such as float and flocculation resistance. Specific pigments included under each chemical type vary from year to year, depending on the availability of individually reported figures. Data probably exclude food, drug and cosmetic lakes and fluorescent pigments, both of which are made from dyes and are probably reported as dye production. Data may include monoazo brown, naphthol brown, arylide orange, diarylide orange, dinitraniline and orthonitraniline orange, pyrazolone orange, Lithol red, Lithol rubine, naphthol red, red 2G, para red, parachlor red, chlorinated para red, permanent red, pyrazolone red, red lake C, scarlet 3B lake, toluidine red and unspecified red lakes. Includes all specified azo pigments possessing red Colour Index names and unspecified naphthol azo reds as reported in the source. Includes all specified azo pigments having yellow Colour Index names as reported in the source.
b.
c.
d.
May 2001 575.0006 Y

e. f. Data include phthalocyanine blue and green.
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Data may include alkali blue, peacock blue (before 1966), phloxine red and all blue toners for which individual quantities are not reported. Data for all other blue toners in the source are estimated to be mostly for production of alkali blues. Data may include Victoria blue, basic blue, brilliant green, malachite green, permanent green, methyl violet, ethyl violet, fuschine, rhodamine red and violet and all violet toners for which individual quantities are not reported. Data include quinacridone violet and red, alizarine red and maroon, pigment green B (before 1974) and carbazole violet. Data include all yellow, orange, red, green and brown toners for which individual quantities are not reported and unspecified lakes. Data also include black toners in 1973-1977 and 1981-1988 (see the following table for further information on production of black toners). Data include some phthalocyanine green in 1984. Data include black toners in 1973-1977 and 1981-1988. Totals may not equal the sums of the categories because of rounding. Totals are CEH estimates 1993-1999. Data for 1960 are not comparable to data for later years, since the breakdown of production data was changed by the source beginning in 1961. Includes an estimated 0.6 thousand metric tons of quinacridone production omitted from the quantity reported in the source.
g.
h. i.
j.
k.
l.
m. Includes an estimated figure for 1988 unspecified red toner production. SOURCES: (A) CEH estimates (data for 1966 and 1991-1995 for CONDENSATION ACID, UNSPECIFIED and TOTAL; data for 1983 for AZO, CONDENSATION ACID, UNSPECIFIED and TOTAL; data for 1988 for OTHER and TOTAL; datum for TOTAL for 1989; all data for OTHER AZO, PHTHALOCYANINE; data for DYE and OTHER for 1991 and 1993-1995; data for AZO RED for 1993 and information in footnotes a, d, l and m and all data for 1996-1999). (B) Synthetic Organic Chemicals, U.S. Production and Sales, U.S. International Trade Commission (all other data 1960-1995 and information in footnotes a, i, j and m). (C) T. C. Patton, ed., Pigment Handbook, vol. 1, John Wiley & Sons, Inc., New York, 1973 (information in footnotes b, c and e-h).
Growth in organic pigment production is generally related to the overall economy and more directly to the largest market segment, printing inks. Growth in production over the past two decades has been concentrated in phthalocyanine pigments and the high-performance pigments, such as quinacridones and perylenes. Data for U.S. production of organic color pigments by color are presented in the following tables:
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U.S. 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. 7.81 9.33 10.08 9.25 11.22 12.51 12.56 13.36 13.55 13.25 14.22 15.21 15.69 17.16 18.45 15.97 19.23 19.62 19.75 18.4 18.5 19.0 20.9 21.4 Blue c 4.15 5.54 6.00 4.78 7.94 8.91 7.64 8.62 9.76 9.38 11.23 11.86 13.15 14.54 16.1 15.57 16.97 18.34 19.40 18.0 18.0 18.5 19.3 19.6 Yellowd 2.20 3.15 4.64 5.28 9.01 9.31 9.10 10.08 11.08 10.21 10.54 11.10 12.56 13.12 14.18 14.55 15.81 16.16 18.57 17.6 17.6 18.5 20.3 21.6 Violetb 0.46 0.55 1.07 1.03 1.03 1.11 1.00 1.17 1.71 1.46 1.37 1.67 1.81 2.55 1.72 2.31 1.94 2.06 2.16 2.1 2.1 2.2 2.2 2.3 Green 1.38 2.22 1.81 1.23 1.12 1.32 0.81 1.00 1.00 0.91 1.10 1.06 1.16 1.28 1.42 1.39 1.43 1.75 1.76 1.7 1.7 1.8 1.9 2.0 Orange 0.26 0.46 0.37 0.63 0.77 0.98 1.02 1.04 1.27 1.09 1.33 1.31 1.14 1.3 1.29 1.22 1.42 1.46 1.68 1.6 1.6 1.7 1.7 1.7 Otherbe 0.40 0.39 1.57 0.32 0.30 0.24 0.21 0.38 0.54 0.41 0.40 0.44 0.39 0.41 0.29 0.30 0.15 0.21 0.24 0.8 0.8 0.8 1.3 2.9 Totalf 16.66 21.64 25.54 22.53 31.41 34.38 32.32 35.64 38.85 36.68 40.15 42.60 45.85 50.36 53.45 51.31 56.94 59.60 63.56 60.2 60.3 62.5 67.6 71.5
The net weight of synthetic organic pigments represents the weight of lakes, full-strength toners and the active coloring portion of extended toners and flush colors. Inert materials added to extended toners to contribute certain properties or reduce cost are not included in the data. Data probably exclude food, drug and cosmetic lakes and fluorescent pigments, both of which are made from dyes and are probably reported as dye production. Data for RED include some violet in 1965. Datum for RED in 1988 includes an estimated figure for unspecified red toner production. Datum for VIOLET in 1988 includes an estimated 0.6 thousand metric tons of quinacridone violet production omitted from the reported figure. Data for 1970 and 1980-1988 exclude lakes. Data for 1965, 1970, 1975, 1981 and 1983-1992 exclude lakes. Data include brown pigments and unspecified synthetic organic pigments. Prior to 1973, black pigments were not included in the data. Totals may not equal the sums of the categories because of rounding. (A) CEH estimates (data for 1983 for BLUE, RED and TOTAL; data for 1988 for RED, VIOLET and TOTAL; data for 1989; and information in footnotes a and c and all data for 1995-1999). (B) Synthetic Organic Chemicals, U.S. Production and Sales, U.S. International Trade Commission (all other data).
b.
c. d. e.
f.
SOURCES:
May 2001 575.0007 A
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Historical USITC reported production may have been understated or overstated. Typical reporting problems included individual companies not returning replies to the USITC survey, causing production omissions, and production reported on a wet basis instead of conversion to a dry weight basis, causing production overstatement. The USITC discontinued its full reporting in 1995 and all reporting in 1996. Published data from the USITC for U.S. 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. 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 5.22 5.28 5.42 6.04 7.03 6.30 6.87 7.34 7.57 8.19 8.85 9.04 9.92 10.67 12.22 12.65 13.61 14.1 15.3 15.9 Phthalocyanine Blue (beta) (PB-15:3) 3.53 3.84 3.31 4.08 3.64 4.33 5.35 5.93 6.98 8.02 8.75 8.62 9.11 9.96 10.76 11.57 12.70 13.2 13.9 14.4 Lithol Rubine, Calcium Salt (PR-57:1) 2.08 2.47 2.85 3.52 4.08 3.87 4.51 5.39 6.01 7.22 8.25 7.31 9.49 9.16 10.78 10.95 11.57 12.0 12.6 12.6 Alkali Blue a (PB-19 and PB-61) 3.48 3.59 3.29 3.98 3.65 3.92 3.91 4.64 3.91 5.08 5.96 na na na na na na na na na Diarylide Yellow AAOT (PY-14) 1.34 1.66 1.60 1.69 1.91 1.98 1.97 2.00 2.36 2.37 2.86 2.96 2.82 2.85 3.08 2.26 na na na na Red Lake C, Barium Salt (PR-53:1) 1.77 1.95 1.92 2.16 2.20 2.02 2.00 1.71 2.02 1.16 1.96 1.39 1.71 1.39 1.41 1.42 1.36 1.4 1.5 1.6 Percent of Total Lithol Permanent Production, Red, Red 2B, All Organic Barium Barium Color Salt Salt (PR-49:1) (PR-48:1) Totalb Pigments 2.54 2.65 2.93 2.97 2.79 2.71 2.37 2.58 2.12 1.93 2.30 na 1.61 0.96 0.92 1.12 0.91 na na na 0.22 0.27 0.20 0.30 0.21 0.33 0.91 1.02 0.94 1.11 0.90 0.78 0.74 0.59 0.42 na na na na na 20.16 21.71 21.52 24.73 25.52 25.46 27.90 30.59 32.09 35.08 39.83 30.10 35.40 35.58 39.87 39.97 40.15 40.7 43.3 44.5 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. b.
5.9%
5.6%
3.6%
--
--
3.0%
--
--
2.7%
--
Data for all other blue toners in the source are estimated to be mostly for production of alkali blues. Totals may not equal the sums of the categories because of rounding. (A) CEH estimates (all data for ALKALI BLUE; datum for LITHOL RED, BARIUM SALT for 1983; data for PHTHALOCYANINE BLUE and LITHOL RUBINE, CALCIUM SALT for 1991 and 1995; datum for DIARYLIDE YELLOW AAOT for 1992; and all data for 1996-1999).
SOURCES:
May 2001 575.0007 B
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(B) Preliminary Report on U.S. Production of Selected Synthetic Organic Chemicals, U.S. International Trade Commission (all data for RED LAKE C, BARIUM SALT and LITHOL RED; data for BARIUM SALT for 1992-1993; and data for LITHOL RUBINE, CALCIUM SALT and DIARYLIDE YELLOW AAOT for 1993). (C) Synthetic Organic Chemicals, U.S. Production and Sales, U.S. International Trade Commission (all other data).
U.S. production of all organic color pigments grew at an average annual rate of about 5.8% from 1996 to 1999.
Consumption Consumption of organic pigments is dependent on demand in three major end-use marketsprinting inks, paints and coatings, and plastics. Inks are used primarily in publishing, advertising and packaging materials and growth within these markets resembles growth of the U.S. economy, with advertising spending significantly impacted by corporate profits.* Paints and plastics are consumed largely in the automotive and construction industries and these markets are also tied to the growth of the U.S. economy and factors such as interest rates. Estimated consumption of organic pigments since 1980 is shown in the following table:
U.S. 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 25.1 30.8 29.7 32.7 40-44 38.4 41.3 42.8 44.3 50.0 53.9 52.0 52.6 54.8 56.4 56.0 58.1 60.7 63.8 66.9
Advertising spending tends to exaggerate cycles of corporate profitability, since companies typically slash or eliminate advertising during downturns but renew spending as optimism returns with upturns. This was particularly evident in the 1990-1991 recession. The dot.com (e-commerce) explosion of advertising spending in 1999 to early 2000 rapidly accelerated advertising and color pigment for printing demand. 2001 by the Chemical Economics HandbookSRI International
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U.S. Consumption of Organic Color Pigmentsa (continued) Average Annual Growth Rate (percent) 19992004 a. Data represent dry weight pigment. CEH estimates.
2.5-3.1%
SOURCE:
Consumption of all organic pigments by major end-use market is listed in the following table:
U.S. Consumption of Organic Color Pigments by End Use 1996 Quantity Thousands of Metric Tonsa Printing Inks Paints and Coatings Plastics, Pigmented Fibers and Rubber Otherb Total a. b. 36.0-38.4 9.2-10.4 7.5-9.4 2.8-3.3 58.1 Percent of Total 62-66 16-18 13-16 5-6 100% Value Millions of Dollars 607-668 297-322 198-235 74 1,238 Percent of Total 49-54 24-26 16-19 6 100% Quantity Thousands of Metric Tonsa 43.1 10.7 9.7 3.4 66.9 Percent of Total 64 16 15 5 100% 1999 Value Millions of Dollars 555 255 222 78 1,110 Percent of Total 50 23 20 7 100%
Data represent dry pigment weight. Includes consumption for paper, textiles and miscellaneous uses, such as crayons, markers and artists colors. CEH estimates.
SOURCE:
Consumption of organic color pigments is expected to grow from 1999 to 2004 at the following rates:
Average Annual Growth Rates for U.S. Consumption of Organic Color Pigments by End Use1999-2004a (percent) Plastics/Rubber Printing Inks Paints and Coatings Otherb Average for All End Uses a. b. Based on consumption volumes, dry pigment weight. Includes paper, textiles and miscellaneous applications. CEH estimates. 3.5 3.0 2.0 2.0 3.3
SOURCE:
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Consumption data on end uses of selected organic pigments are presented in the following table:
U.S. Consumption of High-Volume Organic Color Pigments by Volume1999 (percent) Inks Blue Phthalocyanine Blue (alpha) (PB-15, 15:1, 15:2) Phthalocyanine Blue (beta) (PB-15:3) Phthalocyanine Blue (beta) (PB-15:4) Alkali Blue (PB-19, 61) Green Phthalocyanine Green (PG-7, 36) Orange Dinitraniline Orange (PO-5) Dianisidine Orange (PO-16) Red Naphthol Red (PR-2, 5, 17, 23) Toluidine Red (PR-3) Permanent Red 2B (PR-48, 48:2, 48:3, 48:4) Permanent Red 2B, Barium Salt (PR-48:1) Lithol Red (PR-49, 49:1, 49:2, 49:3) Red 2G (PR-52, 52:1, 52:2) Red Lake C (PR-53, 53:1, 53:2) Red Lake C, Barium Salt (PR-53:1) Lithol Rubine (PR-57, 57:1, 57:2) Rhodamine Red (PR-81) Violet Quinacridone Red (PV-19) Carbazole Violet (PV-23) Yellow Arylide Yellow (PY-1, 3, 65, 73, 74) Diarylide Yellow (PY-12, 13) Diarylide Yellow (PY-14, 17, 83) a. b. Includes alkali blue used in carbon paper. Includes some textiles. CEH estimates. 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:
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Average Annual Growth Rates for U.S. Consumption of Selected Organic Color Pigments by Volume1999-2004a (percent) Phthalocyanine Blue (beta) (PB-15:3) Alkali Blue (PB-19 and PB-61) Phthalocyanine Green (PG-7) Lithol Red, Barium Salt (PR-49:1) Red Lake C, Barium Salt (PR-53:1) Lithol Rubine, Calcium Salt (PR-57:1) Diarylide Yellow AAA (PY-12) Diarylide Yellow AAOT (PY-14) Quinacridone Violet (PV-19) a. Dry pigment weight. CEH estimates. 4 1-2 1-2 (4)-0 (2)-0 4-5 3.5-4 2-3 5-7
SOURCE:
The quinacridones, perylenes, diketo-pyrrolo-pyrroles, the arylide traffic yellow PY-75 and some organic fluorescent pigments are expected to have the highest average annual rates of growth. Projections for the U.S. organic pigments industry are based on the assumption that the industry will generally follow the growth of the U.S. economy and that environmental regulations will continue to move in their present direction (see ENVIRONMENTAL ISSUES and discussions on the individual markets). 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. In 1996, over 30% of U.S. 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.
Printing inks Printing inks are the major end use for organic color pigments, accounting for more than half of their total consumption by volume in recent years. The most important organic colors in inks are phthalo blues, alkali blues, azo reds (including Lithol red, Lithol rubine, red 2G and red lake C) and diarylide yellows. Together, these pigments make up almost all of the volume of organic colorants used in ink formulations. On a dry pigment equivalent value basis, diarylide yellows account for more than one-fourth of total U.S. sales of organic pigments (produced and imported) for inks; Lithol reds and Lithol rubines, red 2G and red lake C account for up to one-third; and phthalocyanine blues account for almost one-fourth. The major printing inks by printing processes are as follows (from greatest to smallest in domestic consumption): lithographic, flexographic and gravure. In terms of end-use markets, publications account for 34% by volume of all printing inks domestically consumed; packaging, 32%; newsprint, 20%; commercial, 10%; and specialty, 4%. Lithographic printing inks are used mainly in publication, commercial, newsprint and packaging markets; gravure inks are used mainly in publication and packaging; flexographic inks are used almost entirely in packaging; and letterpress is used mainly in newsprint, packaging and publication.
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The value of U.S. consumption of organic color pigments by ink process is distributed as follows:
U.S. Consumption Value of Organic Color Pigments by Printing Ink Application1999 (percent) Lithography or Offset Flexography Gravure Letterpress Othera Total a. Includes screen, intaglio and other applications. CEH estimates. 50 26 19 neg 5 100%
SOURCE:
Major organic pigments include PB-15:3, PR-57:1 and diarylide yellows for lithographic inks; PR-49:1, PR-57:1, PB-15:3, PG-15:4 and diarylide yellows for gravure inks; and PB-15:3, PG-7, PO-5, PO-16, PR52:1, PR-57:1 and diarylide yellows for flexographic inks. Printing inks, as fluids or pastes, are generally a mixture of pigments dispersed in different oils, resins, organic solvents, water and chemical additives. Pigments are the essential and most expensive ingredient in nearly all printing inks, varying between 45% and 70% of the total raw material cost.* Because of the variable conditions in U.S. printing operations, up to 80% of all ink sales are customized. In printing inks, pigments are selected to accommodate the end-use requirement. Flush color is by far the largest form in which organic pigments are used in inks, accounting for roughly 80% of all organic pigments consumed for inks, followed by powders, aqueous dispersions, presscakes and concentrated chips, which are used like aqueous dispersions, but are more concentrated. Phthalocyanine blues, beta form (PB-15:3 and 15:4, green shade) have several advantages for printing ink formulators. They are highly stable with excellent color and brightness. They are suitable for use in all types of inks. They also deliver good tinting strength per unit of cost. Preferred grades are those with the most uniform small particle size, which have the greatest cleanliness and transparency. (Transparency is required for inks that are used in three- and four-color printing processes.) The alpha-form phthalo blues (PB-15, 15:1 and 15:2, red shade) are suitable for flexographic and gravure inks. PB-15 cannot be used in solvent-type inks because it converts to the beta form (and hence changes color) in polar solvents, but PB15:1 and 15:2 are specially treated to be noncrystallizing and can be used in these inks. In the late 1980s, phthalocyanine pigments replaced inorganic Milori blue pigments in gravure printing at several printing houses, largely because of their greater stability and higher value (see discussion below on trends in the ink industry). Milori blues have also been replaced by phthalo blue in publication gravure ink processes, which are solvent processes. Gravure solvent processes dominate the U.S. archival publications sector. Alkali blues (PB-19 and 61) are used mainly for the toning of carbon black inks, to deepen the opacity (also known as adding jetness) and increase the covering ability of the ink. Their advantages, high tinting strength and low price, are undercut by poor bleed resistance and lightfastness. They are usually
In radiation-curable inks, the resins used are more expensive than the pigments typically used. 2001 by the Chemical Economics HandbookSRI International
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supplied as flush colors. Dry alkali blues are difficult to disperse and, therefore, flush formulations are preferred. Lithol reds (PR-49) are low-cost pigments with bright, strong color and good bleed resistance. They are useful in liquid ink formulations, particularly gravure and flexographic inks, because of their good viscosity and ease of dispersion. They may be prepared in resinated forms, which have increased brightness and transparency. PR-49:1 is experiencing some replacement by PR-57:1 because, in general, Lithol rubine has better properties for matching the colors used in interchangeable printing processes. Lithol rubine (PR-57) and red 2G (PR-52) pigments are available in several blue-red shades. They are attractive to ink makers because of their bright, strong colors, good prices and good physical properties. PR-57:1 is among the oldest and most important reds for oleo resinous printing inks (oil or paste inks). It is usually sold as a product containing 20-30% by weight resinous additives. Like the Lithol reds, Lithol rubine and red 2G pigments can be resinated to give high tinctorial strength and glossiness and to improve color, transparency and dispersibility. However, their fastness to soap, alkali and acid is poor. Red lake C (PR-53) is another low-cost red pigment that is used in inks for its good color, strength and printing qualities. In resinated form it has excellent transparency, improved brightness and cleanliness, and excellent waterfastness. The barium salt PR-53:1 is the most important for use in inks. In resinated form, red lake C is used in gravure, letterpress, flexographic and offset inks. However, because of the chemical constitution of red lake C, its inks are not fast to soap, alkali and acid. The nonresinated form is useful for inks requiring a more opaque colorant. Diarylide yellows are popular with ink makers because of their bright shades and their outstanding tinting strength. They have good printing qualities and are economical on the basis of cost per unit of tinting strength. Although semiopaque, they can be resinated to produce transparent grades for three- and fourcolor printing processes. With the largest volume of all organic pigments, PY-12 is used in lithographic, letterpress and publication gravure inks. Other diarylide yellows, including PY-13, 14, 17 and 83, are more heat-resistant and lightfast and less reactive with aromatic solvents than PY-12. Thus, they are preferred for packaging gravure inks, as well as for all inks that require greater heat resistance and lightfastness. Naphthols are becoming increasingly popular for use in water-based inks, because of their good fastness qualities and because they are among the standard Pantone colors for matching ink colors. A small amount of fluorescent ink is produced from fluorescent organic pigments. Between 1999 and 2004, overall consumption of organic pigments in printing inks is expected to grow at about 3-3.5% per year. Several market developments have accelerated growth including:
q
Color inks in newspapersThe growth and spread of color newspapers has stimulated organic pigment consumption. An additional trend is the shrinkage of the size of newspapers from a 54inch width to a 50-inch width. The size shinkage will cause some existing consumption of color pigments by newspapers to slightly decline. Digital printing/publishingcomputer-operated personalized direct mail, targeted and personalized magazines and desktop publishing. In the recent past, dyes were largely used for these ink jet printing applications. Increasingly, newly developed inks containing pigments in dispersions will supplement these dye-based inks since (1) dyes are more expensive and lack the
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performance qualities of pigments as they are more prone to flaking, and (2) in paper recycling, dye-based inks, such as those found in most ink jet printers today, are not easily deinked. 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.S. Consumption of Organic Color Pigments by Volume in Printing Ink Applications1999-2004 (percent) Gravure Inks Publication Gravure Inks Packaging Gravure Inks Flexography Inks Lithography Inks Letterpress Inks Other SOURCE: CEH estimates. 1 1 1-1.5 4 2.5-3 (10) 3
Over the past ten years, the trend has been toward the use of water-based inks instead of solvent-based inks. The advantage of using water-based inks is that fewer volatile organic compounds (VOCs) are emitted, thereby enabling compliance with air pollution regulations and also reducing worker health risks associated with VOCs. As a result, demand for flexography, which uses water-based inks, is growing faster than for lithography. Water-based inks have been used for nearly fifty years in various flexographic printing applications, on absorbent substrates like paper, corrugated board or cartons, to produce items such as sacks, bags, plates, envelopes, boxes and cups and for screen printing of textiles. More than 50% of all packaging material (mostly from flexographic printing) in the United States is printed with waterbased inks. In packaging, these inks are increasingly applied to nonabsorbent surfaces, such as polyvinyl chloride and polyolefin films and aluminum foils. With the increased use of waterborne systems on nonabsorbent substrates, 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. Use of water-based pigment dispersions is growing more quickly than use of powders and presscakes, especially in flexography and packaging gravure. In addition, a small but growing market for acrylic color concentrates (in chip forms) is developing in highquality water-based inks, such as those for printing foil substrates. Flexography is also expected to gradually make inroads into non-heat-set web printing. In addition to its environmental and safety benefits, water-based flexography is gaining market share because its print quality and color have improved, its use allows high press speeds and low paper waste, and it reduces show-through and ink rub-off. In light of regulatory restrictions regarding VOCs, gravure printers for packaging have shifted modestly to water-based inks to reduce emissions and air pollution abatement investments. 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. Very little color is used in letterpress printing; most involves only black inks and, therefore, its share of the organic pigments market is small and declining.
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Paints and coatings The paints and coatings industry is the second-largest U.S. market for organic pigments, accounting for 16% of the total consumption volume. The most important organic pigments used in paints and coatings are arylide and diarylide yellows, phthalo blues and greens, dinitraniline orange, naphthol reds, toluidine reds, quinacridones, perylenes, quinophthalones, isoindolines, tetrachloroisoindolinones and carbazole violet. On a dry pigment equivalent value basis, arylide yellows account for at least 15% of the total U.S. sales of organic pigments (produced and imported) in paints, high-performance red organic pigments account for more than 50%, violets account for 10-15% and phthalo blues account for over 15-20%. 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.S. Consumption of Organic Colored Pigments in Surface Coatings by Value1999
Other OEM and Special Purpose 15%
Architectural 30%
Automotive OEM 55%
Coatings that require the highest finished quality and, therefore, the highest-priced high-performance organic pigments are the automotive OEM topcoats and refinishes. Other industrialized coatings may use mid- to lower-price-range organic pigments. In North America, the trend in autos between 1999 and 2000 has been growth of metallic silver and white at the expense of colors. Red and green have lost the most share to metallic silver. Architectural coatings containing organic pigments include interior water-based flat paints, interior solvent-based semigloss and gloss paints and exterior water-based flat house paints. The arylide yellows are the highest-volume organic yellows used in paint formulating. They are superior to the inorganics in tinting strength and replace the chrome yellows where lead-free pigments are required. They are popular in the trade sales paint market, especially in water-based paints, where their high degree of alkali resistance is important. Some arylides tend to bleed in certain solvent-based paints, but several of the more recently developed arylide pigments have improved bleed resistance, making them attractive to paint formulators.
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Diarylides find only limited use in paints because of poor lightfastness, although they do find some use in interior paints and in baked finishes. Phthalocyanine pigments are used in all types of paints and coatings, including all kinds of OEM product finishes, such as for automotive topcoats and major appliances, interior and exterior architectural coatings (especially water-based paints) and special-purpose coatings such as auto refinishing. Their primary advantages are their excellent color, tinting strength, chemical stability and lightfastness. The noncrystallizing phthalo blues are necessary in the preparation of phthalo-pigmented solvent-based paints. Dinitraniline orange has many qualities that make it appropriate for use in the paint industry. These include low cost, clean color, good chemical resistance and lightfastness in full to medium tones. It is used in both industrial and architectural coatings, in lacquers, alkyds, enamels and emulsion paints. It is sometimes blended with organic reds, as an alternative to lead-containing inorganic red colorants. Naphthol reds are notable for their excellent chemical resistance and good durability, but are generally limited by bleeding and poor lightfastness, with the exception of PR-170. They were formerly used to some extent in automotive lacquer finishes (which have been largely eliminated), but have been replaced in this market by more durable organic reds such as the quinacridones and perylenes. Currently they are applied in interior emulsion and masonry paints. Because of its high opacity and good fastness properties, PR-170 is increasingly used in full-shade applications to replace lead chrome pigments. Toluidine reds are available in a range of semiopaque bright red shades. They are lightfast for exterior use, but only in full strength, so they find use in trim paints and farm machinery coatings. In tints they can be used for interior architectural coatings. They show good alkali resistance in aqueous paint systems, but their bleeding tendencies eliminate them from use in solvent-based paints. Quinacridone pigments have premium qualities for the paints and coatings industry, combining excellent aesthetic properties with a high degree of durability and lightfastness. Their high cost is offset somewhat by their high tinting strength, which allows lower pigment loadings to achieve the same deep shades as with other pigments. They are compatible with all paint formulations and so find wide application, especially in automotive finishes and in high-quality enamels. Their use has grown as replacements for heavy metal pigments in coatings, particularly in automotive OEM paints and in coil coating applications. Perylenes compete by color with quinacridones in some automotive and other high-performance applications. DPP pigments are growing in their range of applications and also compete for market share with quinacridones. Quinacridone supply in the United States expanded in 2000 when Ciba completed construction of a new quinacridone pigment plant at Newport, Delaware. This quinacridone plant shares the site of Cibas Diketo Pyrrolo pigment plant, which opened in 1997. Perylenes generally have similar premium qualities to quinacridones and can be used where greater light fastness is required (higher UV tolerance). Perylenes compete on price with some quinacridones in several 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. They are typically used in auto metallic finishes. Perylenes are used to a lesser extent in high-quality industrial and architectural coatings. They provide a wide latitude to the coatings formulator and are currently in tight supply. Perylenes have excellent chemical stability, high resistance to bleeding in most solvents and excellent lightfastness. Transparent grades, such as PR-179, are used in conjunction with metallic flake in coatings, whereas opaque versions like PR-178 are used in highly durable solid colors with bright red
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shades. Perylenes and quinacridones are sometimes combined in high-performance coatings applications. High-performance 1,4-diketo-pyrrolo-pyrroles (DPP) pigments compete in several perylene markets. Quinophthalone yellows, such as PY-138, have a clean greenish-yellow shade. They are formulated into high-quality coatings as a replacement for chrome yellow, because of their high opacity, good weatherfastness and favorable rheology. Isoindoline pigments, such as PY-139, are used in lead- and cadmium-free coatings because of their high weatherfastness, good rheological properties and high opacity. Their hues cover the color range from reddish yellow to deep orange (PO-69 and PR-260). These pigments are typically found on school buses and heavy duty trucks and mobile equipment fleets. Consumption of these pigments will be affected by slowing capital spending. Tetrachloroisoindolinones are premium pigments, valued in paint formulations for their transparency and outstanding fastness. They are used in metallic and solid-shade automotive finishes, as well as industrial and architectural paints. Dioxazine (carbazole) violet, like the quinacridones, possesses high tinting strength and excellent heat and bleed resistance. These attributes compensate for its high price. It is commonly used in blends with blue or white pigments. Along with demand for reds, blues and greens, 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. U.S. phthalo blue and green demand is increasingly satisfied by competitively priced imports from China and India. Durability is always the most important consideration for coating suppliers to the automotive industry. The pigment industry is investing in research to find more durable pigments. New developments include a novel class of heterocyclic pigments called 1,4-diketo-pyrrolo-pyrroles (DPPs), PR-254 and PR-255, which are being imported by Ciba from Switzerland. 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, cleanness and opacity are needed. The consumption of organic color pigment blends in traffic paints has become the norm in over half of the states of the United States, representing over 75% of the U.S. highway miles. The organic yellow pigments PY-75 and PY-65 are used in this market, replacing lead chromate yellow pigments. The publics desire to decrease exposure to lead in paints underlies the increase in organic pigment consumption. Fifteen years ago, total U.S. organic pigment consumption in traffic paints was only a few metric tons, whereas in 1999, organic pigment consumption in this market was over 2.3 thousand metric tons. The market share of organic yellows in the traffic paints market segment will continue to grow at the expense of lead chromates. Growth in the consumption volume of organic color pigments in surface coatings for 1999-2004 is expected to be about 2.0% per year, with industrial paints increasing at an average annual rate of 1.52.0% and traffic paints at more than 5%. Among water-based paints, consumption is expected to increase by an average annual rate of 3-4%, while consumption of solvent-based paints should continue to decrease by an average annual rate of 2%. 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. New organics and
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inorganics continue to be developed to replace lead and cadmium pigments in surface coatings because of environmental and health concerns. However, most organic replacements do not have the same opacity, lightfastness and heat stability of the inorganics, limiting their utility in paints and coatings.
Plastics, pigmented fibers and rubber An estimated 14% of total U.S. organic color pigment consumption goes into these markets, mainly for plastics and to a minor extent in rubber markets. Organic pigments, because of their generally poor heat resistance, find only limited use in these industries. However, 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. Among them are disazo condensation and diarylide yellows, phthalocyanine blues and greens, permanent red 2B, quinacridones, perylenes and tetrachloroisoindolinones. Phthalocyanine pigments, most of which are copper-based, can be used in many plastic and rubber products because of their satisfactory performance properties in both types of materials. In plastics, phthalocyanines tend to be difficult to disperse, so they are sold in predispersed forms. Phthalo pigments are preferred for their bright, clean, transparent shades, good lightfastness and excellent tint strength. Metallized azos typically used in plastics include permanent red 2B (PR-48:1 and PR-48:2), lake red C (PR-53:1) and pigment scarlet (PR-60:1). In particular, the calcium and barium salts of permanent red 2B have found wide acceptance in plastics because of their low cost, good color strength and bleed resistance and acceptable heat stability. Benzimidazolones have excellent heat stability for use in engineering thermoplastics, such as polycarbonate and ABS. In addition, benzimidazolones have good bleed and chemical resistance, with fair to good lightfastness. Polyazo organic pigments, such as disazos, have better resistance to heat, bleeding and chemicals than the monoazos. Polyazos are particularly useful for elastomeric and thermosetting systems, where strong curing and oxidizing agents are often used. Examples of typical polyazos used in plastics are disazo condensation pigments in yellows and reds and diarylide yellow and orange. Quinacridones, available in orange, red and violet, are useful in plastics because of their excellent color, durability, lightfastness, tint strength and bleed resistance, but they are very costly. They can be used in most plastics, except nylons and have limited application in polystyrenes and acrylics at low temperatures. Quinacridones are also used in blends with inorganic molybdate orange pigments to produce different reds with good lightfastness at a lower cost. The plastics industry is increasingly using quinacridones and solvent dyestuffs as replacements for the less expensive cadmium- and lead-containing inorganic pigments, particularly in response to environmental regulations concerning postconsumer waste, such as Coalition of Northeastern Governors (CONEG) legislation (see the U.S. Environmental and Health Regulations Affecting Pigments table). 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, such as ABS. Perylenes are widely used in plastics, especially vinyl, polypropylene and cellulosic plastics, as well as in pigmented synthetic fibers. Their superior chemical and bake resistance makes them suitable for most polymer systems.
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Tetrachloroisoindolinones, in yellow, orange and red, are resistant to the high processing temperatures used in plastics manufacture and are also nonbleeding and nonmigratory in most polymer formulations. However, their high cost has limited their use to specialty plastics, such as those in automotive applications. They are used in thermoplastics, including ABS and polypropylene; in thermosetting plastics, especially gel coats; in synthetic fibers and monofilaments; and in vinyl plastisols. A new addition for the plastics industry is the the family of pigments known as chromophtal diketopyrrolo-pyrrole (DPP). Recently launched by Ciba in commercial volumes, these pigments are heat-stable to 272-288C and can be used in polyolefins, PVC, PS and ABS. Chromophtal DPP pigments are available in red shades varying from a very yellow red to a mid-red shade. New trends developing in the plastics coloration market include granite or speckle colorants; pearlescents, sparkle or glitter pigments; marbles; and neon or edge glow types. Organic color pigments used in a variety of plastics are summarized in the following table:
U.S. 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
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U.S. 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 Thermosets
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
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U.S. 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. X X X X X X X X Phenolic Unsaturated Polyester Polyurethane Silicone
X X
Only recommended applications for each pigment type are indicated; limited applications are not indicated. (A) Colorants, Plastics Compounding 1988/1989 Redbook, pp. 51 and 52. (B) CEH estimates.
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. Typical products include detergent bottles and toys. Approximately 40% of the total fluorescent organic pigment market is plastics. The average annual rate of growth in the volume of organic pigments consumed in the plastics industry is expected to be about 3.5% for 1999-2004. Growth in volume for organic pigments by major market is shown in the following table:
Average Annual Growth Rates for U.S. Consumption of Organic Color Pigments in Plastics1999-2004 (percent) Automotive Commerciala Packaging Building and Construction a. Includes products for both household and business uses. CEH estimates. 4 3.5 4 2
SOURCE:
No growth is foreseen for consumption of organic colorants in the rubber industry. The continued replacement of heavy metal pigments by high-performance organic pigments, 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. The total 1999 domestic market for organic color pigments in pigmented fibers was as high as 2.0 thousand metric tons, dry weight basis. Growth in this market is expected to be about 3.5% per year from 1999 to 2004. The major fibers involved are nylon and polypropylene, mainly for carpeting and interior automotive upholstery. In pigmented fiber, the pigment is distributed throughout the fiber, rather than being printed or dispersed onto the fiber or textile surface, as is the practice in traditional textile dyeing and printing (see the section on Other for further information on textile printing).
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The largest of the ten or so U.S. producers/importers of organic pigments for pigmented fibers, on a value basis, include Ciba, with roughly 60% of the total U.S. supply; Magruder Color; and Sun Chemical. Cibas imported line consists largely of disazo red and yellow chromophthals.
Other Other markets that consume small quantities of organic color pigments include paper, textiles, artists colors, childrens crayons, watercolors and markers, and food, drugs and cosmetics. Paper consumes an estimated 1.5 thousand metric tons per year and textiles consume roughly 1.6 thousand metric tons per year. The other markets account for smaller quantities. Domestic growth of organic colorants by volume in these combined markets for 1999-2004 is expected to be 2.0%. One possible growth area is in the drug and cosmetic colorants market. However, this area consumes a very low volume of organic color pigments and thus would not significantly influence total consumption. In terms of sales value, Bayer is the largest supplier of organic pigments to the U.S. paper industry, followed by BASF and Ciba Specialty. In the paper industry, water-insoluble organic pigments are used as aqueous dispersions, providing high brightness, high lightfastness and bleed resistance, but with poor fiber affinity. Organic pigments used in colored paper are primarily for coatings, matte board and laminated base paper for countertops. Total 1999 U.S. consumption of organic pigments in paper is valued at about $20 million. Organic pigments for textile printing are mainly naphthol red, diarylide yellow, phthalocyanine blue and green, carbazole violet and quinacridone. (Textile printing is considered as a separate market from pigmented fibers, which is covered in the section on Plastics, pigmented fibers and rubber.) Individual pigments typically used include PB-15, 15:1, 15:2, 15:3 and 15:4; PG-7 and 36; PO-13, 14 and 16; PR-23 and 170; PV-19 and 23; and PY-13, 14, 17 and 83. One of the most significant individual pigments is carbazole violet (PV-23), which is consumed in large amounts in textile printing. The most important naphthols used in textile printing do not have assigned Colour Index names, but are also consumed in sizable quantities. Fastness to dry cleaning is the single most important factor in determining which organic pigments are suitable. Textile pigments may be applied as color-concentrate chips, which are solids containing organic pigment held in a vehicle, such as a water-soluble acrylic resin. Other pigment forms include dry pigment and presscakes. Major organic pigment suppliers to the textile industry include Bayer, Clarient Galaxie Chemical, HiltonDavis, Magruder Color, European Colour and Sun Chemical. The use of fluorescent organic pigments is growing rapidly in textile/apparel printing (a category that includes silk screens), which is about a $20 million domestic market in pigment sales value. Textile/apparel printing accounts for approximately 40% of the total domestic market value for fluorescent organic pigments. The domestic market for organic pigments in cosmetics is worth roughly $15 million. However, because these are mostly laked organic dyes, their reported production is included with dyes. For more information, refer to the CEH marketing research report on Dyes.
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Price The following table provides U.S. reported prices and unit sales values for selected organic color pigments:
U.S. 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. 1997 1998 1999
na na na na na na na 43.70 na 7.56 11.38 na na
18.40 4.82 9.38 15.62 10.55 32.03 32.81 13.52 19.59 5.59 4.86 5.59 4.08
17.28 4.64 9.49 15.11 8.27 31.49 27.34 8.57 19.19 5.26 4.87 5.26 4.66
17.00 4.09 8.99 14.93 8.56 18.32 29.76 14.81 16.72 5.42 4.44 5.42 3.47
Unit sales vales for dispersions. U.S. Imports, U.S. Department of Commerce, Bureau of the Census.
SOURCE:
The price for dry quinacridone violet (PV-19) pigment was in the range of $20-$30 per pound in 1999, while dry dioxane violet (PV-23) pigment was at about $30 per pound in 1999. Flush colors, dispersions and color chips are the most costly forms in which organic pigments are sold, in terms of value per dry pigment weight equivalent, followed by powder and then presscakes; presscakes are usually the least expensive forms. Roughly 65% of the selling price of organic pigments is for raw material costs, namely the cost of pigment intermediates and crude pigments. Some of the raw materials used to produce organic pigments are exclusively foreign-made.
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Trade Historical trade data for U.S. organic color pigments are listed in the following table:
U.S. Trade in Organic Color Pigments Importsa Thousands of Metric Tons, 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. 0.15 1.64 2.41 2.32 4.04 4.06 5.53 8.61 8.75 9.28 11.40 10.42 16.39 21.26 21.84 21.42 16.64 8.26 9.07 9.44 10.48 11.62 13.07 Millions of Dollars 0.8 10.6 18.4 36.4 49.7 45.5 62.4 88.1 90.3 106.2 92.4 143.7 177.1 207.8 244.2 274.0 259.2 123.8 165.2 171.6 184.4 185.4 197.9 Exportsb Thousands of Metric Tons, Dry Weight 1.90 3.81 5.50 9.10 7.69 6.69 8.48 7.86 7.09 8.20 11.21 13.21 16.78 20.00 21.06 25.78 na 12.93 13.29 11.60 12.3 15.4 17.7 Millions of Dollars 8.0 14.3 25.1 79.5 80.4 75.8 77.5 79.9 74.0 87.5 120.4 144.7 178.5 213.8 201.1 245.4 na 263.7 235.0 287.0 278.5 309.5 328.0
Until 1977, data were reported in the sources as Color Lakes and Toners Made from Alizarin and Indigo. From 1978 to 1980, data were reported as Color Lakes and Toners of various specified colors. After 1980, data were no longer broken down by colors or chemical types. Dry weight data for 1989 through 1992 may not be comparable to other years, as it may be overstated 25% to 40%. Reported data for concentrated dispersions from 1980 to 1988 and 1994-1999 are estimated to contain approximately 40% dry pigment by weight; this factor was used to obtain the data on a dry weight basis. Dry weight data for 1989 through 1992 may not be comparable to other years, as it may be overstated 25% to 40%. (A) U.S. Imports, U.S. Department of Commerce, Bureau of the Census (data for IMPORTS). (B) CEH estimates based on U.S. Exports, U.S. Department of Commerce, Bureau of the Census (data for EXPORTS).
b.
SOURCES:
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Imports Reported imports of organic color pigments by major country of origin in 1999 were as follows:
U.S. Imports of Organic Color Pigments1999 Country of Origin China Germany India Other Total SOURCE: Quantity (thousands of metric tons, dry weight) 3.7 2.4 1.3 5.7 13.1 Market Share (percent) 28 18 10 44 100%
In 1999, the single largest source of color pigment imports was China with a 28% market share, an increase of over 50% from its market share in 1996. China has become the leading source of blue (PB15:3), green (PG-7, PG-36) and red pigments (PR-57:1). The second-largest source of imports was Germany with 18% of imports. A large portion of the imports from Germany is exported by BASF and Clariant (formerly Hoechst); some is imported by Ciba Specialty for its U.S. subsidiaries. India has emerged as the third-largest U.S. source for organic color pigments, with a concentration in phthalocyanine pigments, particularly green (PG-7). As recently as 1992, Japan, was the largest source of color pigment imports with a 25% market share, but in 1999 its market share fell to only 7%. Together, BASF, Bayer, Ciba, Hoechst Celanese and Sun Chemical may hold as much as 55% of the total U.S. imports value.
Exports Exports by major country of destination in 1999 were distributed as follows:

U.S. Exports of Organic Color Pigments1999 Country of Destination Belgium Canada United Kingdom Other Total SOURCE: Quantity (thousands of metric tons, dry weight) 5.4 3.8 3.0 5.5 17.7 Market Share (percent) 31 21 17 31 100%
CEH estimates based on U.S. Exports, U.S. Department of Commerce, Bureau of the Census.
In terms of export value, Sun Chemical is the largest U.S. exporter of organic pigments, followed by Bayer and Ciba.
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CANADA Producing Companies Dominion Colour Corporaton is Canadas sole producer of orange, red and yellow organic pigments; the largest-volume organic color pigments produced at its Ajax, Ontario plant include Diarylide Yellow PY-12, PY-13, PY-14 Lithol Rubine, 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, as is basis) 1997 1998 1999 SOURCE: 12.6 11.9 12.7 Statistics Canada. Value (millions of Canadian dollars) 152.6 151.8 163.9
The majority of Canadas organic pigment imports come from the United States. Canadas organic pigment export data are listed below.
Canadian Exports of Organic Color Pigments Quantity (thousands of metric tons, as is basis) 1997 1998 1999 SOURCE: 3.8 3.3 3.7 Statistics Canada. Value (millions of Canadian dollars) 30.9 31.6 31.7
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MEXICO Producing Companies The following table lists the production of organic pigments by Mexicos two producers:
Mexican Producers of Major Organic Color PigmentsMarch 2001 Phthalocyanine Blue (PB-15) Phthalocyanine Green (PG-7) Permanent Red 2B, 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 Mxico, S.A. de C.V. Lerma, Edo. de Mxicoa Clariant (Mxico), S.A. de C.V. Santa Clara, Edo. de Mxicob Ftalmex, S.A. de C.V. Monterrey, Nuevo Len Pyosa, S.A. de C.V. Monterrey, Nuevo Lenc a.
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, 3, 65 PB 15:3, 15:4 PR 48:1, 48:2, 49:1, 53:1, 57:1 and 112 PR 81 PV 1 PG 8 PV 3
b.
Clariant also produces the following organic pigments in Mexico: Alkali Blue Pyrazolone Orange Pyrazolone Red PB 56 PO 13 PR 38
c.
Pyosa also produces the following organic pigments in Mexico: Monoazo Red Monoazo Yellow PR 3, 48, 49, 53 PY 1, 3, 14, 17, 83
SOURCE:
CEH estimates.
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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: 1.55 2.06 1.71 na 4.43 4.58 5.02 (A) Sistema de Informacin, Comercial de Mxico, Banco Nacional de Comercio (1993-1995). (B) Secretary of Economy, Mexico (1997-1999).
In 1999, 56% of Mexicos organic pigment imports originated in the United States. 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: 0.18 0.24 0.34 na 0.73 0.88 1.55 (A) Sistema de Informacin, Comercial de Mxico, Banco Nacional de Comercio. (1993-1995). (B) Secretary of Economy, Mexico (1997-1999).
Mexicos organic pigment exports have risen eightfold since 1993. In 1999, 56% of Mexicos organic pigment exports went to the United States while the next-largest destination was Germany, at nearly 17%, reflecting a shift of some of Bayers pigment production to Mexico.
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SOUTH AMERICA The following table lists the producers of organic pigments in South America:
South American Producers of Organic Color PigmentsMarch 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.A. Mathew-Pdo. de Pilar, Buenos Aires Oscar Carlos Rapp e Hijos S.R.L. Pilar, Buenos Aires Brazil Brancotex Indstrias Qumicas Ltda. Barueri, So Paulo Cleomar Qumica Indstria e Comrcio Ltda. Indaiatuba, So Paulo Venezuela C. A. Venezolana de Pigmentosa Valencia, Carabobo a.
Venezolana produces an additional number of azo red and yellow pigments. CEH estimates.
SOURCE:
WESTERN EUROPE In 1999, Western European consumption of organic color pigments was valued at roughly $525 million, a decline from $600 million in 1996. Despite volume growth, the market value has declined during the last three years because of price erosion. Though declining in output, Western Europe remains the leading region for organic pigments production. In 1999, Western Europe accounted for about 29% of the total world organic pigments production in volume terms and for at least 36% in value terms. 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- to medium-tier pigments. In addition, Western European producers will, for cost reasons, continue to relocate production of their low- 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). Unlike inorganic pigments, organic pigments are in the hands of only a few producers. The leading Western European suppliers of organic pigments are Clariant, Ciba Specialty Chemicals and BASF. The smaller organic pigment producers are Avencia and Bayer, followed by two foreign producers, Dainippon Ink (Kemisk Vaerk Kge and INTORSA) and Toyo Ink (Francolor Pigments), all internationally operating companies.
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The following table summarizes the Western European supply/demand situation for organic pigments in 1999:
European Union Supply/Demand for Organic Color Pigments1999 (thousands of metric tons, dry weight) Production Imports Exports Consumption SOURCE: CEH estimates. 65.2 39.0 33.0 71.2
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 Pigments2001 Azo Company Avencia BASF Aktiengesellschaft Ciba Specialty Chemicals Clariant European Colour Francolor Pigments Gebroeders Cappelle Intermedios Orgnicos Kemisk Vaerk Kge Socit Languedocienne de Micron-Couleurs Tennants Textile Colours SOURCE: CEH estimates. 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, the German company, Heubach, manufactures phthalocyanines and a range of other organic pigments at its subsidary in India.
Azo pigments The following table shows Western European producers of azo pigments, along with capacities and types of pigments produced:
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Western European Producers of Azo Pigments2001 Red Yellow Company and Plant Location Belgium Gebroeders Cappelle nv Menen Denmark Sun Chemical A/S Kge France Francolor Pigments SA (owned 100% by Toyo Ink Mfg. Co., Ltd., Japan) Rieux Germany BASF Aktiengesellschaft Ludwigshafen Stuttgart-Besingheim Clariant GmbH Frankfurt am Main Italy BASF Italia Spa Cesano Maderno Spain Intermedios Orgnicos, SAINTORSA (owned 92.5% by Dainichiseika Color & Chemicals Mfg. Co., Ltd. [Japan]) Montcada i Reixac Switzerland Ciba Specialty Chemicals Inc. Schweizerhalle Monoazo Disazo Naphthol AS Pigments Red Lakes Other
X X
X X
Metal complex
Benzimidazolones
Red disazo pigments- Cromophthal
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Western European Producers of Azo Pigments2001 (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
Classical a 20 pigments (Eljon, Corfast and Cortone)
SOURCE:
CEH estimates.
Phthalocyanine pigments Western European producers of phthalocyanine pigments and the pigments they produce are shown in the following table:
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Western European Producers of Phthalocyanine Pigments2001 Pigment Blue Company and Plant Location Belgium Gebroeders Cappelle nv Menen Denmark Kemisk Vaerk Kge A/S Kge France Cappelle Frres, SARL Halluin Francolor Pigments SA (owned 100% by Toyo Ink Mfg. Co., Ltd. [Japan]) Villers-Saint-Paul Socit Languedociene de Micron-Couleurs SASLMC (owned 100% by Total) Narbonne Germany BASF Aktiengesellschaft Fine Chemicals Department Kln 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
Isophthal
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Helioecht
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BASF Italia Spa Cesano Maderno
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Western European Producers of Phthalocyanine Pigments2001 (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.
Irgalith
Previously owned by Zeneca Limited (United Kingdom). CEH estimates.
SOURCE:
May 2001 575.0008 B
Monastral; PG-7 is main pigment
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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.A. Huningue Germany BASF Aktiengesellschaft Ludwigshafenb Ciba Spezialittenchemie Grenzach GmbH Grenzach-Wyhlenc Clariant GmbH Frankfurt am Main Spain Intermedios Orgnicos, SA INTORSA (owned 92.5% by Dainichiseika Color & Chemicals Mfg. Co., Ltd. [Japan]) Montcada i Reixac Switzerland Ciba Specialty Chemicals Inc. Montheyd United Kingdom European Colour PLC London a. b. c. d. Blue and violet.
Anthraquinonoide
Dioxazine
Perinone/ Perylene
Quinacridone
Thioindigo
Triphenylmethane
Xa
Also produces quinophthalone at this location. Also produces specialty grades of diketo-pyrrolo-pyrrol-(DPP) at this location. Also produces standard grades of diketo-pyrrolo-pyrrol-(DPP) and isoindolinone yellow at this location. CEH estimates.
SOURCE:
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Production The following tables summarize 1999 Western European production of organic pigments by type and color.
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Western European Production of Organic Color Pigments by Type and Color1999a (thousands of metric tons, 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. b.
Orange
Red
Violet
Blue
Green
Major Pigments Produced
0.3
0.1
neg
--
--
--
neg
0.4
PO-61, 69; PR-260
0.1 ------0.1 --0.2 15.0
neg --neg --neg ---0.2 2.9
0.4 0.5 -0.3 --0.2 -0.3 0.5 0.5 21.6
0.1 -0.4 neg --0.4 --0.7 na 1.9
0.3 ---13.7 ----3.9 0.3 18.2
-----4.5 ---0.1 0.1 4.7
---neg ------0.5 0.9
0.9 0.5 0.4 0.3 13.7 4.5 0.6 0.1 0.3 5.2 1.8 65.2
PY-24, 108, 147; PO-51; PR-83, 168, 177; PV-5:1; PB-60 PR-254, 255 PV-23, 37 PO-43; PR-149, 224 PB-15:1, 15:3, 15:4 PG-7, 36 PV-19; PR-122, 209 PY-138 PR-181 PR-81; PV-3; PB-19 PBk-1; other
Color definition according to the Colour Index. Anthraquinone, anthanthrone, anthrapyrimidine, flavanthrone, indanthrone, isoviolanthrone and pyranthrone pigments. CEH estimates.
May 2001 575.0008 E
SOURCE:
4.0 9.0 ---0.6 0.4 0.3
0.1 0.5 0.5 0.3 0.4 0.6 0.1 0.1
-0.5 1.0 4 12.0 0.6 0.8 neg
---0.2 -0.1 ---
---neg -----
-------neg
---neg 0.1 0.1 0.2 --
4.1 10.0 1.5 4.5 12.5 2.0 1.5 0.4
PY-1, 65, 74, 111, 168 PY-12, 13, 14, 83; PO-16 PO-5; PR-1, 3, 4 PO-22, 38; PR-2, 22, 23, 31 PY-17, 46; PR-48:1, 48:2, 49:1, 49:2, 52:1, 53:1, 57:1 PY-180; PO-36; PR-185 PY-128; PR-144, 166, 242 PY-150; PO-59, 68; PR-257
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Western European production of phthalocyanine pigments fell with significant import competition, primarily from China followed by India. Most Western European producers have tried to develop new, higher value-added grades and forms of phthalocyanine pigments (e.g., granules and highly micronized types) in order to gain a competitive advantage. 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
Consumption It is estimated that Western Europe consumed some 71 thousand metric tons of organic pigments (dry weight basis) in 1999. The following table gives an estimate of Western European consumption by pigment type:
Western European Consumption of Organic Color Pigments by Pigment Type1999 (thousands of metric tons, 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. 46.2
14.6 3.4 3.9 0.6 0.4 0.4 0.2 0.2 0.2 1.1 71.2
The largest market segment is printing inks, which accounted for about 45% of total organic color pigments consumption in volume terms in 1999. The second-largest segment is paints and coatings with about 30% market share. With about 14% of total consumption, the plastics and rubber segment is the third-largest segment. Smaller volumes are consumed in pigmented fibers, textile printing and in paper coloration. In volume terms, it is expected that the printing inks market will be growing fastest during the next five years. In value terms, however, the plastics and rubber segment will be the most promising.
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The following table gives a breakdown of organic pigment applications in Western Europe, together with volume growth projections:
Western European Consumption of Organic Color Pigments (thousands of metric tons, dry weight) Average Annual Growth Rate, 1999-2004 (percent) 3.0 1.2 1.5 1.9 0.8 0 1.5 2.1%
1993 Printing Inks Paints and Coatings Plastics and Rubber Pigmented Fibers Other Textiles Paper Miscellaneous Total SOURCE: 25.6 16.9 7.9 2.5 2.2 0.7 1.1 56.9 CEH estimates.
1996 28.0 18.6 8.9 3.5 2.4 0.7 1.2 63.3
1999 32.0 20.3 10.2 4.1 2.5 0.8 1.3 71.2
2004 37.1 21.5 11.0 4.5 2.6 0.8 1.4 78.9
The following table gives a consumption breakdown by application for phthalocyanine pigments:
Western European Consumption of Phthalocyanine Pigments by Application1999 (thousands of metric tons) Printing Inks Paints and Coatings Plastics and Rubber Textile Printing Pigmented Fibers Other Total SOURCE: CEH estimates. 7.9 3.8 3.5 1.2 0.8 0.8 18.0
Printing inks In Western Europe, printing inks are the largest application for organic pigments in volume terms. It is estimated that printing inks contain about 15-20% pigments, the rest being resins, solvents and additives. In 1999, the average organic pigment content in printing ink formulations was about 19%. The types of pigments consumed are mostly low-cost pigments, but also include high-performance pigments. In Western Europe, the production of printing inks has significantly increased over the last decade. The following table lists production since 1984:
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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 1,058 CEH estimates based on data from CEPE, European Confederation of Paint, Printing Inks and Artists Colour Manufacturers Associations.
The future of the Western European printing ink industry is promising, especially when considering the rapidly increasing export potential to Eastern Europe and Asia. This, coupled with the growing trend toward more color printing in journals and newspapers will generally cause growth in organic pigments consumption. However, the cyclicity of advertising spending will amplify growth above or below GDP, depending on the growth or shrinkage of advertising budgets. Overall growth is expected to continue for the next five to ten years, leading to strong consumption growth averaging 4% per year. Four organic color pigment producers, have captive demand for printing inks: BASF Aktiengesellschaft Kemisk Vaerk Kge (through Sun Chemical/Danippon Ink and Chemicals) Intermedios OrgnicosINTORSA (through Dainichiseika Color & Chemicals) Francolor Pigments SA (through Toyo Ink) In spite of the increasing competition and globalization of the printing industry, the number of printing ink producers has remained relatively constant. Also the trend toward downstream integration by pigment producers has come to a halt, as the larger companies began to concentrate more on their core business activities. Further changes in the printing ink industry have affected pigment production. Ink producers are gradually switching to flushed pigments from dry pigments, as flushed pigments are easier to handle, resulting in lower ink production costs. The fast expansion of the water-based flexographic ink market for packaging applications in Western Europe also affects the types of pigments used. These inks demand that the pigments have special granular characteristics and surface properties to enhance dispersability and compatibility. The development of such pigments is ongoing.
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Color organic pigments, in general, have a greater choice of brilliant colors than inorganic pigments. Yellows consist mainly of diarylide yellows and yellow lakes; Hansa yellow is used to some extent when extreme lightfastness is required. In order to avoid the use of lead compounds, these organic pigments are being used more and more as replacements for the inorganic chrome yellows. Reds consist of the Lithol reds, para reds, toluidines, rhodamine reds, lake red C and also eosine lakes. Blues consist of peacock blue (PB-24), phthalocyanine blues, Victoria blue and alkali blues. A wide range of other color pigments are also available for use in printing inks.
Paints and coatings Western Europe is the worlds leading region for paints and coatings production, accounting for about 25% of total world production. Although the bulk of pigments used are inorganic, the use of organic pigments is substantial and increasing. Since 1985, the consumption of organic pigments in paints and coatings has been higher than the growth rate of paints and coatings production, because of substitution of inorganic pigments such as lead chromate and cadmium. It is expected that this substitution trend is maturing. By far the largest organic pigmentconsuming country for paints and coatings is Germany, accounting for almost 30% of total Western European consumption.
Plastics and rubber The third-largest application of organic pigments in volume terms is for plastics and rubber. Organic pigments are used in practically all types of plastics and rubber. The primary plastics pigmented are PVC, polyolefins, polystyrene, acrylics, nylon, polycarbonate and polyester, as well as cellulosics. The use of organic pigments has grown more or less in line with total plastics consumption. As in other applications, the demand for organic pigments has benefited from substitution of toxic inorganic pigments. New inorganic pigments, such as bismuth vanadate and rare earth sulfides, are, however, increasingly used and may limit the penetration of organic pigments. As in to the printing ink industry, a concentration of the plastic masterbatch producers is in progress. In addition, organic pigments producers are tending toward downstream integration into polyolefin color concentrate (masterbatch) production.
Pigmented fibers Basically three different methods give color to fibers and textiles: dyeing (with dyestuffs), printing (with either dyestuffs or pigments) and spin dyeing (primarily with pigments but also dyestuffs, i.e., solvent dyes). Polyolefin fibers are difficult to color with the currently available textile dyestuffs, so most polyolefin fibers are pigmented. There are only a few exceptions where dyestuffs can be used in coloring polyolefin fibers , such as dyeable nickel-modified polypropylene fibers.
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Spin dyeing has certain advantages over the conventional dyeing technique. One of the major advantages is the availability of pigments with significantly superior light- and weatherfastness, which in most cases cannot be matched with conventional textile dyestuffs. A further advantage is the fact that in spin dyeing the color is added to the polymer prior to extrusion without creating wastewater. In the wet and dry spinning process, solvents are used that can be recovered with virtually no loss. During the last few years, spin dyeing of chemical fibers has become more popular, primarily because of technological advances in producing esthetic, low-priced polypropylene fiber carpets and rugs. In particular, the use of pigments for spin-dyed polyolefin fiberbased carpets and rugs has grown significantly, by more than 10% per year between the mid-1980s and mid-1990s. Organic pigments are used in practically all chemical fibers, but it is estimated that polypropylene fibers account for about 70% of all spin-dyed fibers produced in Western Europe. The next most-important fibers that are spin dyed are, in decreasing order, acrylic, polyester, polyamide and polyethylene fibers. Shown in the table below are the type of synthetic fibers that are pigmented, together with an estimate of color pigments consumed.
Western European Consumption of Spin-Dyed Synthetic Fibers and Color Pigments1999 (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. Through conventional textile dyeing processes. CEH estimates.
20.2
0.7 0.6 0.2 0.1 na 21.8 17.7 4.1
SOURCE:
Probably one of the most widely used organic pigments in spin dyeing is phthalocyanine green, required for the manufacture of outdoor grass-type carpets. From an environmental point of view, the spin-dyeing technique has considerable advantages over the conventional dyeing technique. However, spin dyeing is only possible for chemical fibers and only for a limited number of final fiber applications. Hence, pigments will not be used extensively as dye substitutes given the current product range. There is, however, a certain substitution possibility in textile printing. For further information, see the Textile printing section. 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, such as polyolefin fibers) and dispersibility of the
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pigment. The cost for suitable pigments is generally higher than that for dyestuffs. In addition, the required unit consumption per ton of fiber spin dyed is about 1.5 times higher than when dyeing with textile dyestuffs. Hence, from the cost point of view, inorganic pigments have considerable advantages over organic pigments in this particular application.
Textile printing Although textile dyestuffs are by far the largest type of colorants used to color textiles, the use of pigments in textile printing has increased. The textile printing boom in the last twenty years has been characterized by increased productivity, improved quality and the introduction of environmentally friendlier printing processes. It is estimated that in 1999, Western Europe consumed about 1.2 thousand metric tons of organic color pigments for textile printing.
Pigments for paper In Western Europe, organic pigments are used by the paper industry in the form of aqueous dispersions. They provide improved high brightness, high lightfastness and bleed resistance, but have poor fiber affinity. They are used primarily for coatings, matted boards and laminated base paper for countertops. 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 Paper1999 Trade Name Aveinca Monastral Monolite Pigmosol Basoflex Levanyl Heliocet Irgalith Flexonyl Hydroplast CEH estimates.
BASF
Bayer
Ciba Clariant SOURCE:
Other Organic pigments are used in a number of smaller applications. Some uses include coloring wood, office products, accessories, artist colors and drawing materials and cosmetics (including soaps). Although the volumes consumed in these applications are small, the value of some of these specialty markets is appreciable. A relatively new application of pigments is in the manufacture of digital printing and ink jets. Although color ink jets are manufactured primarily with dyestuffs, efforts have also been made to use
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pigments. The use of pigments in this application provides the advantage of increased light- and waterfastness. The main disadvantage is that pigments are solid and tend to clog up the jet orifices.
Price Historically, prices for organic pigments have differed substantially from country to country, but prices are becoming homogeneous throughout the region because of the growing awareness of international price levels. For commodity-type azo pigments prices have decreased substantially since 1992, with price declines accelerating from 1997 to 1999. Particularly for the large-volume products, such as PY-13 and PR-57:1, prices declined up to 20% during 1992-1996. One of the main reasons for this general price decline is the global overcapacity and the increasing supply from low-cost producers in Asia. All of the large, global producers source increasing volumes of commodity-type pigments from their overseas subsidiaries. The average Western European import value for organic colored pigments and preparations was (8.21 euros per kilogram in 1999, versus (10.06 euros per kilogram in 1997. During this same period Western European organic pigment imports rose by over 25%.
Imports In 1999, the European Union imported 63 thousand metric tons of organic pigments and pigment preparations on an as-is basis. It is estimated that this volume, calculated on a dry pigment weight basis, was about 39 thousand metric tons. In spite of the uncertainties about actual dry weight traded, it can be seen from the table below that imports of organic colored pigments into Western Europe have increased nearly eight-fold since 1988. The dominant country of origin was the United States, followed by China, Japan and India. Imports from the United States have increased significantly; however, these volume increases are inflated somewhat because flushed pigments, which are not reported on a dry pigment weight basis, represent a large portion of the increased volume. 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, as is) Country of Origin Brazil China Czech Republic India Japan Korea, Republic of United States Other Total 1988 86 96 59 779 3,620 579 2,262 464 7,945 1992 na 602 243 2,408 6,066 903 7,287 2,385 19,894 1995 718 1,485 665 3,176 5,956 2,933 19,574 1,609 36,116 1999 616 8,278 1,971 5,396 6,222 4,879 28,092 7,216 62,670 Import Trends 1999-2004 Moderately increasing Increasing Increasing Increasing Flat Increasing Moderately increasing Increasing
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a.
Import code # 3204.17.00. Includes pigments and pigment mixtures. Data do not include volumes imported by Finland, Norway and Sweden. NIMEXE, Analytical Tables of Foreign Trade: Products-Countries, Eurostat, Statistical Office of the European Community.
SOURCE:
The availability of low-priced organic pigments with acceptable quality, coupled with the increased competition in the Western European pigment-consuming industries, have been the prime reasons for growing imports from Asian countries. Like the developments in dyestuff imports, commodity-type organic pigments imports from China, India and Korea are expected to increase further. As a result of the increased competition, Western European producers of organic pigments will increasingly concentrate on the most specialized, highest-value-added pigments.
Exports Until the late 1990s, Western Europe was traditionally a net exporter of organic pigments in value and volume. Now it is a net exporter only in value terms. The main exporting countries in terms of value are Germany and Switzerland, followed by France and the United Kingdom. In 1999, Western Europe exported approximately 40 thousand metric tons of organic pigments and pigment preparations, equivalent to about 33 thousand metric tons on a dry pigment weight basis. Overall, exports of organic pigments have increased slightly over the last few years. Although pigments are exported throughout the world, the largest export destination by far is the United States, which in 1999 accounted for nearly 17% of total Western European exports in volume terms. The pigments exported to the United States are primarily those products that are not manufactured by the U.S. subsidiaries of the Western European producers. Many of these products are high-value-added pigments, such as perylenes from BASF (Germany) and diketo-pyrrolo-pyroles from Ciba (Switzerland). 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, as is) 1988 1992 1995 1999 a. Exports to outside Western Europe. Eurostat, Statistical Office of the European Community. 33.5 30.9 26.8 39.5
SOURCE:
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EASTERN EUROPE Producing Companies Major producers of organic pigments are listed in the following table:
Central and Eastern European Producers of Organic Colored Pigments2001 Company and Plant Location Czech Republic Spolek pro Chemickou a Hutn Vyrobu, a.s. st nad Labem Synthesia a.s. Pardubice Pigments Produced
Azo pigments.
Azo pigments. Phthalocyanine pigments. Capacity will be expanded to 1.2-1.5 thousand metric tons per year.
Hungary Nicolor Rt. (joint venture between Dainichiseika Color & Chemicals [Japan] and Nitrokmia Rt.) Fzfgyartelep Poland Wolskie Zaklady Przemyslu Barwnikow Organika Wola Krzyszoporska
Phthalocyanine pigments.
Formerly about 95% of the Polish organic pigments production was produced by Organika. However, in 1991, azo- and phthalocyanine pigments production was terminated.
Romania Colorom Codlea Russia Koloros AO Moscow Krata, AO Pigment (shareholding company) Tambov Sawolshski Chimsawod Sawolshsk Ukraine Krasitel Rubezhanskoe SOURCE: CEH estimates.
Azo pigments.
Various organic pigments.
Azo pigments.
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Production Hungary, followed by the Czech Republic are the main organic pigmentsproducing countries in the region. One of the newer joint ventures, in Hungary, Nicolor, manufactures phthalocyanine pigments. The plant is reportedly running at high operating rates, with the output destined primarily for export to Japan. Organic pigment production in Romania, Russia and the Ukraine has declined significantly.
Czech Republic VCHZ Synthesia Pardubice is the main organic pigments producer in the Czech-Slovak region. Spolek at Usti nad Labem is producing a few organic pigments but total production is small.
Hungary Hungarys production of pigments was limited to a range of inorganic pigments until the start-up of Nicolor, a joint venture of Nitrokmia and Dainichiseika (Japan), in the 1990s. The majority of the phthalocyanine pigments produced are exported by Dainichiseika to Japan.
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. Production of organic pigments started in the 1950s and peaked in 1985. The following table presents historical production data for organic pigments:
Former USSR Production of Organic Colored Pigmentsa (thousands of metric tons, dry weight basis) 1965 1970 1975 1980 1985 1986 1987 1993 1996 a. 3.4 5.4 7.4 9.0 10.8 10.4 10.6 7.0 1.0
Data after 1991 are for the CIS countries only, which include Armenia, Azerbaijan, Belarus, Georgia, Kazakhstan, Kyrgyzstan, Moldavia, Russia, Tajikistan, Turkmenistan, Ukraine and Uzbekistan. CEH estimates.
SOURCE:
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J APAN Producing Companies The major producers of organic colored pigments are listed in the following table:
Major Japanese Producers of Selected Organic Colored Pigments2000 a
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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., Ltd. Clariant Japan Ltd.b Daido Chemical Industry Co., Ltd. Dainichiseika Color & Chemicals Mfg. Co., Ltd. Dainippon Ink and Chemicals, Inc. Fuji Pigment Co., Ltd. Kikuchi Color & Chemicals Corp. Kiwa Chemical Industry Co., Ltd. Noma Chemical Industry & Co., Ltd. Sansui Color Co., Ltd. Sanyo Color Works, Ltd. Sumika Color Co., Ltd. Tokyo Sikizai Industry Co., Ltd. Toyo Ink Mfg. Co., Ltd.
X X X X X X X X X
Tartrazine, Rhodamine Quinacridone, Anthraquinone Quinacridone, Anthraquinone, Benzimidazolone Anthraquinone
PIGMENTS
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
Dioxazine
Anthraquinone
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a. b.
Most of the companies produce color formulations or inks from the pigments produced. Hoechst Japans (formerly Hoechst Mitsubishi Kasei Co., Ltd.) pigment business was acquired by Clariant (Japan) K.K. on July 1, 1997. CEH estimates based on the Directory of Chemical Producers, SRI Consulting.
SOURCE:
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Dainichiseika, Dainippon Ink and Chemicals (DIC) and Toyo Ink are the top three organic pigment manufacturers in Japan. Those companies have significant quantities of captive consumption to produce downstream products such as inks and colored concentrates. DIC has expanded its share in the automotive basecoat market, having bought out Tosohs quinacridone business unit in 1993. Three major ink producers, DIC, Toyo Ink and Sakata Inx, consume significant quantities of pigments in ink. DIC and Toyo Ink also consume pigments in plastics, color concentrates and can coatings. Dainichiseika consumes more pigments in plastics and color concentrates than in inks. The major two coating companies, Kansai Paint and Nippon Paint, also consume significant quantities of pigments in automobile OEM and other coatings. DIC produces phthalocyanine blue crude and pigments at its Kashima plant. DICs subsidiary, Sun Chemical in the United States and Denmark, also produce organic pigments. DIC has a joint venture in India (29% ownership), Sudarsham Chemicals. 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. Toyo Ink also established a joint venture, Phthalomex in Mexico, with Pyosa in January 1997 to produce phthalocyanine blue and green. This plant was expected to have an annual capacity of 1.85 thousand metric tons by the year 2000. Toyo Ink also has a joint venture, Tianjin Toyo Ink Co., Ltd., in Tianjin, China, with a facility integrated from pigments to printing ink, producing phthalocyanine blue crude. Francolor Pigments S.A. in France is also owned by Toyo Ink and one of its plants at Oissel produces quinacridone pigment. Dainichiseika has a pigment production joint venture, Nicolor Co.,Ltd., in Hungary. DIC, Dainichiseika and Toyo Ink have been importing and exporting pigments, crude, and/or surface treated pigment (treated by resin and dispersants, color chip or master batch) each with affiliated companies from outside Japan. Fuji Color has its strength in red pigments. Kiwa Chemical consumes pigments in fibers and textiles. Sansui Color has a variety of insoluble azo pigments. Kikuchi Color, which is the leading producer of chrome pigments, recently started organic pigments production. Nippon Pigment has reportedly ceased its production of pigments. Concerning imports, Chiba Specialty Chemicals participates in the market by importing specialty pigments, such as diketo-pyrrolo-pyrrole (DPP) and anthraqinone (A2B). 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, such as benzimidazolone, dimethylquinacridone and isoindolinone, from plants in Europe. Bayer and BASF participate in the import market by supplying perylene.
Production Historical data on production of organic colored pigments are shown in the following table:
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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 6.38 7.63 7.87 8.26 8.43 8.34 9.23 9.56 9.84 9.77 10.48 10.08 10.60 11 12 6.55 10.31 5.00 5.38 5.51 5.82 6.71 6.71 6.95 7.29 7.32 7.63 8.07 7.86 8.54 9 10 Insoluble Phthalocyanine 7.25 9.77 12.20 11.73 12.17 12.24 12.46 12.93 12.89 13.14 13.36 13.32 14.12 14.25 14.33 15 16.5 Lakes 0.64 0.91 0.29 0.32 0.79 0.76 0.73 0.64 0.61 0.29 0.31 0.30 0.30 0.26 0.25 0.2 0.3 Othera 0.6 0.52 0.43 0.61 0.75 0.83 0.81 0.80 0.78 0.76 0.72 0.54 0.73 0.62 0.65 0.8 1 Total 15.04 21.51 24.30 25.68 27.10 27.91 29.13 29.41 30.45 31.04 31.55 31.56 33.70 33.07 34.37 36 39.8
Average Annual Growth Rate (percent) 20002005 a.
1.8%
2.1%
1.9%
8.4%
4.6%
2.0%
Includes production of high-performance organic pigments such as quinacridones and imidazolones. (A) Japan Dyestuff & Chemical Industry Association. (B) CEH estimates (estimate for 2005).
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, resulted from a significant increase of offset ink shipments. Although the pigment demand in ink is expected to increase 2.3% annually, as a result of continuing competition with imported products, production of organic colored pigments is expected to increase 2% through the year 2005.
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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, 48:2, 48:3) (Insoluble Azo type) 2.93 1.97 1.61 1990 4.10 2.00 1.74 1992 4.34 1.79 1.74 1996 5.67 1.76 1.86 1999 7.02 1.45 1.74 Major Application Basic magenta color for off-set ink Advertising in newspaper (inexpensive) Basic magenta color for gravure ink, paint, plastic, rubber
Insoluble Azo Type 1987 Disazo Yellow (PY 12,13,14) 3.92 1990 4.56 1992 4.97 1996 5.75 1999 6.78 Major Application Basic yellow color for off-set / gravure ink
Phthalocyanine Type 1987 Phthalocyanine Bluea 9.38 1990 10.02 1992 10.73 1996 11.14 1999 12.38 Major Application Basic blue color for off-set/gravure ink, paint, plastic Green color for off-set/gravure ink, paint, plastic
Phthalocyanine Greena
2.37
2.22
2.06
2.18
1.88
a.
Excludes crude cakes. (A) Japan Dyestuff & Chemical Industry Association. (B) CEH estimates.
SOURCES:
As a result of the continuous increase of ink shipments, production of each organic pigment has shown healthy growth in recent years, excepting Red Lake C and phthalocyanine green. Red Lake C is used for red color ink in advertising (generally local supermarket advertising) in newspapers. But the color quality of the pigment is considered poor, and recently major supermarkets have preferred better color quality in advertising, such as Brilliant Carmine 6B. Although the phthalocyanine green consumption in the domestic market is steady, production has decreased, probably the result of decreased exports.
Consumption Consumption of organic pigments in Japan in selected years is shown in the following table:
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Japanese Consumption of Organic Colored Pigments 1996 Quantity Printing Inks Paints Plastics Textile Dyeing and Printing Othera Totalb a. b. 17.3 4.4 2.8 1.0 0.3 25.8 1998 Quantity 18.2 3.9 2.6 1.0 0.3 26.0 1999 Quantity 19.8 4.2 2.8 1.0 0.3 28.2 Quantity 20.9 4.3 3.0 1.0 0.4 29.7 2000 Percent 70.3 14.6 10 3.4 1.2 100 2005 Quantity 25.0 4.3 3.0 0.7 0.3 33.3
Includes drawing inks, crayons, leather and other uses. Totals may not equal the sums of the columns because of rounding. CEH estimates.
SOURCE:
In general, moderate growth in demand for organic pigments is expected for the following reasons:
q
Consumption in printing inks will grow at around 2.3% per year and this end-use market is expected to be the only driving force for the growth of pigments in Japan. Among the ink shipments, offset ink and gravure ink on film substrate (packaging application) will be the major growth area. Chrome pigments will continue to be replaced by organic colored pigments in plastics and surface coating applications. By 2005, 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. 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. Manufacturers are trying to expand into other applications, including color filter, color toner and other coating applications. State-of-the-art pigment applications, such as bubble jet inks, color toner and color filters for LCDs are currently very small quantitively, but, will grow at a high rate. In these areas, the main competition is with dyes, and the key success of pigments are to make particle sizes smaller and increase transparency. TFT (thin film transistor) displays are the fastest-growing application of color filters for LCD, which has grown drastically in recent years, replacing CRT (cathode ray tube) displays and it is believed that Toyo Ink has a strong share of phthalocyanine blue and green pigments, and Ciba Specialty Chemicals has the biggest share of red pigment (DPP). For ink jet applications, color printer manufacturers recently commercialized pigment type, by replacing dyes, and according to one printer manufacturer, Seiko Epson, the color in printed pigment materials has 200 years of durable light-stability. The disadvantage of pigments in this area is that the pigments may clog inkjet nozzles, however, DIC developed microcapsled pigments, which prevents the clogging.
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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, PY-147 PR-254, PR-255 2005 (Expectation) 200 100-120 60-70 40-60
2000 200 60-70 50-60 30-40
Major Application Auto OEMa, PCMb Color Toner, auto OEM, PCM Auto OEM, color filter, plastic Chrome pigment replacement, auto OEM, color filter Chrome pigment replacement, auto OEM, PCM, benzidine-free pigment Pigment resin color in textile, ink, auto OEM, industrial coating Chrome pigment replacement, auto OEM, PCM, plastic, color toner Auto OEM
Isoindoline/one
PY-139, PO-69, PY-110, PY-173, PO-61
70-80
80-90
Dioxazine
PV-23
40-50
50-60
Benzimidazolone
PY-151, PY-180
120-150
250-300
Perylene a. b.
PR-179
30-40
40-50
Automobile basecoat at original equipment manufacture. Precoated metal, coating is processed on metal first and then processed to fabrication. Coil coating is included in this category in appliances, but PCM also includes industrial coating in larger structures (such as trains, trucks). CEH estimates.
SOURCE:
Among the specialty pigments, quinacridone has a sizable market share. The major end-use market for specialty pigments is for automobile basecoats in OEM. 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). Instead, pigment suppliers are trying to develop markets for quinacridone in other coatings, such as in train cabins and PCM used on vending machines. An increase of some other specialty organic pigments are expected, mainly because of chrome yellow replacement. In the past, most of the quinacridone pigments were imported, primarily from Europe, but now domestic production supplies the majority of demand. Some benzimidazolones, dimethylquinacridones, dioxazines and anthraquinones are produced domestically, but many other specialty pigments continue to be imported from European companies.
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Price
Japanese Unit Values for Selected Inorganic Pigments Yen per Kilogram Azo Lakes 1995 1996 1997 1998 1999 SOURCES: 2,224 2,192 2,191 1,920 1,880 Phthalocyanine 2,160 2,156 2,104 2,027 2,012 Exchange Rate (yen per dollar) 94 108.8 121.0 130.9 113.7
(A) Yearbook of Chemical Industries Statistics, Ministry of International Trade and Industry (data for YEN PER KILOGRAM). (B) International Financial Statistics, International Monetary Fund (data for EXCHANGE RATE).
Market prices of organic pigments have reportedly dropped in recent years, reflecting the lower prices for Chinese and/or Indian imports. Estimated prices for selected organic colored pigments in selected years are shown below.
Japanese Prices for Selected Organic Colored Pigments2000 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
1,400-2,000 1,700-3,000 1,500-2,500 2,500-3,000 6,000-8,000 800-1,000 1,140-1,160
13.0-18.5 15.7-27.8 13.9-23.1 23.1-27.8 55.6-74.1 7.4-9.3 10.6-10.7
a. Data are based on an exchange rate of 108 per dollar. SOURCES: (A) CEH estimates. (B) International Financial Statistics , International Monetary Fund (information in footnote a).
Trade Trade in organic colored pigments since 1981 is shown below.
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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: 1.66 2.45 3.25 3.70 3.22 2.84 3.63 5.14 4.87 5.42 5.66 4.66 Exports 9.05 13.09 16.98 18.40 19.90 19.82 20.92 19.63 19.69 22.48 21.10 18.63 Imports 0.09 0.07 0.11 0.05 0.03 0.02 0.08 0.08 0.11 0.07 0.10 0.09 Lakes Exports 0.47 0.42 0.85 0.86 0.80 0.70 0.71 0.64 0.66 0.42 0.08 0.12
Japan Exports & Imports, Japan Tariff Association.
The figures above include exports of phthalocyanine crude. Also, both phthalocyanine crude and various surface-treated pigments (treated with resin and dispersant) are included in the imports. The estimated pure pigment imports and exports in 1999 are listed below.
Estimated Japanese Trade of Pigments (thousands of metric tons) Import of Pigments by Country of Origin Germany 1999 0.5 Switzerland 0.4 France 0.2 United States 0.1 United Kingdom 0.1 Others neg Total 1.4
Export of Pigments by Destination Country United States 1999 SOURCE: 1.3 CEH estimates. Hong Kong/China 1.2 Taiwan 0.9 France 0.9 Thailand 0.5 Others 2.8 Total 7.6
The other destinations include Malaysia, the Republic of Korea, the United Kingdom, Singapore, the Philippines and Indonesia. There is trading (both imports and exports) of pigments, both crude and surface-treated pigments, between DIC, Dainichiseika and Toyo Ink, each with affiliated companies from outside Japan. Also, specialty pigments are imported by European companies, such as Ciba Specialty Chemicals, Bayer, Clariant and BASF.
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O THER ASIAN COUNTRIES The major producers of organic colored pigments are listed in the following table:
Major Asian Producers of Selected Organic Colored Pigments2000 Insoluble Azo Soluble Azo Lake Red (betaPhthalo naphthol) Blue
Company Korea, Republic of Daihan Swiss Chemical Co., Ltd. Songwon Color Co., Ltd.
Monoazo Permanent Brilliant (nonDisazo Toluidine Naphthol (Watching) Carmine laked) Yellow Red Red Red 6B
Other
Pyrazolone
Pyrazolone, Dioxazine Pyrazolone, Rhodamine
Ukseung Chemical Company Ltd. Taiwan Cosmos Colorants Co., Ltd. Fu Tai Chemical Industry Co., Ltd. Janie Color Works Ltd. Maintop Industrial Co., Ltd. Nan Tsan Industry Co., Ltd. New Hsin Jung Enterprise Co., Ltd. Sigma Pigments Mfg. Co., Ltd. Tah Kong Chemical Ind. Corp. Tong Kung Industrial Corp. Well Chem Products Inc. Yih Chen Chemical Industry Co., Ltd. Indonesia Monokem Surya PT SOURCE:
X X
X X
X X
X X
CEH estimates based on Directory of Chemical Producer, SRI Consulting
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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 2.3 2.8 na Phthalocyaninies 2.3 2.1 na Lakes 0.4 0.3 na Other 2 2 na Production Total 7.0 7.2 15.0 Pigment Apparent Consumption 11.9 10.5 15.0 Import 11.7 11.7 14.4 Export 7.1 8.7 14.8 Trade Lakes Import 0.3 0.3 0.4 Export 0 0 0
Korea, Republic of Production of Organic Pigments in the Republic of Korea Azo 1997 1998 1999 2.6 2.3 1.0 Lake 1.2 1.0 1.4 Phthalo Blue 2.0 1.6 1.6 Phthalo Green 0.2 0.1 0.2 Other 1.4 1.4 2.4 Production Total 7.4 6.4 6.5 Taiwan Production of Organic Pigments in Taiwan Diazo 1997 1998 1999 na 1.4 1.8 Monoazo na 1.8 1.9 Phthalocyanine na 1.4 1.2 Naphthol na 0.1 0.1 Other na 0.5 0.7 Production Total 4.5 5.3 5.7 Apparent Consumption 4.6 4.4 4.3 Pigment Import 2.1 0.5 0.4 Export 1.9 1.3 1.8 Trade Lakes Import 0 0 0.1 Export 0.1 0.1 0.1 Apparent Consumption 5.1 3.2 3.6 Pigment Import 1.1 0.9 1.4 Export 3.4 4 4.4 Trade Lakes Import 0.1 0 0.2 Export 0.1 0.1 0.2
SOURCES:
(A) Korean Dyestuff and Pigments Industrial Association (Republic of Korea production). (B) Taiwan Dyestuff and Pigments Industrial Association (Taiwan production). (C) China Chemical Industry Yearbook, China National Chemical Information Center (China production). (D) Trade data of each country. (E) CEH estimates.
China The major Chinese producers of organic pigments are listed in the following table:
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Major Chinese Producers of Organic Colored Pigments2001 Company Anhui Sanquen General Chemical Plant BASF Colorants & Chemicals Co., Ltd. Beijing Chemical Industry Group Corp. Changshu Chemical & Medical Industry Bureau Chongqing Dyestuff Factory Clariant Pigments (Tianjin) Ltd. Dainippon Ink and Chemicals Meileda Pigment Industry Co., Ltd. Nangong Qing-Alpha Chemical Co., Ltd. Ningbo Jinbao Group Co., Ltd. Qingdao Chiba Pigmentsb Qingdao Dyestuff Factory Ruian Wanlong Chemical General Manufactory Shanghai Dyestuff Co. Shanghai No. 1 Dyestuff Chemical Plant Shanghai Toyo Ink Co., Ltd. Shenyang General Fertilizer Plant Tianjin No. 2 Dyestuff Chemical Factory Tianjin No. 8 Dyestuff Chemical Plant Tianjin Toyo Inc Co., Ltd. Wenzhou Huanan Chemical Industry Corp. Xiangtan Chemicals and Pigments Co., Ltd.b Yancheng County No. 2 Fertilizer Plant Zhejiang General Chemical Industry Corp. Zhejiang Xiaoshan Pigment Chemical Plant Zhenjiang City Paint Factory a. b. Through joint ventures. Ciba Specialty Chemicals joint ventures. (A) The Peoples Republic of China Chemical Industry , The Scientific & Technical Information Research Institute of the Ministry of Chemical Industry of the Peoples Republic of China. (B) 2000-2001 Directory of Chemical ProducersChina, SRI Consulting. 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, with an azo pigments production capacity of 3.5 thousand metric tons. Chiba announced scrap-and build operations (to scrap 1.7 thousand metric tons capacity and build up new capacity of 2 thousand metric tons) to enhance competitiveness with the latest equipment by 2000. Clariant Chemical has a majority share of its joint venture (ownership of 51%), Songwon Color. The Republic of Koreas organic pigment market share is almost evenly divided by three companies (these two joint ventures and Ukseung Chemical). Concerning the specialty pigments, the consumption of quinacridone is estimated around 50-80 metric tons in 1999, which is supplied by Ciba Specialty Chemicals and Clariant Chemical.
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Taiwan There are several local pigments producers in Taiwan as listed in the table above. Among them, major pigments producers are Tah Kong Chemical Industrial, Janie Color Works and Cosmos Colorants.
China There are numerous pigments producers in China. The production statistics in 1997/1998 may be understated. The domestic organic pigment demand is roughly estimated at around 15 thousand metric tons in 1999. Ciba Specialty Chemicals has two joint ventures in China, one of which, Qingdao Chiba Pigments, 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). Another new joint venture, Xiangtan Chemicals and Pigments Co., Ltd., at Hunan province, constructed 200 metric tons of quinacridone capacity in 2000. Toyo Ink has two joint ventures in China, Shanghai Toyo Ink Co., Ltd. and Tianjin Toyo Ink Co., Ltd., with a total capacity of 4.4 thousand metric tons (this capacity will be increased to 5.6 thousand metric tons in 2003-2004). Chinas exports emphasize phthalocyanine blue (PB-15:3) and green (PG-7).
India There are over 100 pigment producers in India. Production quantities are unknown. DIC has a joint venture, Sudarshan Chemicals Industries, which produces phthalocyanine pigments and other organic pigments, including quinacridone. Hindustan Ink and Resin is a major independent export-oriented producer of finished inks as well as organic pigments such as PY-12, PR-57:1 and PB 15:3. Indias exports emphasize phthalocyanine green and blue; dioxazine pigments (PV-23) and other organic pigments are also exported.
APPENDIXSPECIAL EFFECT PIGMENTS

Special effect pigments are an increasingly important group of pigments. They cause an optical effect by regular reflection or interference. These effects can include viewing angle-dependent color (different viewing positions causing color shifting). Special effect pigments are available as white, black or colored pigments and they are either naturally derived (inorganic and organic) or synthetic (inorganic) pigments. Special effect pigments can be classified further into several groups:
q
Metal effect pigmentsregular reflection takes place on highly refractive parallel pigment platelets (e.g., TiO2 on mica, ultrafine aluminum particle, ultrafine bronze particle). Nacreous pigments (pearlescent pigments)regular reflection takes place mainly on flat and parallel metal pigment particles (e.g., aluminum flakes).
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q
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Interference pigmentsthe optical effect of colored luster pigments is caused entirely or mainly by the phenomenon of interference (e.g., iron oxide on mica).
Although fish silver (natural fish scales based on guanine and hypoxanthin) was the very first commercially used luster pigment, inorganic luster pigments clearly dominate the market today. From a chemical point of view the commercially available nacreous pigments can be classified into the following type of products, in order of importance:
q
Aluminametal oxide, mica. These types of luster pigments have advanced to the most important group of luster pigments, accounting for about 50% of the total world market today. Their main advantages are their favorable optical, chemical, mechanical, toxicological and environmental characteristics. Mica, in in the mineral form of muscovite, can be used alone or in combination with titanium dioxide, iron oxide, tin oxide and chromium oxide. The type of metal oxide and the thickness and number of metal oxide layers determines the final color of the luster pigment. A large number of combination- and metal-color pigments can be produced. Because of their good chemical, thermal and mechanical stability, metal oxidemica pigments are being used in practically all pigment applications where a special optical effect is required. Effects produced include high chroma sparkle. Silica flake. Semitransparent effect pigments can also be produced using silica flakes coated with titanium dioxide or ferric oxide. These pigments can create multicolor effects depending on the viewing angle. Basic lead carbonate. Basic lead carbonate is obtained through the reaction of lead acetate or propionate with carbon dioxide. From an optical perspective, it is an ideal product but some of its physical characteristics limit its use. Basic lead carbonate has poor chemical and thermal stability and its high density leads to a relatively quick sedimentation in the carrier material. More critical today, however, is the fact that this compound contains lead and is therefore under significant pressure from a toxicological and environmental perspective. Still, basic lead carbonate is used in developing countries for the manufacture of buttons and artificial pearls. Bismuth oxychloride. This compound was one of the very first nontoxic pearlescent pigments produced. It is manufactured through the hydrolysis of the chloride ions available in an acidic bismuth salt solution. Depending on the precipitation process, a number of pigments with different optical and physical characteristics can be obtained. Bismuth oxychloride luster pigments are used primarily in cosmetic applications. Because of its relatively low lightfastness, rapid sedimentation and limited mechanical stability, other applications are rather limited. Natural pearlescent (natural fish silver). Fish silver is still commercially produced today. The yield of pearl essence, obtained through solvent extraction of fish scales, depends largely on the type of fish. Some of the fish scales used are of herring, ukelei and sardines. The pigment concentration in fish scale is usually less than 1% and, hence, production costs are relatively high. Fish silver is used mostly in cosmetic applications (primarily in nail enamels), where its physical and chemical sensitivity is not critical. Micronized titanium dioxide. Because of the smaller size of this pigment, a pearlescent effect is caused through interference, as opposed to the opacity caused by standard titanium dioxide pigments.
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The following table lists some of the major world producers of special effect pigments:
Major World Producers of Special Effect Pigments2001 Natural Pearl Basic Lead Carbonate Bismuth Oxychloride Silica Flake Metal Oxide Mica X Trade Names Paliocrom, Sicolux, Variocrom Xab Litho PHOENIX, Toto Flex Roto Safe Mearlin, Mearlite
Company BASF Aktiengesellschaft, Germany
Other
Ecakrt-Werke, Germany
Englehard, Mearl Division., United States J. Jaeger GmbH, Germany Kemira Oy, Finland Mallinckrodt, United States Merck KGaA, Germany
X X X X X Colorstream, Iriodin, Xirallic
Rona, United States (subsidiary) EM Industries, United States (subsidiary) Merck Japan Ltd. (subsidiary) Pacific Chemicals, Republic of Korea Pearl Essence, Norway Poliperl S.A., Argentina Presperse Inc., United States Semo Ltd., Republic of Korea Silberline Manufacturing Company, United Kingdom
X X X
X X X X X Xa SilBerCote Sparkle Silver Tufflake
Sudarshan Chemical Industries Ltd., India Taica, Japan Wacker, Germany
X X Helicone liquid crystal
Williams, United Kingdom Dr. Yang Chemical, Taiwan X
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a. b.
Aluminum pigments. Bronze pigments. CEH estimates.
SOURCE:
Englehard (Mearl Division) and Merck are the leading producers. The total world market size for special effect pigments is estimated at roughly 10 thousand metric tons. Shown in the following table are estimated world consumption figures for special effect pigments:
World Consumption of Special Effect Pigments1999 Metric Tons Metal OxideMica, Silicon Oxide Natural and Synthetic (titanium dioxide) Pearlescent Bismuth Oxychloride Basic Lead Carbonate Others Total SOURCE: CEH estimate. 5,000 3,000 500 <500 1,000 10,000 Consumption Trends Increasing Increasing Stable Declining Increasing
The main applications of special effect pigments are in printing inks, paints and coatings, plastics, textile printing and cosmetics. They are also used in adding special-effect coloring to fine paper, wallpaper and decorative laminates.
BIBLIOGRAPHY
Chemical Economics HandbookThe following CEH marketing research reports, 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 ProgramThe following SCUP reports contain additional information on the subject of this report. Address inquiries concerning this information to Specialty Chemicals Update Program, SRI Consulting, Menlo Park, California 94025. Cosmetic Chemicals Printing Inks Specialty Paper Chemicals

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TABLE OF CONTENTS (continued)

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

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TABLE OF CONTENTS (continued)

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TABLE OF CONTENTS (continued)

AppendixSpecial Effect Pigments ....................................................................................................... 236 Bibliography ............................................................................................................................................ 239

2001 by the Chemical Economics HandbookSRI International

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SUMMARY WORLD MARKET SIZE

Complex Inorganic 12%

Chrome Pigments 6% Azo/Other 23%

World Pigment Production by Region

Western Europe 37%

Other Asia 14%

North America 28%

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a. Includes all organic pigments.

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World Market Value of Organic Pigments by Chemical Class1999

Phthalocyanine Pigments 29%

Total Market Value = $4.9 billion

2001 by the Chemical Economics HandbookSRI International

,551 Azo/Other Phthalocyanine High-Performance Total Total Colored SOURCE:

641 529 395 1,565 2,260

557 446 269 1,272 2,138

406 0 0 406 540

173 183 244 600 846

208 381 141 731 1,038

2,114 1,695 1,099 4,907 7,458

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Elementis, United Kingdom

Rockwood Pigments, United States

Toda Kogyo, Japan SOURCE: CEH estimates.

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Dainichiseika Color and Chemicals Mfg. Co., Ltd., Japan

Toyo Ink Mfg. Co., Ltd., Japan

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Other Pigments 8% Carbon Black 8%

Iron Oxides 16% Titanium Dioxide 68%

Total Production = 5.7 Million Metric Tons

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Other Azo Pigments 8% United States 29% Naphthol AS 8%

Phthalocyanine Blue and Green 29%

Red Lakes 22%

2001 by the Chemical Economics HandbookSRI International

172,304 282,000 19,709 7,250 9,046 6,600 2,000 362 172

47,640 47,640 4,000 2,000 2,154 2,382 538 300 12

94,671 350,000 13,000 22,500 8,077 6,300 4,000 500 300

17,118 30,000 2,500 1,000 400 1,500 400 400 0