Industrial dyes: chemistry, properties, applications

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K. Hunger (Editor)

Industrial Dyes
Chemistry, Properties, Applications


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Furtherof Interest:
Herbst, W., Hunger, K.
Industrial Organic Pigments
Production, Properties, Applications
Third, Completely Revised Edition
2003
ISBN 3-527-30576-9

Buxbaum, G. (Ed.)
Industrial Inorganic Pigments
Second, Completely Revised Edition
1998
ISBN 3-527-28878-3

Smith, H. M. (Ed.)
High Performance Pigments
2002
ISBN 3-527-30204-2

Völz, H. G.

Industrial Color Testing
Fundamentals and Techniques
Second, Completely Revised Edition
2001
ISBN 3-527-30436-3

Freitag, W., Stoye, D. (Eds.)
Paints, Coatings and Solvents
Second, Completely Revised Edition
1998
ISBN 3-527-28863-5

Bieleman, J. (Ed.)
Additives for Coatings
2000
ISBN 3-527-29785-5


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Klaus Hunger (Editor)

Industrial Dyes
Chemistry, Properties, Applications


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Dr. Klaus Hunger (Editor)
Johann-Strau û-Str. 35

D-65779 Kelkheim
Germany
formerly Hoechst AG, Frankfurt, Germany

This book was carefully produced. Nevertheless, editor , authors and publisher do not warrant the
information contained therein to be free of errors. Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate.

Library of Congress Card No.: Applied for.
British Library Cataloguing-in-Publication Data: A catalogue record for this book is available from the
British Library
Bibliographic information published by Die Deutsche Bibliothek
Die Deutsche Bibliothek lists this publication in the Deutsche Nationalbibliografie;
detailed bibliographic data is available in the Internet at <>
ISBN 3-527-30426-6
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

Printed on acid-free paper.
All rights reserved (including those of translation in other languages). No part of this book may be
reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into machine language without written permission from the publishers. Registered names, trademarks, etc. used in this book, even when not specifically marked as such, are not to be considered unprotected by law.
Composition: Kühn & Weyh, 79111 Freiburg
Printing and Bookbinding: Druckhaus Darmstadt GmbH, Darmstadt
Printed in the Federal Republic of Germany.


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Contents

Preface

XXI

List of Contributors

XXIII
1

1

Dyes, General Survey

1.1

Introduction

1.2

Classification Systems for Dyes

1.3

Classification of Dyes by Use or Application Method

1.4

Nomenclature of Dyes

1.5

Equipment and Manufacture

1.6

Economic Aspects

1.7

References

2

Important Chemical Chromophores of Dye Classes
Introduction

2.1
2.1.1
2.1.2
2.1.2.1
2.1.2.2
2.1.2.3
2.1.2.4
2.1.3
2.1.3.1
2.1.3.2

1
2
3

6

7

10

12

13

Azo Chromophore 14
Introduction 14
General Synthesis 16
Diazo Components 16
Diazotization Methods 19
Coupling Components 20
Azo Coupling in Practice 28
Principal Properties 29
Tautomerism 29
Metallized A zo Dyes 32

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VI

Contents

2.1.3.3
2.1.3.4
2.1.4

Carbocyclic Azo Dyes 33
Heterocyclic Azo Dyes 34
References 35

2.2
2.2.1
2.2.2
2.2.3
2.2.3.1
2.2.3.2
2.2.4

Anthraquinone Chromophore 35
Introduction 35
General Synthesis 36
Principal Properties 36
Benzodifuranone Dyes 37
Polycyclic Aromatic Carbonyl Dyes
References 39

2.3
2.3.1
2.3.2
2.3.3
2.3.3.1
2.3.3.2
2.3.3.3
2.3.3.4
2.3.4

Indigoid Chromophore 40
Introduction 40
General Synthesis 40
Principal Properties 41
Color 41
Basic Chromophore 42
Solvatochromism 42
Redox System 43
References 43

2.4
2.4.1
2.4.2
2.4.3
2.4.3.1
2.4.3.2
2.4.4
2.4.4.1
2.4.4.2
2.4.5

Cationic Dyes as Chromophores 44
Introduction 44
General Synthesis 45
Chemical Structure and Classification 45
Dyes with Delocalized Charge 45
Dyes with Localized Charge 49
Principal Properties 52
Cationic Dyes for Synthetic Fibers 52

Cationic Dyes for Paper, Leather, and Other Substrates
References 55

2.5
2.5.1
2.5.2
2.5.3
2.5.3.1
2.5.3.2
2.5.3.3
2.5.3.4

Polymethine and Related Chromophores 56
Introduction 56
General Synthesis 57
Principal Properties and Classification 57
Azacarbocyanines 57
Hemicyanines 57
Diazahemicyanines 58
Styryl D yes 58

38

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Contents

2.6

2.6.1
2.6.2
2.6.3
2.6.4
2.6.5

Di- and Triarylcarbenium and Related Chromophores 59
Introduction 59
Chromophores 60
General Synthesis 62
Principal Properties 65
References 67

2.7
2.7.1
2.7.2
2.7.3
2.7.4
2.7.4.1
2.7.4.2
2.7.4.3
2.7.5

Phthalocyanine Chromophore 68
Introduction 68
General Synthesis 70
Principal Properties 72
Industrial Production 73
Copper Phthalocyanine 73
Phthalocyanine Derivatives 74

Pthalocyanine Sulfonic Acids and Sulfonyl Chlorides
References 76

2.8
2.8.1
2.8.2
2.8.3
2.8.3.1
2.8.3.2
2.8.3.3
2.8.4
2.8.5

Sulfur Compounds as Chromophores 78
Introduction 78
Chromophores 79
General Synthesis 79
Sulfur Bake and Polysulfide Bake Dyes 79
Polysulfide Melt Dyes 81
Pseudo Sulfur Dyes 83
Principal Properties 84
References 84

2.9
2.9.1
2.9.2
2.9.2.1
2.9.2.2
2.9.3
2.9.3.1

2.9.3.2
2.9.3.3
2.9.4

Metal Complexes as Chromophores 85
Introduction 85
Azo/A zomethine Complex D yes 86
General Synthesis 86
Principal Properties 92
Formazan Dyes 97
Introduction 97
General Synthesis 98
Principal Properties 102
References 105

2.10

Fluorescent Dyes

2.11
2.11.1
2.11.2
2.11.3
2.11.4

Other Chromophores 109
Quinophthalone Dyes 109
Nitro and Nitroso Dyes 110
Stilbene D yes 111
Formazan Dyes 111

107

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VIII

Contents

2.11.5
2.11.6

Triphenodioxazine Dyes
References 112

112

3

Dye Classes For Principal Applications

3.1
3.1.1
3.1.2
3.1.2.1
3.1.2.2

3.1.2.3
3.1.3
3.1.3.1
3.1.3.2
3.1.3.3
3.1.3.4
3.1.3.5
3.1.3.6
3.1.4
3.1.5
3.1.5.1
3.1.5.2
3.1.5.3
3.1.5.4
3.1.5.5
3.1.6
3.1.7

Reactive Dyes 113
Introduction 113
Chemical Constitution of Reactive Systems 114
Mono-Anchor Dyes 114
Double-Anchor D yes 117
Multiple-Anchor Dyes 118
Dye Classes (Chromogens) for Reactive Dyes 118
Azo Dyes 119
Metal-Complex Azo D yes 119
Anthraquinone D yes 119
Triphenodioxazine Dyes 120
Formazan Dyes 122

Phthalocyanine Dyes 122
Synthesis 123
Examples of Commercially Available Dyes 129
Azo Dyes 129
Metal Complex Azo D yes 130
Formazan Dyes 130
Anthraquinone D yes 130
Diphenodioxazine Dyes 131
Forms of Supply 131
References 132

3.2
3.2.1
3.2.2
3.2.2.1
3.2.2.2
3.2.2.3
3.2.3
3.2.3.1
3.2.3.2
3.2.3.3
3.2.3.4
3.2.4
3.2.5
3.2.5.1
3.2.5.2
3.2.5.3

Disperse Dyes 134
Introduction 134

Chemical Constitution 135
Azo Dyes 135
Anthraquinone D yes 138
Other Chromophores 139
Synthesis 144
Monoazo Dyes 144
Disazo Dyes 145
Anthraquinone D yes 145
Other Chromophores 145
Aftertreatment 145
Examples of Commercially Available Dyes
Monoazo Dyes 146
Disazo Dyes 154
Anthraquinone D yes 155

113

146


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Contents

3.2.5.4
3.2.6

Other Chromophores
References 156

155

3.3
3.3.1
3.3.2
3.3.2.1
3.3.2.2
3.3.2.3
3.3.3
3.3.3.1
3.3.3.2
3.3.3.3
3.3.3.4
3.3.4
3.3.4.1
3.3.4.2
3.3.4.3
3.3.4.4
3.3.5
3.3.5.1
3.3.5.2
3.3.5.3
3.3.5.4
3.3.6
3.3.6.1
3.3.6.2
3.3.6.3
3.3.6.4
3.3.6.5
3.3.6.6
3.3.6.7

3.3.7

Direct D yes 158
Introduction 158
Chemical Constitution 159
Structural Characteristics 159
Precursors 159
Classification According to the Method of Application
Dye Classes 161
Monoazo Dyes 161
Disazo Dyes 162
Trisazo Dyes 164
Tetrakisazo Dyes 165
Synthesis 168
Monoazo Dyes 168
Disazo Dyes 169
Trisazo Dyes 170
Anthraquinone D irect Dyes 172
Direct D yes with Aftertreatment 172
Aftertreatment with Cationic Auxiliaries 173
Aftertreatment with Formaldehyde 174
Diazotization Dyes 174
Aftertreatment with Metal Salts 175
Examples of Commercially Available Dyes 175
Monoazo Dyes 175
Disazo Dyes 176
Trisazo Dyes 176
Tetrakisazo Dyes 176
Condensation Dyes 177
Direct D yes with a U rea Bridge 177

Triazinyl Dyes 177
References 178

3.4
3.4.1
3.4.2
3.4.2.1
3.4.2.2
3.4.2.3
3.4.3
3.4.3.1
3.4.3.2
3.4.3.3
3.4.3.4
3.4.3.5

Anthraquinone D yes 178
Introduction 178
Chemical Constitution and Properties 180
Disperse Dyes 180
Vat Dyes 187
Acid Dyes 195
Synthesis 200
Introduction 200
Anthraquinonesulfonic A cids 200
Haloanthraquinones 201
Nitroanthraquinones 201
Aminoanthraquinones 201

161

IX


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X

Contents

3.4.3.6
3.4.4
3.4.5

Hydroxyanthraquinones 202
Examples of Commercially Available Dyes
References 203

3.5
3.5.1
3.5.2
3.5.2.1
3.5.2.2
3.5.3
3.5.3.1
3.5.3.2
3.5.4
3.5.4.1
3.5.4.2
3.5.4.3
3.5.5

Indigoid Dyes 204
Introduction 204
Chemical Constitution and Properties 205
Physical Properties 205
Chemical Properties 206
Synthesis 207
Chemical Synthesis 207
Biotechnological Synthesis 211
Commercially Available Dyes 213
Indigo, C.I. Vat Blue 1 , 73000, [482-89-3] 213
Halogen Derivatives 213
Other Indigo Derivatives 214
References 214

3.6
3.6.1
3.6.2
3.6.3
3.6.3.1
3.6.3.2
3.6.3.3
3.6.4
3.6.4.1
3.6.4.2
3.6.4.3

Sulfur Dyes 215
Introduction 215
Chemical Constitution 216

Synthesis 216
Sulfur and Polysulfide Bake or Dry Fusion 216
Polysulfide Melt, Solvent Reflux, or Reflux Thionation Process
Indophenols 219
Modifications; Commercial Forms; Types of Sulfur Dyes 223
C.I. Sulphur Dyes 224
C.I. Leuco Sulphur Dyes 224
C.I. Solubilised Sulphur Dyes
(Bunte Salts, S-Aryl Thiosulfate Dyes) 224
Pseudo (Synthetic) Sulfur Dyes 225
Commercially Available Dyes 226
References 226

3.6.5
3.6.6
3.6.7
3.7
3.7.1
3.7.2
3.7.2.1
3.7.2.2
3.7.2.3
3.7.2.4
3.7.2.5
3.7.2.6

202

219

Cationic Azo Dyes 227
Introduction 227
Chemical Constitution and Synthesis 227
Cationic Charge in the Coupling Component 227
Cationic Charge in the Diazo Component 237
Different Cationic Charges in Both the Coupling and the Diazo
Component 244
Introduction of Cationic Substituents into Preformed Azo Dyes 245
Cationic Dyes with Sulfur or Phosphorus as Charge-Carrying
Atoms 246
Dyes with Releasable Cationic Groups 247


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Contents

3.7.3
3.7.4
3.7.5

Synthesis 248
Examples of Commercially Available Dyes
References 250

3.8
3.8.1
3.8.2
3.8.2.1
3.8.2.2
3.8.2.3

3.8.2.4
3.8.2.5
3.8.3
3.8.4
3.8.5

Cationic Methine Dyes 254
Introduction 254
Chemical Constitution and Synthesis 254
Streptocyanine Dyes 254
Hemicyanine Dyes 255
Higher Vinylogues of Hemicyanine Dyes 260
Phenylogous Hemicyanine Dyes 261
Cyanine Dyes 268
Synthesis 271
Examples of Commercially Available Dyes 272
References 273

3.9
3.9.1
3.9.2
3.9.2.1
3.9.2.2
3.9.2.3
3.9.3
3.9.4

Acid Dyes (Anionic Azo Dyes) 276
Introduction 276
Chemical Constitution and Synthesis 277

Wool Dyes 278
Polyamide Dyes 289
Silk Dyes 291
Examples of Commercially Available Dyes
References 294

3.10
3.10.1
3.10.2
3.10.2.1
3.10.2.2
3.10.2.3
3.10.2.4
3.10.3
3.10.4

Solvent Dyes 295
Introduction 295
Chemical Constitution and Application Properties
Alcohol- and Ester-Soluble Dyes 295
Fat- and Oil-Soluble Dyes 297
Dyes Soluble in Polymers 298
Solvent Dyes for Other Applications 299
Examples of Commercially Available Dyes 300
References 301

3.11
3.11.1
3.11.2
3.11.2.1

3.11.2.2
3.11.2.3
3.11.2.4
3.11.2.5
3.11.2.6
3.11.3

Metal-Complex Dyes 302
Introduction 302
Chemical Constitution and Synthesis 304
Chromium and Cobalt Complexes for Wool and Polyamides
Metal Complexes for Cotton (see also Section 3.1) 311
Metal Complexes for Leather (see also Section 5.1) 313
Copper Complexes for Paper (see also Section 5.3) 315
Metal-Complex Dyes for Polypropylene 316
Formazan Dyes 316
Miscellaneous U ses 319

248

291

295

304

XI


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XII

Contents

3.11.3.1 Azo Metal-Complex D yes
3.11.3.2 Formazan Dyes 324
3.11.4
References 327

319

3.12
3.12.1
3.12.2
3.12.3
3.12.3.1
3.12.3.2
3.12.4
3.12.5

Naphthoquinone and Benzoquinone Dyes 329
Introduction 329
Benzoquinone D yes 330
1,4-Naphthoquinone Dyes 331
Simple 1,4-Naphthoquinones 331
Heteroannelated 1,4-Naphthoquinones 332
1,5-Naphthoquinones 335
References 338

4

Textile Dyeing

4.1
4.1.1
4.1.1.1
4.1.1.2
4.1.1.3
4.1.1.4
4.1.1.5
4.1.2
4.1.3
4.1.4

Introduction 339
Dyeing Technology 340
Principles of Dyeing 341
Bath Dyeing Technology 342
Continuous and Semicontinuous D yeing
Printing 345
Dispensing Dyes and Chemicals 345
Standardization of Textile D yes 346
Colorfastness of Textiles 348
Laboratory Dyeing Techniques 349

4.2
4.2.1
4.2.2
4.2.3
4.2.4

Reactive Dyes on Cellulose and O ther Fibers 349
Fundamentals 350
Dyeing Techniques for Cellulose 353
Reactive Dyes on Wool, Silk and Polyamide Fibers
Reactive Dyes for Printing on Cellulose 357

4.3
4.3.1
4.3.2
4.3.3
4.3.4
4.3.5

Direct D yes on Cellulosic Fibers 358
Dyeing Principle 358
Dyeing Parameters 359
Dyeing Techniques 360
Aftertreatment 361
Direct D yes for Fiber Blends 361

4.4
4.4.1
4.4.2
4.4.2.1
4.4.2.2

Anthraquinone Vat D yes on Cellulosic Fibers 362
Principles of Vat Dyeing 362
The Vat Dyeing Process 363

Vatting 363
Dye Absorption in the Exhaustion Process 364

339

343

356


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Contents

4.4.2.3
4.4.2.4
4.4.3
4.4.4

Oxidation 364
Aftertreatment (“Soaping”) 365
Dyeing Techniques 365
Vat Dyes for Fiber Blends 367

4.5

Leuco Esters of Vat Dyes on Cellulosic Fibers

4.6
4.6.1
4.6.2

Dyeing with Indigo (see 2.3, 3.5) 368
Dyeing Technique on Cotton 368
Indigo on Wool 369

4.7
4.7.1
4.7.2
4.7.3
4.7.4
4.7.5

Sulfur Dyes on Cellulosic Fibers 370
Types and Mode of Reaction 370
Additives to the D ye Bath 371
The Dyeing Process 372
Dyeing Techniques 373
Combination with O ther Dyes 375

4.8
4.8.1
4.8.2
4.8.3

Azo (Naphtol AS) Dyes on Cellulosic Fibers 375
Application of Azo Dyes 375
Dyeing Processes on Cellulosic Fibers 376
Printing with Azo (Naphtol A S) Dyes on Cellulosic Fibers 377

4.9

4.9.1
4.9.2
4.9.3
4.9.4
4.9.5
4.9.6
4.9.7

Dyeing Cellulosic Fibers with Other Dye Classes 377
Mordant Dyes on Cellulosic Fibers 377
Acid Dyes on Plant Fibers 378
Basic Dyes on Cellulose 378
Oxidation Dyes on Cellulosic Fibers 378
Phthalogen D yes on Cellulosic Fibers 379
Coupling and D iazotization D yes on Cellulosic Fibers 379
Pigments and Mineral Dyes on Cellulose 380

4.10
4.10.1
4.10.2
4.10.3
4.10.4
4.10.4.1
4.10.4.2

Acid and Metal-Complex Dyes on Wool and Silk
Principles of Dyeing of Wool and Silk 381
Acid Dyes on Wool 382
Chrome Dyes on Wool 384
Metal-Complex Dyes on Wool 385

1:1 Metal-Complex Dyes 385
1:2 Metal-Complex Dyes 386

4.11
4.11.1
4.11.2
4.11.3
4.11.3.1

Acid and Metal-Complex Dyes on Polyamide 386
Chemical and Physical Structure of the Fiber 386
Interactions Between Dye and Fiber 387
Dyeing Processes with Different Classes of Dyes 388
Acid Dyes 388

367

381

XIII


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XIV

Contents

4.11.3.2 1:2 Metal-Complex Dyes 390
4.11.4
Technology of Dyeing Polyamide

391

4.12
4.12.1
4.12.1.1
4.12.1.2
4.12.2
4.12.2.1
4.12.2.2
4.12.2.3
4.12.2.4
4.12.2.5
4.12.2.6
4.12.2.7
4.12.3
4.12.4
4.12.4.1
4.12.4.2

Disperse Dyes on Polyester and Other Man-Made Fibers 392
General A spects 392
Dyeing in Aqueous Liquor 392
Thermosol Process 395
Dyeing Processes for Polyester Fibers with Disperse Dyes 396
Suitability of Disperse Dyes for Different Applications 396
Dyeing from Aqueous Dye Baths 397
Special Dyeing Processes 398
Continuous and Semicontinuous D yeing Processes 399
Dyeing of PES Microfibers 400

Dyeing of Modified PES Fibers 401
Printing wth Disperse Dyes on Man-Made Fibers 401
Aftertreatment 403
Dyeing Blends Containing Polyester Fibers 403
Polyester–Cellulose Blends 403
Polyester–Wool Blends 407

4.13
4.13.1
4.13.1.1
4.13.1.2
4.13.2
4.13.3

Disperse Dyes on Other Fibers 409
Disperse Dyes on Cellulose Acetate 409
Dyeing Processes for Cellulose 2.5 A cetate 409
Dyeing Processes for Cellulose Triacetate 410
Disperse Dyes on Polyamide Fibers 410
Disperse Dyes on Other Fibers 411

4.14
4.14.1
4.14.2
4.14.3
4.14.4
4.14.5
4.14.6
4.14.7
4.14.8

Cationic Dyes on Acrylic Fibers 412
General A spects 412
Cationic Dyes 412
Retarders and Auxiliaries 413
Exhaustion Process 414
Dyeing of Special Fiber Types with Cationic Dyes by the
Exhaustion Process 416
Continuous Processes with Cationic Dyes 417
Cationic Dyes on Aramide Fibers 418
Cationic Dyes in Fiber Blends 419

4.15

References

5

Nontextile Dyeing

5.1
5.1.1

Leather Dyes 427
Introduction 427

421
427

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Contents

5.1.2
5.1.2.1
5.1.2.2
5.1.2.3
5.1.3
5.1.3.1
5.1.3.2
5.1.3.3
5.1.4
5.1.4.1
5.1.4.2
5.1.5
5.1.5.1
5.1.5.2
5.1.5.3
5.1.5.4
5.1.5.5
5.1.6
5.1.6.1
5.1.6.2
5.1.6.3
5.1.7
5.1.8
5.1.9
5.1.10
5.1.11

Color Selection 428
Aniline Leather 428
Pigmented Leather 429
Colour Index 429
Natural and Mordant Dyes 431
Tanning Agents 431
Dyewood 432
Synthetic Mordant Dyes 433
Basic Dyes 433
Azine Dyes 433
Other Cationic (Basic) Dyes 434
Acid Dyes 434
Amphoteric Dyes 435
Anthraquinone D yes 435
Low-Molecular Azo Dyes 436
Resorcinol Azo Dyes 437
Azo Metal-Complex D yes 437
Direct D yes 439
Condensation Dyes 439
Polyazo Dyes 440
Phthalocyanine Dyes 440
Sulfur Dyes 441
Reactive Dyes 442
Solvent Dyes 443
Pigments 444
References 445

5.2
5.2.1
5.2.1.1

5.2.1.2
5.2.1.3
5.2.1.4
5.2.1.5
5.2.1.6
5.2.1.7
5.2.1.8
5.2.2
5.2.2.1
5.2.2.2
5.2.2.3
5.2.2.4
5.2.2.5
5.2.2.6
5.2.2.7

Fur D yes 446
Introduction 446
Origin of Fur 446
Animal Rights 447
Fur H air and Classification 448
Fur D ressing 448
Fur Finishing 448
The Final Stage 449
Garments and Fashion 450
Labels 450
Fur D yeing 451
History and Outlook 451
Color Selection and Colour Index
Vegetable Dyes 451

Oxidation Bases 452
Disperse Dyes 453
Acid and Direct D yes 454
Metal-Complex Dyes 456

451

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XVI

Contents

5.2.2.8
5.2.3

Other Synthetic Dyes
References 458

457

5.3
5.3.1
5.3.2
5.3.3
5.3.3.1
5.3.3.2
5.3.4

5.3.5
5.3.6
5.3.7
5.3.8
5.3.9

Paper D yes 459
Introduction 459
Classification of Paper Dyes 460
Direct D yes 460
Anionic Direct Dyes 461
Cationic Direct D yes 466
Acid Dyes 469
Cationic (Basic) Dyes 470
Sulfur Dyes 471
Organic Pigments 472
Special Requirements for Paper Dyes
References 472

5.4
5.4.1
5.4.2
5.4.3
5.4.3.1
5.4.3.2
5.4.3.3
5.4.3.4
5.4.3.5
5.4.3.6
5.4.3.7

5.4.4
5.4.5
5.4.6
5.4.7

Hair Dyes 473
Bleaching 473
Dyeing with Oxidation Dyes 475
Dye Classes 479
Direct D yes 479
Nitro Dyes 479
Cationic (Basic) Dyes (see Sections 3.7 and 3.8)
Anionic (Acid) Dyes (see Section 3.9) 480
Disperse Dyes (see Section 3.2) 480
Dyeing with Inorganic Compounds 480
Other Dyes 481
Product Forms 481
Dye-R emoval Preparations 483
Testing Hair Dyes 483
References 484

5.5
5.5.1
5.5.1.1
5.5.1.2
5.5.2
5.5.3
5.5.4
5.5.5
5.5.5.1

5.5.5.2
5.5.5.3
5.5.5.4
5.5.6

Food Dyes 486
Introduction 486
Specifications 487
Uses and Individual Substances 487
Synthetic Dyes Approved for Coloring of Foodstuffs
Examples of Chemical Structures 489
Purity Requirements 491
Legal Aspects 492
Codex Alimentarius 492
EU and other European Countries 492
USA 493
Japan 494
References 494

472

480

487


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Contents

5.6

5.6.1
5.6.2
5.6.2.1
5.6.2.2
5.6.3
5.6.3.1
5.6.3.2
5.6.3.3
5.6.4
5.6.4.1
5.6.4.2
5.6.5
5.6.6

Ink Dyes 495
Introduction 495
Application Principles 495
Ink-Jet Technology 495
Writing, Drawing and Marking Materials 497
Dye Classes 497
Dyes for Ink-Jet Application 497
Dyes for Writing, Drawing, and Marking 501
Fields of Application for Ink-Jet Printing 502
Inks 503
Ink-Jet Inks 503
Writing, Drawing, and Marking Inks 505
Properties of Ink-Jet Prints 507
References 508

5.7

5.7.1
5.7.1.1
5.7.1.2
5.7.1.3
5.7.1.4
5.7.1.5
5.7.2
5.7.3
5.7.4
5.7.4.1
5.7.4.2
5.7.4.3
5.7.4.4
5.7.4.5
5.7.5
5.7.5.1
5.7.5.2
5.7.5.3
5.7.6
5.7.7
5.7.8
5.7.9
5.7.10

Photographic Dyes 509
Cyanine Dyes 509
Introduction 509
Fundamental Aspects 509
Application of Sensitizing D yes 511
Production of Sensitizing Dyes 512

Cyanine Dyes as Sensitizers 512
Merocyanine Dyes 515
Oxonol Dyes 516
Azomethine and Indoaniline Image Dyes 516
Introduction 516
Color Developers 517
Yellow Azomethine Dyes 517
Magenta Azomethine Dyes 518
Cyan Indoaniline Dyes 518
Azo Dyes 519
Diffusion-Transfer Imaging Systems 519
Silver Dye Bleach Processes 520
Color Masking 520
Metallized D yes 521
Xanthene Dyes 521
Triarylmethane Dyes 522
Anthraquinone D yes 523
References 523

5.8
5.8.1
5.8.2
5.8.3
5.8.3.1

Indicator Dyes 526
Introduction 526
General Principles 526
Classes of Indicators 527
ph Indicators 527

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Contents

5.8.3.2
5.8.3.3
5.8.4
5.8.4.1
5.8.4.2
5.8.5

Redox Indicators 537
Metal Indicators 537
Indicator Papers 540
Bleeding Indicator Papers 540
Nonbleeding Indicator Papers 541
References 541

6

Functional Dyes

6.1

Introduction

6.2

Interactions of Functional Dyes

6.3
6.3.1
6.3.1.1
6.3.1.2
6.3.1.3
6.3.1.4
6.3.2
6.3.2.1
6.3.2.2
6.3.3
6.3.3.1
6.3.3.2
6.3.3.3
6.3.3.4
6.3.4
6.3.4.1
6.3.4.2
6.3.4.3
6.3.4.4
6.3.5
6.3.5.1
6.3.5.2

Functional Dyes by Application 545
Imaging 545

Laser Printing and Photocopying 545
Thermal Printing 551
Dyes for Ink-Jet Printing 555
Other Imaging Technologies 558
Invisible Imaging 559
Optical Data Storage 560
Other Technologies 564
Displays 566
Cathode Ray Tube 566
Liquid Crystal Displays 566
Organic Light-Emitting Devices 569
Electrochromic Displays 571
Electronic Materials 572
Organic Semiconductors 572
Solar Cells 573
Nonlinear Optical Dyes 574
Laser Dyes 576
Biomedical Applications 576
Fluorescent Sensors and Probes 577
Photodynamic Therapy 579

6.4

References

7

Optical Brighteners

7.1

7.1.1
7.1.2

Introduction 585
Physical Principles 586
Molecular Structure 588

543

543

581
585

543


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Contents

7.1.3

History of Whitening

589

7.2
7.2.1
7.2.1.1
7.2.1.2

7.2.1.3
7.2.2
7.2.3
7.2.3.1
7.2.3.2
7.2.4
7.2.4.1
7.2.4.2
7.2.5
7.2.5.1
7.2.5.2
7.2.6
7.2.7
7.2.8
7.2.9

Chemistry of Technical Products 590
Carbocycles 590
Distyrylbenzenes 590
Distyrylbiphenyls 592
Divinylstilbenes 593
Triazinylaminostilbenes 593
Stilbenyl-2 H -triazoles 596
Stilbenyl-2 H -naph tho[1,2- d]triazoles 597
Bis(1,2,3-triazol-2-yl)stilbenes 597
Benzoxazoles 598
Stilbenylbenzoxazoles 598
Bis(benzoxazoles) 599
Furans, Benzo[b]furans, and Benzimidazoles
Bis(ben zo[ b]furan-2-yl)biphenyls 601

Cationic Benzimidazoles 602
1,3-D iphenyl-2-pyrazolines 605
Coumarins 607
Naphthalimides 608
1,3,5-Triazin-2-yl Derivatives 610

7.3

Commercial Forms and Brands 610

7.4
7.4.1
7.4.2
7.4.3
7.4.4
7.4.5
7.4.6

Uses 611
General Requirements 611
Textile Industry 611
Detergent Industry 613
Paper Industry 614
Plastics and Synthetic Fibers 614
Other Uses 615

7.5
7.5.1
7.5.2

Analytical Methods and Whiteness Assessment
Analytical Methods 615
Assessment of Whitening Effect 616

7.6

Environmental A spects

7.7

References

8

Health and Safety Aspects

8.1

Introduction

616

617

625

625

601

615

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XX

Contents

8.2
8.2.1
8.2.2
8.2.3
8.2.4
8.2.4.1
8.2.4.2

Toxicology and Toxicity Assessments
Acute Toxicity 626
Sensitization 626
Mutagenicity 628
Carcinogenicity 629
Introduction 629
Metabolism of Azo Dyes 630

626

8.3
8.3.1

8.3.2

Environmental A ssessment / Fate 633
Introduction 633
Treatment of Dye-Containing Wastewater

8.4
8.4.1
8.4.2
8.4.3
8.4.4

Legislation 634
Registration / Notification of New Substances 634
Principal Chemical Legislation also Relevant to D yes
Special Regulations for Dyes (Colorants) 636
Material Safety D ata Sheets 638

8.5
8.5.1
8.5.2

References 639
General References 639
Specific References 639

List of Examples of Commercially Available Dyes
Index

653

633

643

635


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Preface

A great deal of single papers on color chemistry have been published over the
years. Their subjects are preferably theoretical or physico-chemical considerations of dye chemistry. On the other hand, the knowledge of dye chemistry from
a technical point of view is almost entirely concentrated in the chemical industry.
Apart from lectures given at the very few conferences on color chemistry, the current state of industrial dye chemistry can only be extracted from the patent literature. There is little else being published on dyes, especially on industrial dyes and
their applications.
This prompted us to write a reference book comprising the principal classes of
industrially produced dyes with their syntheses, properties and main applications as
well as a toxicological, ecological and legal survey of dyes.
Since the field of dyes has grown so big in recent decades, it cannot be comprehensively covered by one or only a few persons. The various authors are renowned
experts in their different fields of dye chemistry, which guarantees most competent
contributions to this book.
The book provides an overview of the present state of industrial dyes and is divided
into the following chapters: After a general survey on dyes, important dye chromophores are covered in chapter 2, followed by classification of dyes for principal applications. Chapter 4 is devoted to textile dyeing with regard to the various dye classes.
Non-textile dyeing is outlined in the next chapter. Because of their growing potential
and interest, functional dyes are reviewed in a separate chapter. Optical brighteners
make up chapter 7, and a general overview on the toxicology, ecology and legislation
of dyes forms the final chapter 8.
The literature references relating to each chapter are positioned at their respective

ends.
A comprehensive subject index should enable the reader to quickly find any sought
item.
We omitted to use trade names, but tried to designate the dyes with the C.I. Colour
Index Name, and where available, with the C.I. Constitution Number and with the
CAS (Chemical Abstracts Service) Registry Number.
This book is intended for all those who are engaged and interested in the field of
industrial dyes, especially chemists, engineers, application technicians, colorists and
laboratory assistants throughout the dye industry and at universities and technical colleges.


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XXII

Preface

I am very grateful to the authors for their dedicated cooperation for this book. My
appreciation is also extended to the Wiley-VCH publishing company for its good collaboration, in particular to Ms. Karin Sora, for her support in numerous discussions
throughout the project.

Kelkheim, November 2002

Klaus H unger


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List of Contributors

Editor

Dr. K. Hunger
Johann-Strau û -Str. 35
65779 Kelkheim/Ts.
Germany
formerly
Hoechst Aktiengesellschaft
Geschäftsbereich
Feinchemikalien und Farben
65926 Frankfurt am Main
Germany
Sections 2.1 (G regory), 2.7, 3.1, 3.2, 3.3,
3.8, 3.9, 3.10, 3.12, 5.5,
Chapter 8 (Sewekow)

Authors
Dr. W. Bauer
Masurenstr.6
63477 Maintal
Germany
Section 5.6
Dr. H. Berneth
Bayer AG
Farbenforschung SP-FE-PE
Geb. I1
51368 Leverkusen
Germany
Section 2.4

Dr. T. Clausen
Wella AG

Geschäftsleitung
Berliner Allee 65
64274 Darmstadt
Germany
Section 5.4
Dr. A. Engel
R & D PTD DyStar Textilfarben
GmbH & Co.
Deutschland KG
Kaiser-Wilhelm Allee
P.O. Box 100480
57304 Leverkusen
Germany
Section 3.7 (Hunger, Kund e)
Dr. M. Filosa
Polaroid Research Laboratories
Polaroid Corporation
Cambridge, MA 02139
USA
Section 5.7
Dr. P. Gregory
Avecia Research Center
Avecia Ltd.
Blackley Manchester M9 8Z S
UK
Sections 2.1 (H unger), 2.2, 2.5, 2.6,
2.10, 2.11, Chapter 6


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XXIV

List of Contributors

Dr. J. Griffiths
The University of Leeds
Dept. of Colour Chemistry
Leeds LS2 9JT
UK
Section 3.12 (Hunger)

Dr. P. Miederer
BASF AG,
Abt.EFF/AI - D 306
67056 Ludwigshafen
Germany
Sections 2.3, 3.5

Dr. R. Hamprecht
DyStar Textilfarben GmbH & Co.
Deutschland KG
BU D-F & E, Geb. 11
51304 Leverkusen
Germany
Section 3.2

Dr. R. Pedrazzi
Clariant (Schweiz) AG
Head R&D D ystuffs
Rothausstr. 61

CH-4132 Muttenz
Switzerland
Section 5.3

Dr. C. Heid
Lauterbacher Str.10
60386 Frankfurt
Germany
Sections 2.8, 3.6

Dr. A. G. Püntener
TLF France S. A.
4, rue de l’industrie
Boite Postale 310
F-68333 Huningue Cedex
France
Sections 5.1, 5.2

Dr. J. Kaschig
Ciba Speciality Chemicals
K-24.4.18
Klybeckstrasse
CH-4002 Basel
Switzerland
Chapter 7
Dr. K. Kunde
Bayer AG
SP-FE-PV 1
51368 Leverkusen
Section 3.7 (Engel, Hung er)

Dr. H. Leube
Grünberger Str. 6
67117 Limburgerhof
Germany
Chapter 4
Dr. W. Mennicke
Steglitzer Str. 8
51375 Leverkusen
Germany
Sections 2.9, 3.11

Dr. E. Ross
Merck KGaA
USF/Z RW
64271 Darmstadt
Germany
Section 5.8
Dr. Sewekow
Bayer AG, GB Farben Marketing
Allg.Technik
51368 Leverkusen
Germany
Chapter 8 (Hunger)