Industrial Organic Pigments

Klaus Hunger (Dr. rer. nat., TU München) was the research director of the hydrazone pigments unit at Hoechst AG. Today, he is the Managing Director of Decernis GmbH.Martin U. Schmidt (Dr. rer. nat., Aachen) was employed at Hoechst AG, later Clariant, in the pigment research group. Today, he is a professor at the Goethe University in Frankfurt. His main research interest is the determination of crystal structures of industrial organic pigments and pharmaceuticals.

• List of ContributorsPreface to the Fourth Edition xixPreface to the Third Edition xxiPreface to the Second Edition xxiiiPreface to the First Edition xxvList of Abbreviations xxvii1 General 11.1 Definition: Pigments and Dyes 11.1.1 Organic and Inorganic Pigments 21.2 Historical 31.3 Classification of Organic Pigments 41.3.1 Hydrazone Pigments (Formerly Called Azo Pigments) (Chapter 2) 41.3.1.1 Monohydrazone Yellow and Orange Pigments (Formerly Called Monoazo Yellow and Orange Pigments) (Section 2.3) 51.3.1.2 Dihydrazone Pigments (Formerly Called Disazo Pigments) (Section 2.4) 51.3.1.3 β-Naphthol Pigments (Section 2.5) 51.3.1.4 Naphthol AS Pigments (Section 2.6) 51.3.1.5 Hydrazone Pigment Lakes (Formerly Called Azo Pigment Lakes) (Section 2.7) 61.3.1.6 Benzimidazolone Pigments (Section 2.8) 61.3.1.7 Dihydrazone Condensation Pigments (Formerly Called Disazo Condensation Pigments) (Section 2.9) 71.3.2 Polycyclic Pigments (Chapter 3) 71.3.2.1 Phthalocyanine Pigments (Section 3.1) 71.3.2.2 Quinacridone Pigments (Section 3.2) 71.3.2.3 Perylene and Perinone Pigments (Section 3.4) 81.3.2.4 Diketopyrrolopyrrole (DPP) Pigments (Section 3.5) 81.3.2.5 Thioindigo Pigments (Section 3.6) 81.3.2.6 Pigments Derived from Anthraquinone (Section 3.7) 81.3.2.7 Dioxazine Pigments (Section 3.8) 91.3.2.8 Quinophthalone Pigments (Section 3.9) 91.3.2.9 Isoindolinone and Isoindoline Pigments 91.3.3 Miscellaneous Pigments (Chapter 4) 101.3.3.1 Triarylcarbonium Pigments (Section 4.1) 101.3.3.2 Metal Complex Pigments (Section 4.2) 101.4 Relationship between Chemical Structure and Pigment Properties 101.4.1 Hue 111.4.2 Tinctorial Strength 141.4.3 Lightfastness and Weatherfastness 171.4.4 Solvent and Migration Fastness 181.5 Physical Characterization of Pigments 201.5.1 Specific Surface Area 231.5.2 Particle Size Distribution 261.5.2.1 Determination of Particle Size by Ultrasedimentation 271.5.2.2 Determination by Electron Microscopy 281.5.2.3 Data Representation 331.5.3 Crystal Structure and Polymorphism 371.5.3.1 Effect of the Crystal Structure on the Optical Properties 391.5.3.2 Polymorphism 411.5.3.3 Identification of Polymorphic Forms by X-Ray Powder Diffraction 441.5.3.4 Crystal Structure Determination 441.5.3.5 Prediction of Crystal Structures; Crystal Engineering 471.5.4 Crystallinity 481.6 Important Application Properties and Concepts 511.6.1 Colouristic Properties (by F. Gläser) 521.6.1.1 Colour 521.6.1.2 Colour Depth 551.6.1.3 Colour Differences 561.6.1.4 Optical Behaviour of Pigmented Coatings 561.6.1.5 Tinctorial Strength 581.6.1.6 Hiding Power 601.6.1.7 Transparency 611.6.2 Fastness to Solvents and Special Application Fastness 611.6.2.1 Organic Solvents 611.6.2.2 Water, Soap, Alkali and Acids 621.6.2.3 Pigment Performance in Special Applications 651.6.2.4 Textile Fastness Properties 661.6.3 Migration 671.6.3.1 Blooming 681.6.3.2 Bleeding/Overspraying Fastness 711.6.4 Disturbances during the Processing of Pigmented Systems 751.6.4.1 Plate-Out 751.6.4.2 Overpigmentation/Chalking 761.6.4.3 Distortion/Nucleation in Polymers 771.6.5 Dispersion 781.6.5.1 General Considerations 781.6.5.2 Desagglomeration of Pigment Particles 801.6.5.3 Wetting of Pigment Particle Surfaces 801.6.5.4 Distribution of the Dispersed Pigment in its Medium 841.6.5.5 Stabilization 861.6.5.6 Dispersion and the Critical Pigment Volume Concentration 861.6.5.7 Test Methods 871.6.5.8 Flush Pastes 931.6.5.9 Pigment Preparations 941.6.6 Lightfastness and Weatherfastness 941.6.6.1 Definition and General Information 941.6.6.2 Evaluation Techniques and Equipment 951.6.6.3 Factors Determining the Lightfastness 981.6.7 Thermal Stability 1041.6.8 Flow Properties of Pigmented Systems 1101.6.8.1 Rheological Properties 1101.6.8.2 Viscoelastic Properties 1141.6.8.3 Influence on the Flow Properties 1141.6.8.4 Correlation between Flow Behaviour and Rheological Parameters 1151.6.8.5 Rheological Measurements 1161.7 Particle Size Distribution and Application Properties of Pigmented Media 1191.7.1 Tinctorial Strength 1201.7.2 Hue 1221.7.3 Hiding Power, Transparency 1261.7.4 Lightfastness and Weatherfastness 1311.7.5 Dispersibility 1331.7.6 Gloss 1361.7.7 Solvent and Migration Fastness 1391.7.8 Flow 1411.8 Areas of Application for Organic Pigments 1421.8.1 Printing Inks 1441.8.1.1 Offset Printing 1441.8.1.2 Gravure Printing 1491.8.1.3 Solvent-Based Flexographic Packaging Printing 1521.8.1.4 Non-impact Printing 1541.8.1.5 Security Printing 1551.8.2 Coatings 1551.8.2.1 Oxidatively Drying Paints 1561.8.2.2 Oven Drying Systems 1561.8.2.3 Emulsion Paints 1621.8.3 Plastics 1631.8.3.1 Polyolefins 1671.8.3.2 Poly(vinyl chloride) (PVC) 1691.8.3.3 Polyurethane 1741.8.3.4 Polyamide, Polycarbonate, Polyester, Polyoxymethylene 1751.8.3.5 Polystyrene, Styrene-Copolymers, Poly(methyl methacrylate) 1751.8.3.6 Elastomers 1771.8.3.7 Thermoplastic Elastomers (TPEs) 1781.8.3.8 Thermosets (Thermosetting Plastics) 1791.8.3.9 Spin Dyeing 1811.8.4 Other Areas of Application 1831.8.4.1 Miscellaneous Applications 1831.8.4.2 Colouration of Glass with Organic Pigments 184References for Chapter 1 1842 Hydrazone Pigments (Formerly Called Azo Pigments) 1932.1 Starting Materials 1962.1.1 Diazo Components 1972.1.1.1 Reduction Methods 1992.1.2 Coupling Compounds 2002.1.2.1 Acetoacetic Anilides 2012.1.2.2 β-Naphthol and its Derivatives 2012.1.2.3 Pyrazolone Derivatives 2042.1.3 Important Intermediates 2042.2 Synthesis of Hydrazone Pigments 2052.2.1 Diazotization 2062.2.1.1 Diazotization Mechanism 2072.2.1.2 Methods of Diazotization 2072.2.2 Coupling 2092.2.2.1 Coupling Techniques 2112.2.3 Finishing 2132.2.4 Filtration, Drying and Milling 2142.2.5 Hydrazone Pigment Synthesis by Continuous Operation 2152.2.5.1 Diazotization by Continuous Technique 2162.2.5.2 Coupling by Continuous Process 2182.2.5.3 Process Control 2192.2.6 Production Units for Hydrazone Pigment Manufacture by Batch Operation 2192.3 Monohydrazone Yellow and Orange Pigments (Formerly Called Monoazo Yellow and Orange Pigments) 2212.3.1 Chemistry, Manufacture and Crystal Structures 2232.3.1.1 Non-laked Monohydrazone Yellow and Orange Pigments 2232.3.1.2 Monohydrazone Yellow Pigment Lakes 2272.3.2 Properties 2322.3.2.1 Non-laked Monohydrazone Yellow and Orange Pigments 2322.3.2.2 Monohydrazone Yellow Pigment Lakes 2332.3.3 Application 2332.3.4 Commercially Available Monohydrazone Yellow and Orange Pigments 2352.3.4.1 General 2352.3.4.2 Individual Non-laked Monohydrazone Yellow and Orange Pigments 2352.3.4.3 Monohydrazone Yellow Pigment Lakes 2472.4 Dihydrazone Pigments (Formerly Called Disazo Pigments) 2512.4.1 Diarylide Yellow Pigments 2532.4.1.1 Chemistry, Manufacture and Crystal Structures 2532.4.1.2 Properties 2582.4.1.3 Application 2592.4.1.4 Commercially Available Diarylide Yellow Pigments 2622.4.2 Bisacetoacetarylide Pigments 2782.4.2.1 Chemistry, Manufacture and Crystal Strctures 2782.4.2.2 Properties and Application 2802.4.2.3 Commercially Available Bisacetoacetarylide Pigments 2812.4.3 Dihydrazonepyrazolone Pigments (Formerly Called Disazopyrazolone Pigments) 2842.4.3.1 Chemistry, Manufacture and Crystal Structures 2842.4.3.2 Properties 2852.4.3.3 Application 2852.4.3.4 Commercially Available Dihydrazonepyrazolone Pigments 2852.5 β-Naphthol Pigments 2902.5.1 Chemistry, Manufacture and Crystal Structures 2912.5.1.1 Crystal Structures 2922.5.2 Properties 2932.5.3 Application 2932.5.4 Commercially Available β-Naphthol Pigments 2962.6 Naphthol AS Pigments 3002.6.1 Chemistry, Manufacture and Crystal Structures 3022.6.1.1 Crystal Structures 3032.6.2 Properties 3072.6.3 Application 3092.6.4 Commercially Available Naphthol AS Pigments 3102.6.4.1 General 3102.6.4.2 Naphthol AS Pigments with Simple Substituents 3102.6.4.3 Naphthol AS Pigments with Sulfonamide or Carbonamide Groups 3242.7 Red Hydrazone Pigment Lakes (Formerly Called Red Azo Pigment Lakes) 3372.7.1 β-Naphthol Pigment Lakes 3382.7.1.1 Chemistry, Manufacture and Crystal Structures 3382.7.1.2 Properties 3412.7.1.3 Application 3422.7.1.4 Commercially Available β-Naphthol Pigment Lakes 3422.7.2 BONA Pigment Lakes 3492.7.2.1 Chemistry, Manufacture and Crystal Structures 3492.7.2.2 Properties 3502.7.2.3 Application 3512.7.2.4 Commercially Available BONA Pigment Lakes 3522.7.3 Naphthol AS Pigment Lakes 3622.7.3.1 Chemistry, Manufacture, Crystal Structures, Properties and Applications 3622.7.3.2 Commercially Available Naphthol AS Pigment Lakes 3622.7.4 Naphthalene Sulfonic Acid Pigment Lakes 3662.7.4.1 Chemistry, Manufacture, Crystal Structures, Properties and Applications 3662.7.4.2 Commercially Available Naphthalene Sulfonic Acid Pigment Lakes 3662.8 Benzimidazolone Pigments 3702.8.1 Chemistry, Manufacture and Crystal Structures 3722.8.1.1 Coupling Components for Yellow and Orange Benzimidazolone Pigments 3722.8.1.2 Coupling Components for Red Benzimidazolone Pigments 3732.8.1.3 Pigment Synthesis and Aftertreatment 3732.8.1.4 Crystal Structures 3742.8.2 Properties 3802.8.3 Application 3812.8.4 Commercially Available Benzimidazolone Pigments 3822.8.4.1 The Yellow and Orange Series 3822.8.4.2 The Red and Brown Series 3932.8.5 Quinoxalinedione Pigments 4002.8.5.1 Chemistry, Manufacture and Crystal Structures 4002.8.5.2 Properties and Applications 4022.9 Dihydrazone Condensation Pigments (Formerly Called Disazo Condensation Pigments) 4032.9.1 Chemistry, Manufacture and Crystal Structures 4042.9.2 Properties 4072.9.3 Application 4072.9.4 Commercially Available Dihydrazone Condensation Pigments 4092.9.4.1 General 4092.9.4.2 Yellow Series 4092.9.4.3 Orange, Red and Brown Pigments 414References for Chapter 2 4213 Polycyclic Pigments 4253.1 Phthalocyanine Pigments 4263.1.1 Starting Materials 4273.1.1.1 Phthalic Anhydride 4283.1.1.2 Phthalonitrile 4283.1.2 Manufacture 4283.1.2.1 Phthalonitrile Process 4293.1.2.2 Phthalic Anhydride/Urea Process 4323.1.2.3 Manufacturing the Different Crystal Modifications 4353.1.2.4 Phase- and Flocculation-Stabilized Copper Phthalocyanine Blue Pigments 4373.1.2.5 Manufacture of Green Types 4383.1.2.6 Metal-Free Phthalocyanine Blue 4393.1.3 Crystal Structures and Properties 4403.1.4 Application 4453.1.5 Commercially Available Phthalocyanine Pigments 4473.2 Quinacridone Pigments 4603.2.1 Starting Materials, Manufacture and Crystal Structures 4613.2.1.1 Thermal Ring Closure 4613.2.1.2 Acidic Ring Closure 4633.2.1.3 Dihalo-terephthalic Acid Process 4633.2.1.4 Hydroquinone Process 4643.2.1.5 Substituted Quinacridones 4653.2.1.6 Quinacridone Quinone 4663.2.1.7 Polymorphism 4663.2.1.8 Crystal Structures 4683.2.1.9 Solid Solutions 4753.2.2 Properties 4773.2.3 Application 4773.2.4 Commercially Available Quinacridone Pigments 4773.3 Vat Dyes Prepared as Pigments 4873.4 Perylene and Perinone Pigments 4883.4.1 Perylene Pigments 4883.4.1.1 Preparation of the Starting Materials 4893.4.1.2 Chemistry, Manufacture 4893.4.1.3 Crystal Structures and Properties 4913.4.1.4 Application 4983.4.1.5 Commercially Available Perylene Pigments 4983.4.2 Perinone Pigments 5043.4.2.1 Preparation of the Starting Materials 5043.4.2.2 Chemistry, Manufacture and Crystal Structures 5053.4.2.3 Properties 5103.4.2.4 Commercially Available Perinone Pigments and Their Application 5103.4.3 Semiperinone Pigments and Similar Pigments 5133.5 Diketopyrrolopyrrole (DPP) Pigments 5143.5.1 Chemistry, Manufacture and Crystal Structures 5143.5.2 Properties and Application 5203.5.3 Commercially Available DPP Pigments 5203.6 Indigo, Thioindigo and Thiazine Indigo Pigments 5253.6.1 Indigo 5253.6.1.1 Crystal Structure 5253.6.1.2 Properties and Application 5253.6.2 Thioindigo Pigments 5263.6.2.1 Chemistry, Manufacture and Crystal Structures 5263.6.2.2 Properties and Application 5283.6.2.3 Commercially Available Thioindigo Pigments and Their Application 5293.6.3 Thiazine Indigo Pigments 5323.6.3.1 Chemistry, Manufacture and Crystal Structures 5323.6.3.2 Properties 5343.6.3.3 Commercially Available Thiazine Indigo Pigments and Their Application 5343.7 Various Polycyclic Pigments Derived from Anthraquinone 5343.7.1 Aminoanthraquinone Pigments 5353.7.1.1 Synthesis of 1-Aminoanthraquinone 5353.7.1.2 Anthraquinone-Hydrazone Pigments 5363.7.1.3 Other Aminoanthraquinone Pigments 5383.7.1.4 Commercially Available Aminoanthraquinone Pigments 5423.7.2 Hydroxyanthraquinone Pigments 5443.7.2.1 Commercially Available Hydroxyanthraquinone Pigments 5463.7.3 Heterocyclic Anthraquinone Pigments 5463.7.3.1 Anthrapyrimidine Pigments 5463.7.3.2 Indanthrone and Flavanthrone Pigments 5483.7.4 Polycarbocyclic Anthraquinone Pigments 5573.7.4.1 Pyranthrone Pigments 5573.7.4.2 Anthanthrone Pigments 5613.7.4.3 Isoviolanthrone Pigments 5653.7.4.4 Violanthrone Pigments 5673.8 Dioxazine Pigments 5693.8.1 Preparation of the Starting Materials 5703.8.2 Chemistry, Manufacture and Crystal Structures 5703.8.2.1 Crystal Structures 5743.8.3 Properties 5743.8.4 Commercially Available Dioxazine Pigments and Their Application 5773.9 Quinophthalone Pigments 5813.9.1 Chemistry, Manufacture and Crystal Structures 5813.9.2 Properties and Application 5853.9.3 Commercially Available Quinophthalone Pigments 5853.9.3.1 Pigment Yellow 138 5853.10 Isoindolinone and Isoindoline Pigments 5863.10.1 General 5863.10.1.1 Isoindolinone Pigments 5863.10.1.2 Isoindoline Pigments 5873.10.2 Chemistry, Manufacture and Crystal Structures 5883.10.2.1 Isoindolinone Pigments 5883.10.2.2 Isoindoline Pigments 5913.10.3 Properties 5973.10.3.1 Isoindolinone Pigments 5973.10.3.2 Isoindoline Pigments 5973.10.4 Application 5973.10.5 Commercially Available Isoindolinone and Isoindoline Pigments 597References for Chapter 3 6064 Miscellaneous Pigments 6134.1 Triarylcarbonium Pigments 6134.1.1 Inner Salts of Sulfonic Acids (Alkali Blue Types) 6144.1.1.1 Chemistry, Manufacture 6154.1.1.2 Properties and Application 6194.1.1.3 Commercially Available Alkali Blue Pigments 6194.1.2 Dye Salts with Complex Anions 6224.1.2.1 Chemistry, Manufacture and Crystal Structures 6234.1.2.2 Properties 6294.1.2.3 Application 6304.1.2.4 Commercially Available Dye Salts with Complex Anions 6304.1.3 Aluminium Pigment Lakes 6384.2 Metal Complex Pigments 6404.2.1 Chemistry, Synthesis and Crystal Structures 6414.2.1.1 Azo Metal Complexes 6424.2.1.2 Azomethine Metal Complexes 6434.2.2 Properties 6474.2.3 Application 6474.2.4 Commercially Available Metal Complex Pigments 6474.3 Pigments with Known Chemical Structure Which Cannot be Assigned to Other Chapters 6554.3.1 Pigment Yellow 101 6554.3.2 Pigment Yellow 148 6574.3.3 Pigment Yellow 182 6574.3.4 Pigment Yellow 201 6594.3.5 Quinolonoquinolone Pigments (P.Y.218, P.Y.220, P.Y.221) 6594.3.6 Pigment Orange 64 6614.3.7 Pigment Orange 67 6614.3.8 Pigment Red 90 6624.3.9 Pigment Red 252 6644.3.10 Pigment Blue 63 6644.3.11 Pigment Brown 22 6654.3.12 Pigment Black 1 6654.4 Pigments with Hitherto Unpublished Chemical Structures 6664.4.1 Pigment Yellow 99 6664.4.2 Pigment Yellow 187 6674.4.3 Pigment Yellow 214 6674.4.4 Pigment Orange 83 6674.4.5 Pigment Red 204 6674.4.6 Pigment Red 278 6684.4.7 Pigment Red 285 6684.4.8 Pigment Red 293 6684.4.9 Pigment Violet 51 6694.4.10 Pigment Black 20 6694.5 Organic/Inorganic Hybrid Pigments 669References for Chapter 4 6735 Legislation, Ecology, Toxicology 6755.1 Introduction 6755.2 Chemicals Legislation 6765.2.1 General 6765.2.1.1 Chemical Inventories 6765.2.1.2 GHS – Globally Harmonized System 6775.2.1.3 REACH (European Union) 6795.2.1.4 REACH Restricted Substances List 6795.2.2 Legislation Concerning Organic Pigments 6815.2.2.1 Food Packaging/Food Contact 6835.2.2.2 Purity Criteria 6855.2.2.3 Toys 6875.2.2.4 Consumer Goods 6885.3 Ecology 6915.4 Toxicology 6925.4.1 Acute Toxicity 6935.4.2 Irritation of Skin and Mucous Membrane 6935.4.3 Toxicity after Repeated Application 6945.4.4 Mutagenicity 6945.4.5 Chronic Toxicity – Carcinogenicity 694References for Chapter 5 696Reaction Schemes 699A1 Starting Materials (Section 2.1) 699A2 Synthesis of Hydrazone Pigments (Section 2.2) 700A3 Monohydrazone Yellow and Monohydrazone Orange Pigments (Section 2.3) 702A4 Dihydrazone Pigments (Section 2.4) 704A5 ß-Naphthol Pigments (Section 2.5) 705A6 Naphthol AS Pigments (Section 2.6) 706A7 Red Hydrazone Pigment Lakes (Section 2.7) 706A8 Benzimidazolone Pigments (Section 2.8) 709A9 Dihydrazone Condensation Pigments (Section 2.9) 710A10 Phthalocyanine Pigments (Section 3.1) 713A11 Quinacridone Pigments (Section 3.2) 715A12 Perylene and Perinone Pigments (Section 3.4) 721A13 Diketopyrrolopyrrole (DPP) Pigments (Section 3.5) 722A14 Indigo, Thioindigo and Thiazine Indigo Pigments (Section 3.6) 723A15 Various Polycyclic Pigments Derived from Anthraquinone (Section 3.7) 725A16 Dioxazine Pigments (Section 3.8) 729A17 Quinophthalone Pigments (Section 3.9) 730A18 Isoindolinone and Isoindoline Pigments (Section 3.10) 731A19 Triarylcarbonium Pigments (Section 4.1) 733A20 Metal Complex Pigments (Section 4.2) 736List of Commercially Available Pigments 739Index 755

"...eignet sich das Buch zur Einfuhrung in die Thematik, aber auch erfahrene Anwender und Entwickler werden es als wertvolles Nachschlagewerk zu schatzen wissen.... Der "Herbst/Hunger" ist auch in der dritten Auflage seinem Genre zwischen Lehrbuch und Nachschlagewerk treu geblieben. Es gibt kein vergleichbares Buch, das einem die physikalischen Grundlagen, die Chemie und die Anwendungseigenschaften organischer Buntpigmente so umfassend, kompakt und eingangig erschließt."—Peter Erk, BASF Aktiengesellschaft, Ludwigshafen, Angewandte Chemie, 2004-116/34