Contents
Preface XIX
List of Contributors XXI
Part I
1 Introduction to Inorganic High Performance Pigments 3
Gunter Buxbaum
1.1 Introduction 3
1.2 Survey of Inorganic Pigments 4
1.3 New Candidates on the Catwalk of Color 5
1.4 Challenges for the Future 6
2 Bismuth Vanadates 7
Hartmut Endriss
2.1 Introduction 7
2.2 Historical Background 7
2.3 Manufacture 8
2.4 Properties and Applications 8
2.4.1 Chemical Properties 8
2.4.2 Physical Properties 9
2.4.3 Coloristic Properties 9
2.4.4 Dispersibility 10
2.4.5 Light Fastness and Weather Resistance 10
2.4.6 Chemical and Solvent Resistance 10
2.5 Applications 10
2.5.1 Coatings 10
2.5.2 Plastics 11
2.5.2.1 Properties 11
2.5.2.2 Applications 11
2.5.2.3 Conformity of Pigments for Plastics Coloration to Food
and Drug Regulations 11
2.6 Toxicology 12
2.6.1 Acute Toxicity 12
2.6.2 Chronic Toxicity 12
2.7 Ecology 12
3 Cadmium Pigments 13
Paul Dunning
3.1 Introduction 13
3.2 Pigment History 13
3.2 Raw Materials 15
3.2.1 Cadmium 15
3.2.2 Selenium 15
3.3 Chemistry of Cadmium, Selenium and Cadmium Sulfide 16
3.3.1 Cadmium 16
3.3.2 Selenium 16
3.3.3 Substitution in the CdS Lattice 17
3.4 Method of Pigment Manufacture 17
3.4.1 General Points 17
3.4.2 Cadmium Oxide Formation 19
3.4.3 Cadmium Metal Dissolution 19
3.4.4 Other Solution Making 20
3.4.5 Precipitation 20
3.4.6 Filtration and Washing 21
3.4.7 Drying 21
3.4.8 Calcination 21
3.4.9 Wet Milling 22
3.4.10 Removal of Soluble Cadmium 22
3.4.11 Final Drying and Milling 22
3.5 Physical Properties 22
3.6 Regulatory Issues 24
3.7 Uses 25
4 Cerium Pigments 27
Jean-Noel Berte
4.1 Introduction 27
4.2 Rare Earth Sulfides and the Origins of their Color. 28
4.3 Cerium Sulfide Pigment: Manufacture 31
4.4 Properties and Applications 34
4.4.1 Coloration of Plastics 34
4.4.2 Paint and Coatings Application 38
4.4.3 Miscellaneous Applications 39
4.5 Toxicology and Environmental Aspects 39
4.6 Toxicological and Environmental Concerns during the Manufacturing
Process 40
5 Complex Inorganic Color Pigments: An Overview. 41
James White
5.1 Introduction 41
5.2 Structures of CICPs 42
5.3 Production of CICPs 44
5.4 Titanate Pigments 44
5.4.1 Rutile Titanates 45
5.4.2 Spinel Titanates 46
5.4.3 Other Titanates 47
5.5 Aluminate Pigments 47
5.6 Cobalt Aluminates 47
5.7 Cobalt Chromium Aluminates 48
5.8 Chromites and Ferrites 49
5.9 Black CICPs 49
5.10 Brown Pigments 50
5.11 Green Chromites 51
6 Titanate Pigments: Colored Rutile, Priderite,
and Pseudobrookite Structured Pigments 53
John Maloney
6.1 Introduction 53
6.2 History 55
6.2.1 Doped-Rutile (DR) Pigments 57
6.2.2 Priderite Pigments 58
6.2.3 Pseudobrookite Pigments 58
6.3 Synthesis 58
6.3.1 DR Pigments 59
6.3.2 Priderite Pigments 61
6.3.3 Pseudobrookite Pigments 62
6.4 Applications 62
6.5 Properties 63
6.5.1 Spectral Properties 63
6.5.1.1 Visible Spectral Characterization 63
6.5.1.2 UV and NIR Spectral Characterization 66
6.5.2 Physical Properties 66
6.5.2.1 Particle Size Distribution 66
6.5.2.2 X-ray Diffraction Characterization 67
6.5.2.3 Specific Gravity 68
6.5.2.4 Oil Absorption and Specific Surface Area 69
6.5.2.5 Powder Flow and Dusting 70
6.5.3 Chemical Properties 70
6.5.3.1 pH Measurement 70
6.5.3.2 Weathering 71
6.5.3.3 Particle Chemistry 72
Part II
7 Special Effect Pigments 77
Gerhard Pfaff
7.1 Introduction 77
7.2 Pearlescent and Interference Pigments 78
7.2.1 Optical Principles of Pearlescent and Interference Pigments 79
7.2.2 Substrate-Free Pearlescent Pigments 82
7.2.2.1 Natural Pearl Essence 82
7.2.2.2 Basic Lead Carbonate 82
7.2.2.3 Bismuth Oxychloride 82
7.2.2.4 Micaceous Iron Oxide 83
7.2.2.5 Titanium Dioxide Flakes 83
7.2.3 Pigments Formed by Coating of Substrates 84
7.2.3.1 Metal Oxide-Mica Pigments 84
7.2.3.2 Silica Flake Pigments 90
7.2.3.3 Alumina Flake Pigments 94
7.2.3.4 Borosilicate-based Pigments 96
7.3 Effect Pigments Formed by Coating of Metal Flakes 96
7.4 Pigments Formed by Grinding a Film 97
7.5 Pigments Based on Liquid Crystal Polymers 98
7.6.1 Diffractive Pigments 101
7.6.2 Pigments Based on Holography and Gratings 102
Acknowledgments 103
8 Crystal Design of High Performance Pigments 105
Martin Schmidt
8.1 Introduction 105
8.2 Crystal Engineering of Organic Pigments 106
8.2.1 Close Packing 106
8.2.2 Crystal Energy 108
8.2.3 Specific Interactions 109
8.3 Crystal Structure Determination 113
8.4 Crystal Structure Calculation 115
8.4.1 General Methods 115
8.4.2 Crystal Structure Calculations of Pigments 116
8.4.3 Crystallochromy 118
8.4.4 Morphology Calculation 119
8.4.5 Pigment Morphologies 121
8.5 Control of Interfacial Properties Through Tailor-Made Additives 122
Part III 129
9 The Global Market for Organic High Performance Pigments 131
Fritz Brenzikofer
9.1 Introduction 131
9.2 The 1999 Market for Organic High Performance Pigments 132
9.3 The Producers of High Performance Pigments 133
9.4 The Demand for HPP by Consumer Market Segments 133
9.4.1 The Demand by Regions 134
9.4.2 The Trade Balance of HPP among these Regions 134
9.5 Demand Factors for HPPs 137
9.5.1 Market Requirements and Trends 138
9.5.1.1 Industrial/Decorative Paints 138
9.5.1.2 Plastics 138
9.5.1.3 New Markets 138
9.5.2 Marketing Strategies of Main HPP Producers 138
9.5.3 Globalization Prozess 138
9.6 Conclusions/Outlook 138
10 Benzimidazolone Pigments and Related Structures 139
Hans-Joachim Metz and Frank Morgenroth
10.1 Introduction 139
10.2 Historical Background 143
10.3 Method of Manufacture 145
10.4 Typical Properties and Major Reasons for Use 146
10.5 Pigment Grades, Discussion of Individual Pigments 154
10.6 Pigment Manufacturers, Economics 158
10.7 Safety, Health and Environmental Aspects 164
11 Diketopyrrolopyrrole (DPP) Pigments 165
Olof Wallquist and Roman Lenz
11.1 Introduction 165
History 165
11.2 Syntheses 166
11.2.1 Reformatsky Route 166
11.2.2 Succinic Ester Route 168
11.2.3 Succinic Amide Route 169
11.2.4 Miscellaneous Routes 169
11.3 Molecular Structure and Properties 170
11.3.1 Spectral Properties 170
11.3.2 Spectral Properties – Fluorescence 172
11.3.3 Single X-ray Structure Analysis 174
11.4 Chemical Properties 176
11.4.1 Electrophilic Aromatic Substitution 177
11.4.2 Nucleophilic Aromatic Substitution 177
11.4.3 N-Alkylation 178
11.4.4 Transformations on the Carbonyl Group 179
11.5 Solid-State Properties 180
11.5.1 General Properties 180
11.5.2 Particle Size Control 180
11.5.3 Polymorphism 181
11.5.4 Solid Solutions 182
11.5.5 Surface Modifications 184
11.6 Conventional Applications 185
11.7 Nonconventional Applications 190
12 Dioxazine Violet Pigments 195
Terence Chamberlain
12.1 Introduction 195
12.1.1 The Chemistry of Dioxazine Pigments 195
12.2 Synthesis 196
12.2.1 Dianil Formation 197
12.2.2 Cyclization of the Dianil 197
12.3 Pigmentation and Properties 202
12.3.1 Pigment Violet 23 202
12.3.2 Pigment Violet 37 203
12.4 Recent Developments 203
12.4.1 Preparation/Production Methods 203
12.4.2 New Products 204
13 Disazocondensation Pigments 205
Fritz Herren
13.1 Introduction 205
13.2 Historical Background 205
13.3 Chemistry 206
13.3.1 Commercialized Pigments (Past and Present [4]) 207
13.3.2 Recent Developments 212
13.4 Synthesis and Manufacture 214
13.5 Characterization, Properties, Application 216
13.5.1 Physical Characterization 216
13.5.2 Available Grades 216
13.5.3 Properties and Applications 217
14 Isoindoline Pigments 221
Volker Radtke, Peter Erk, and Benno Sens
14.1 Introduction 221
14.2 Historical Background 224
14.3 Methods of Manufacture 226
14.4 Typical Properties and Major Reasons for Use 229
14.5 Crystal Structures of Isoindoline Pigments 229
14.5.1 Structure Determination 229
14.5.2 Discussion 232
14.5.3 ESA Data 233
14.5 Pigment Grades; Discussion of Individual Pigments 236
14.6 Pigment Manufacturers; Economics 239
14.7 Toxicology and Ecology 240
15 Isoindolinone Pigments 243
Abul Iqbal, Fritz Herren, and Olof Wallquist
15.1 Introduction 243
15.2 Chemistry 244
15.2.1 Azomethine-Type Isoindolinones 244
15.2.2 Methine-Type Isoindolinones 252
15.2.3 Metal Complexes Based on Isoindolinones 253
15.3 Physicochemical Properties 254
15.4 Commercial Products and Applications 257
16 Perylene Pigments 261
Brian Thompson
16.1 Definition of Perylene Pigments 261
16.1.1 History 261
16.1.2 Color Index and Identity 261
16.2 Synthesis of Perylenes 263
16.2.1 Conversion of Perylenes: Acenaphthene to Perylene Tetracarboxylic Acid
Diimide (PTCI, Pigment Violet 29) 263
16.2.2 Synthesis of Perylene Tetracarboxylic Acid Dianhydride (PTCA) by
Hydrolysis of PTCI to PTCA, and PTCA as a Pigment (Pigment Red
224) 265
16.2.3 Alkylation of PTCI to Pigment Red 179 and other Perylene Pigments
265
16.2.4 Synthesis of Perylene Pigments and MixedCrystals by Condensation of
PTCA with Amines 266
16.2.5 Half Imide, Half Anhydrides of PTCA (10) 266
16.2.6 Derivatives of Perylene as Performance Enhancers 267
16.3 The Conditioning of Perylene Diimide Pigments 267
16.4 Mixed Crystals and Solid Solutions of Perylene Diimide Pigments 268
16.5 Drying of Perylene Pigments 268
16.6 Physical Chemistry and Color Physics of Perylene Pigments 269
16.7 Perylene Pigments and their Applications 270
16.8 Perylenes as Functional Colorants 271
16.9 Current Producers 271
16.10 Pricing Trends and Economics of Use 272
16.11 Health, Safety, and Environmental Considerations 272
17 Phthalocyanines – High Performance Pigments
and Their Applications 275
Masao Tanaka
17.1 Introduction 275
17.2 Application of Optical Properties 276
17.2.1 Color Filters for Liquid Crystal Display Devices 276
17.2.2 Ink Jet Inks 277
17.2.3 Infrared Ray Absorbents 279
17.2.4 CD-R 281
17.3 Application of Optoelectronic Properties 282
17.3.1 Electrophotographic Photoreceptor 282
17.3.2 Nonlinear Optical Devices 286
17.4 Application of Catalysis 287
17.4.1 Deodorizers 287
17.4.2 Photodynamic Therapy 288
17.5 Conclusion 289
18 Quinacridone Pigments 293
Terence R. Chamberlain (modification of original chapter by Edward E. Jaffe)
18.1 Introduction 293
18.2 Historical Background 293
18.3 Quinacridone Syntheses 295
18.3.1 The Synthesis of DMSS from Dimethyl Succinate 295
18.3.1.1 By-Products Produced During the Synthesis and Isolation of DMSS 295
18.3.2 Synthesis of DMSS from Diketene (Methyl 4-Chloroacetoacetate) 297
18.3.3 Synthesis of Quinacridones by the Thermal Process 298
18.3.4 Synthesis of Quinacridones by the PPA Process 300
18.3.5 Synthesis of Quinacridones by Application of the Ullmann
Reaction 303
18.4 Recently Introduced Quinacridone Products 304
18.5 Structural Data and Spectra 305
18.6 Polymorphism 308
18.7 Substituted Quinacridones 311
18.8 Photostability and a Suggested Mechanism 313
18.9 Quinacridonequinone 315
18.10 Other 6,13-Disubstituted Quinacridones 317
XII
18.11 Solid Solutions 318
18.12 Conditioning and Surface Treatment of Quinacridones 323
18.13 Applications 325
18.14 Health and Safety Factors 326
18.15 Business Aspects 326
19 Quinophthalone Pigments 331
Volker Radtke
19.1 Introduction 331
19.2 Historical Background 333
19.3 Methods of Manufacture 334
19.4 Typical Properties and Major Reasons for Use 335
19.5 Pigment Grades and Discussion of Individual Pigments 336
19.5.1 Discussion of Individual Pigments 338
19.6 Pigment Manufacturers: Economics 339
19.7 Toxicology and Ecology 340
20 Imidazolone-Annellated Triphenedioxazine Pigments 341
Martin U. Schmidt
20.1 Introduction 341
20.2 On the Structure of Pigment Violet 23 342
20.3 Imidazolone-Annellated Triphenedioxazine Pigments 344
20.3.1 Syntheses 345
20.3.2 Properties 346
20.3.2.1 Pigment Blue 80 346
20.3.2.2 Other Imidazolone-Annellated Triphenedioxazine Pigments 347
20.3.3 Crystal Engineering on Imidazolone-Annellated Triphenedioxazine
Pigments 347
20.3.3.1 Structure Determination from X-Ray Powder Data 348
20.3.3.2 Crystal Structures of Pigment Blue 80 and the Dimethyl Derivative
(4b) 349
20.3.3.3 Crystal Engineering: Pigment Violet 57 351
Part IV 355
21 Chemical and Physical Characterization of High Performance
Organic Pigments 357
Constantinos Nicolaou
21.1 Introduction 357
21.2 Visible Spectrophotometry 359
21.2.1 Introduction 359
21.2.2 Applications of Visible Spectroscopy 362
21.2.2.1 Copper Phthalocyanines 362
XIII
21.2.2.2 Visible Spectra of Quinacridone Pigments 364
21.2.2.3 Visible Spectra of Other Pigments 366
21.3 Applications of FT-IR Spectroscopy 368
21.3.1 Introduction 368
21.3.2 Applications of Infrared Spectroscopy 370
21.4 Mass Spectrometry Techniques 373
21.4.1 Introduction 373
21.5 High-Performance Liquid Chromatography 378
21.5.1 Introduction 378
21.5.2 HPLC Applications 378
21.6 Powder X-ray Diffraction 380
21.6.1 Introduction 380
21.6.2 XRD Sample Preparation 382
21.6.3 Applications of XRD 382
21.7 Particle Sizing Techniques 390
21.7.1 Introduction 390
21.7.2 Transmission Electron Microscopy 393
21.7.2.2 Sample Preparation for TEM Analysis 393
21.7.2.3 Applications of TEM 394
21.7.3 Optical Microscopy 396
21.7.3.1 Introduction 396
21.7.3.2 Applications of Optical Microscopy 397
21.7.4 Particle Size by Ultracentrifugal Sedimentation and Comparison to
TEM 398
21.7.4.1 Introduction 398
21.7.4.2 Applications of Particle Sizing by Ultracentrifugation 399
21.8 Thermal Analysis and Decomposition Temperatures of HPOPs 404
21.9 Product Safety and Environmental Testing of HPOPs 407
22 Regulatory Affairs for High Performance Pigments: North America 409
Harold F. Fitzpatrick, Esq. and Glenn C. Merritt, Esq.
22.1 Introduction 409
22.2 Toxic Substances Control Act 409
22.3 Canada 411
22.3.1 Assessment of the Canadian DSL 412
22.4 Mexico 413
22.5 Toxic Release Inventory Reporting 414
22.6 Regulation of de minimis Levels 414
22.7 Food and Drug Administration 415
22.8 Color Pigments in General 415
22.9 PBT-TRI Rules 418
22.10 Nanotechnology and Regulation 420
22.11 High Production Volume (HPV) Substances 423
22.12 Phthalocyanine Pigments 424
22.13 Quinacridone Pigments 424
22.14 Carbazole Violet Pigments 425
22.15 Perylene Pigments 426
22.16 Inorganic Pigments 426
22.16.1 Complex Inorganic Color Pigments 426
22.16.2 Cadmium Pigments 427
22.17 Conclusion 428
23 Regulatory and Legislative Aspects of Relevance to High Performance
Pigments: Europe 431
Eric Clarke and Herbert Motschi
23.1 Introduction 431
23.2 The European Union and its Institutions 431
23.2.1 European Commission 432
23.2.2 European Parliament (E.P.) 433
23.2.3 The Council of the European Union and other Institutions 434
23.2.4 Legal Instruments 434
23.3 The Major EU Directives Governing Chemical Control 435
23.3.1 Dangerous Substances (Commission Directive 67/548/EEC) 436
23.3.1.1 Some Differences between EU and US Requirements 437
23.3.1.2 Notification 438
23.3.1.3 Classification and Labeling 440
23.3.2 Dangerous Preparations (E.P. and Council Directive 1999/45/EEC) 444
23.3.3 Safety Data Sheets (Commission Directive 2001/58/EC) 444
23.3.4 Existing Substances, Priority Lists, Risk Assessment (Council Regulation
EEC 793/93) 444
23.3.5 Restrictions of Marketing and Use 445
23.3.6 REACH 447
23.3.7 Pollution Control 448
23.3.8 Packaging and Packaging Waste (E.P. and Council Directive
94/62/EC) 448
23.3.9 Eco-Labels 448
23.3.10 Food Packaging Legislation 449
23.3.11 Technical Barriers to Trade 452
23.4 National Regulations 452
23.4.1 Germany 453
23.4.1.2 Wassergefährdungsklassen (Water-Hazard Classes) 453
23.4.1.3 Dioxin Limits 454
23.4.2 France 455
23.4.3 Switzerland 457
23.5 Future Enlargement of the EU (PHARE and similar programs) 458
23.6 Nonregulatory Initiatives 460
23.6.1 High Production Volume (HPV) Chemicals Testing Initiative 460
23.6.2 Precautionary Principle 460
23.6.3 Black-listing 461
23.7 Confidentiality 462
23.8 Availability of Information on Current Regulations 462
23.9 Future Outlook 463
24 Infrared Reflecting Complex Inorganic Colored Pigments 467
Terry Detrie and Dan Swiler
24.1 Introduction 467
24.2 Background/Physics 468
24.2.1 Source of Infrared Light 468
24.2.2 Heating Mechanisms 469
24.2.3 Cooling Mechanisms 470
24.3 Measurement 471
24.3.1 ASTM E903: Integrating Sphere Spectrophotometer [3] 471
24.3.2 ASTM C1549: Portable Solar Reflectometer [4] 471
24.3.3 ASTM E1918: Pyranometer [5] 472
24.3.4 ASTM D4803: Heat Buildup [6] 472
24.4 Pigments 473
24.4.1 Introduction 473
24.4.2 Doped Rutile Titanate Yellows and Tans 473
24.4.3 CICP Tans and Browns 475
24.4.4 CrFe and Other CICP IR Blacks 476
24.4.5 New Inorganic IR Black Pigments 479
24.4.6 Blue Pigments 480
24.4.7 Green CICP Pigments 481
24.5 Formulation with IR Pigments 482
24.5.1 Opacity 483
24.5.2 Absorptions 484
24.6 Market Driving Forces 485
24.6.1 Studies 485
24.6.2 Specifications on “Cool Roof” 486
24.6.3 Rebate Programs 486
24.7 Conclusions 487
25 Toxicology and Ecotoxicology Issues with High Performance
Pigments 489
Robert Mott (revision of original chapter by Hugh M. Smith)
25.1 Introduction 489
25.2 Recent Toxicological Testing of High Performance Pigments 489
25.3 Past Confusion in Assessment of HPPs 490
25.3.1 Confusion between Water Soluble Salts of Inorganic Metals and Related
but Insoluble Pigments 490
25.3.2 Confusion bBetween Pigments and their Associated Impurities 491
25.3.3 False Positives in Genotoxicity Testing of Organic HPPs 491
25.3.3 Over-Reliance on Structure Activity Relationship (SAR) Assessment of
HPPs 491
25.3.4 Confusion over Inaccurate “PBT” Classifications of HPPs 492
25.3.4 Inadequacy of Recent Computer-Driven Models for Substance
Profiling 492
25.3.5 Inadequacy of Partition Coefficient Calculations in Evaluating
Bioaccumulation 492
25.3.6 Continued Polarization Between Environmental NGOs and Industry
Groups 493
25.4 Current Programs for Toxicological and Ecotoxicological Assessment of
HPPs 493
25.5 The Way Ahead 494
25.5.1 Future Protocols for HPPs 494
25.5.2 Implementation of the Prior Informed Consent (PIC) Treaty 494
Appendix 497
Index 503