Industrial Coloration of Plastics

Pigments Dyestuffs Fillers and

Nanomaterials 1st Edition Günter
Etzrodt
Visit to download the full and correct content document:
https://ebookmeta.com/product/industrial-coloration-of-plastics-pigments-dyestuffs-fill
ers-and-nanomaterials-1st-edition-gunter-etzrodt/
More products digital (pdf, epub, mobi) instant
download maybe you interests ...

Inorganic Pigments Pfaff G

https://ebookmeta.com/product/inorganic-pigments-pfaff-g/

Sustainable Plastics Environmental Assessments of

Biobased Biodegradable and Recycled Plastics 2nd
Edition Joseph P. Greene

https://ebookmeta.com/product/sustainable-plastics-environmental-
assessments-of-biobased-biodegradable-and-recycled-plastics-2nd-
edition-joseph-p-greene/

Plastics and Sustainability Grey is the New Green

Exploring the Nuances and Complexities of Modern
Plastics 2nd Edition Tolinski

https://ebookmeta.com/product/plastics-and-sustainability-grey-
is-the-new-green-exploring-the-nuances-and-complexities-of-
modern-plastics-2nd-edition-tolinski/

Illustrated Manual of Injectable Fillers Neil S. Sadick

https://ebookmeta.com/product/illustrated-manual-of-injectable-
fillers-neil-s-sadick/
The Sage Encyclopedia of Industrial and Organizational
Psychology 2nd Edition Steven G. Rogelberg

https://ebookmeta.com/product/the-sage-encyclopedia-of-
industrial-and-organizational-psychology-2nd-edition-steven-g-
rogelberg/

Chess Explained The c3 Sicilian 1st Edition Sam Collins

https://ebookmeta.com/product/chess-explained-
the-c3-sicilian-1st-edition-sam-collins/

Starting Out The c3 Sicilian 1st Edition John Emms

https://ebookmeta.com/product/starting-out-the-c3-sicilian-1st-
edition-john-emms/

The Paper Issue 83 1st Edition Origamiusa

https://ebookmeta.com/product/the-paper-issue-83-1st-edition-
origamiusa/

Chemistry of Nanomaterials Volume 1 B Metallic

Nanomaterials Part B 1st Edition Unknown

https://ebookmeta.com/product/chemistry-of-nanomaterials-
volume-1-b-metallic-nanomaterials-part-b-1st-edition-unknown/
Etzrodt
Industrial Coloration of Plastics
Günter Etzrodt

Industrial
Coloration of
Plastics
Pigments, Dyestuffs, Fillers, and
Nanomaterials

Translated by Nora Catalina Restrepo-Zapata

Hanser Publishers, Munich

The Author:
Dr. rer. nat Günter Etzrodt
Pigments.Consulting UG (haftungsbeschränkt)
Rebmannstraße 6
D-70180 Stuttgart
Germany
www.pigments-consulting.com

:Für bearbeitungen im DTP

PROOF, ANJA, BERND :
21-Feb-19 : Page: 1

®
MIX
Papier aus verantwor-
tungsvollen Quellen

www.fsc.org FSC® C083411

Distributed by:
Carl Hanser Verlag
Postfach 86 04 20, 81631 Munich, Germany
Fax: +49 (89) 98 48 09
www.hanserpublications.com
www.hanser-fachbuch.de

The use of general descriptive names, trademarks, etc., in this publication, even if the former are not especially
identified, is not to be taken as a sign that such names, as understood by the Trade Marks and Merchandise Marks
Act, may accordingly be used freely by anyone. While the advice and information in this book are believed to be true
and accurate at the date of going to press, neither the authors nor the editors nor the publisher can accept any legal
responsibility for any errors or omissions that may be made. The publisher makes no warranty, express or implied,
with respect to the material contained herein.

The final determination of the suitability of any information for the use contemplated for a given application r­ emains
the sole responsibility of the user.

All rights reserved. No part of this book may be reproduced or transmitted in any form or by any means, electronic
or mechanical, including photocopying or by any information storage and retrieval system, without permission in
writing from the publisher.

© Carl Hanser Verlag, Munich 2022

Editor: Mark Smith
Production Management: Cornelia Speckmaier
Coverconcept: Marc Müller-Bremer, www.rebranding.de, Munich
Coverdesign: Max Kostopoulos
Typesetting: Eberl & Kœsel Studio GmbH, Altusried-Krugzell, Germany
Printed and bound by CPI books GmbH, Leck
Printed in Germany

ISBN: 978-1-56990-852-5
E-Book ISBN: 978-1-56990-853-2
ePub ISBN: 978-1-56990-854-9
Dedicated to Heidi
The Author

Dr. rer. nat. Günter Etzrodt, chemist, is the CEO and owner of Pigments Consulting
UG (Limited) based in Stuttgart, Germany. He founded the company Pigments Con-
sulting UG (Limited) after 35 years at BASF SE. He gained experience in pigment
research, process engineering, pigment production, patent management, and ad-
vanced training in management positions. He was the chairman of the DIN stan-
dardization committee “Pigments and Fillers” and the ISO TC 356 for many years.
He advises pigment producers, masterbatchers, paint factories, and other users of
pigments. In quality management, his focus is on the creation of “Food Contact
Certificates” and safety data sheets.
The consulting services include problem solutions for product, process, and pro-
cess development, product testing, creation of test regulations, and product ana­
lysis. He also advises on patent issues and prepares the registration documents for
patents and utility models.
He also offers technical seminars on the use of pigments and fillers in coatings and
on plastic coloring.
VIII  The Author

Pigments.Consulting UG
(haftungsbeschränkt)
Dr. rer. nat. Günter Etzrodt
Stuttgart, Germany
www.pigments-consulting.com
Contents

The Author . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . VII

1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

2 Color and Color Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

2.1 Basics of Color Measurement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
2.1.1 Spectrophotometer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.2 CIELAB Method . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
2.1.3 Influences of Sample Quality and Temperature
during Color Measurement [3] . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

3 Plastic Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.1 History of Development . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
3.2 Thermoplastic Polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
3.2.1 Chemical Composition and Material Properties . . . . . . . . . . . . . . . . 18
3.2.1.1 Polyvinyl Chloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.1.2 Polyolefins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
3.2.1.3 Styrene Polymers and Copolymers . . . . . . . . . . . . . . . . . . . . 19
3.2.1.4 Acrylic Resins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
3.2.1.5 Polyamide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.2.1.6 Polycarbonate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.2.1.7 Other Thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
3.3 Bioplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23

4 Basics of Colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.1 General Characteristics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
4.2 Colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 28
X Contents

4.3 Requirements for Color Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31

4.4 Color Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32

5 Colorant Properties and Test Methods . . . . . . . . . . . . . . . . . . . . . . . 33

5.1 Color Strength . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
5.2 Transparency/Glaze . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.3 Opacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
5.4 Chemical Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
5.5 Light Fastness/Weather Fastness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
5.6 Thermal Resistance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
5.7 Migration Fastness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5.8 Shrinkage/Warpage . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
5.9 Abrasiveness . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.10 Dispersibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 51
5.11 Viscosity Behavior in the Plastic Melt (Melt Flow Index) . . . . . . . . . . . . . 53
5.12 Metamerism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 54
5.13 pH Value . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
5.14 Conductivity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56

6 Inorganic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
6.1 White Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 65
6.2 Black Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 69
6.3 Color Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.3.1 Blue Inorganic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 76
6.3.2 Yellow and Brown Inorganic Pigments . . . . . . . . . . . . . . . . . . . . . . . 79
6.3.3 Green Inorganic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
6.3.4 Red/Orange Inorganic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
6.3.5 Violet Inorganic Colored Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . 94

7 Functional Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
7.1 Metal Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
7.2 Pearlescent Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
7.3 Other Effect Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
7.3.1 Bismuth Oxychloride . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
7.3.2 Glass Pearls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
Contents XI

7.4 Conductive Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112

7.5 Laser Technology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
7.5.1 Pigments for Laser Marking . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 113
7.5.2 Laser Welding of Thermoplastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115
7.6 Photoluminescent (Afterglow) Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7.6.1 Phosphorescent Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
7.7 Functional Pigments for Thermal ­Management . . . . . . . . . . . . . . . . . . . . . 120
7.8 Effect Colorants . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.8.1 Fluorescent Colors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
7.8.2 Optical Brighteners . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
7.8.3 Thermal Colors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 126

8 Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
8.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
8.2 Fillers for Plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
8.3 Influence of Fillers on the Properties of Finished Parts . . . . . . . . . . . . . . 132
8.4 Manufacture of Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 136
8.5 Properties of Important Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137
8.6 Functional Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
8.7 Other Fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
8.8 Plastic-Technological Properties of Important Fillers . . . . . . . . . . . . . . . . . 146

9 Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
9.1 Blue Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
9.2 Yellow Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 164
9.3 Green Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
9.4 Orange Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
9.5 Red Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
9.6 Violet Dyes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186

10 Organic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193

10.1 Azo Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
10.1.1 Monoazo Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
10.1.1.1 Monoacetoacetaryl Pigments . . . . . . . . . . . . . . . . . . . . . . . . 197
XII Contents

10.1.1.2 β-Naphthol Pigments/Naphthol Pigments . . . . . . . . . . . . . . 200

10.1.1.3 Benzimidazolone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . 211
10.1.2 Disazo Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.1.2.1 Disazodiarylide Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.1.2.2 Bisacetoacetarylide Pigments . . . . . . . . . . . . . . . . . . . . . . . . 233
10.1.2.3 Disazopyrazolone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . 234
10.1.3 Laked Azo Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
10.1.3.1 β-Naphthol Pigment Lakes . . . . . . . . . . . . . . . . . . . . . . . . . . . 247
10.1.3.2 Monoacetoacetarylide Pigments . . . . . . . . . . . . . . . . . . . . . . 258
10.1.3.3 Pyrazolone Pigment Lakes . . . . . . . . . . . . . . . . . . . . . . . . . . . 262
10.2 Polycyclic Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 264
10.2.1 Phthalocyanine Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 265
10.2.2 Quinacridone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 270
10.2.3 Perylene Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
10.2.4 Perinone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
10.2.5 Thioindigo Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 282
10.2.6 Dioxazine Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 284
10.2.7 Diketo-Pyrrolo-Pyrrole Pigments (DPP) . . . . . . . . . . . . . . . . . . . . . . . 286
10.3 Miscellaneous Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
10.3.1 Metal Complex Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 293
10.3.2 Isoindoline/Isoindolinone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . 298
10.3.3 Aminoanthraquinone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 304
10.3.4 Indanthrone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 306
10.3.5 Flavanthrone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 307
10.3.6 Pyranthrone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 308
10.3.7 Quinophthalone Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 309
10.3.8 Additional Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 310

11 Additives for Polymer Processing . . . . . . . . . . . . . . . . . . . . . . . . . . . 317

11.1 Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 319
11.2 Long-Term Thermal Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 324
11.3 UV Stabilizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
11.4 Flame Retardant Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 325
11.5 Antistatic Additives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 327
Contents XIII

11.6 Anti-Blocking Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 328

11.7 Nucleating Agents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
11.8 Antimicrobial Substances . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 329
11.8.1 Biocidal Active Ingredients . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 330
11.8.2 Test Procedure for Biocidal Effect . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
11.9 Blowing Agent . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 331
11.10 Plasticizers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 333
11.11 Dispersants, Lubricants, and Release Agents . . . . . . . . . . . . . . . . . . . . . . 336

12 Pigment Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 339

12.1 Preparation Type . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 340
12.1.1 Monopigment Preparations, Color Concentrates . . . . . . . . . . . . . . . 340
12.1.2 Granulate Preparations/Masterbatches . . . . . . . . . . . . . . . . . . . . . . . 342
12.1.3 Liquid Colors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 347
12.1.4 Powder Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 349
12.1.5 Evaluation of the Preparations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 351
12.1.6 Quality Assurance of Pigment Preparations . . . . . . . . . . . . . . . . . . . 351

13 Application Methods of Colored Plastics . . . . . . . . . . . . . . . . . . . . . 353

13.1 Injection Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 353
13.2 Extrusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 355
13.3 Blow Molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 356
13.4 Calendering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
13.5 Rotomolding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 358
13.6 Melt Spinning . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359
13.7 Processing Problems and Solutions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 359

14 Nanomaterials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 365
14.1 Definitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 366
14.2 Nanostructured Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 367
14.3 Pictures of Nanopigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
14.3.1 Phthalocyanine Pigments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
14.3.2 Nano Iron Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 368
14.3.3 Nano Titanium Dioxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 369
XIV Contents

14.3.4 Nano Zinc Oxide . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 370

14.3.5 Carbon Black . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 371
14.3.6 Nanomaterials in Plastic Food Packaging . . . . . . . . . . . . . . . . . . . . . 372
14.4 Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 372
14.4.1 How Are Nanomaterials Regulated in the EU? . . . . . . . . . . . . . . . . . 373
14.4.2 Nano-Pigments on the EU Market . . . . . . . . . . . . . . . . . . . . . . . . . . . 374

15 Quality Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377

15.1 ISO 9000 ff. Series . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 377
15.1.1 Contents of the ISO 9000 Series of Standards . . . . . . . . . . . . . . . . . 378
15.1.2 ISO 9001 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 379
15.1.3 Relationship with ISO 9004 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 380
15.1.4 ISO 9001:2015 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 382
15.1.4.1 Strategic Direction of the Organization . . . . . . . . . . . . . . . . 382
15.1.4.2 Expansion of the Target Groups . . . . . . . . . . . . . . . . . . . . . . 383
15.1.4.3 Process Management Is Becoming more Important . . . . . . 383
15.1.4.4 Distribution of Responsibilities . . . . . . . . . . . . . . . . . . . . . . . 383
15.1.4.5 Risk Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 383
15.1.4.6 Knowledge Management . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
15.1.4.7 Documentation – Paper Quality Manual Was Yesterday . . 384
15.1.4.8 Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
15.2 Environmental Management Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
15.2.1 EN ISO 14001:2009 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 384
15.3 Safety Data Sheet (SDS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 387
15.3.1 Purpose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 388
15.3.2 Format of the Safety Data Sheet . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 389

16 Chemical Safety, CLP Regulation, Toxicology . . . . . . . . . . . . . . . . . 393

16.1 REACH Regulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
16.1.1 Basics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 393
16.1.2 Scope . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 394
16.1.3 Abuse . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
16.1.4 Registration . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 395
16.1.5 Chemical Safety Report . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396
Contents XV

16.1.6 Risk Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 396

16.1.7 Internet Access to the REACH Data . . . . . . . . . . . . . . . . . . . . . . . . . . 397
16.1.7.1 Information Requirements . . . . . . . . . . . . . . . . . . . . . . . . . . 397
16.2 CLP Regulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 398
16.3 Toxicology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
16.3.1 Acute Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 401
16.3.2 Chronic Toxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 402
16.3.3 Mutagenicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
16.3.4 Teratogenicity/Embryotoxicity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
16.3.5 Generation Test . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 403
16.3.6 Ecology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 404

17 Laws and Regulations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405

17.1 Directive 2009/48/EC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 405
17.2 Safety of Toys – Part 3: Migration of Certain Elements;
EN 71-3:2021-06 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 406
17.3 EU AP (89)1 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 407
17.4 Commission Regulation (EC) No 975/2009 . . . . . . . . . . . . . . . . . . . . . . . . . 410
17.5 Commission Regulation (EU) No. 10/2011 . . . . . . . . . . . . . . . . . . . . . . . . . . 411
17.6 Directive 2002/61/EC (Azo Colorants) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 414
17.7 Directive 2011/65/EU . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 415
17.8 Food, Consumer Goods and Feed Code (LFGB) . . . . . . . . . . . . . . . . . . . . . . 416
17.9 BfR IX. (Germany) – Colorants for ­Plastics and Other Polymers
Used in Commodities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 416
17.10 Directive (EU) 2018/852 (Packaging and Packaging Waste) . . . . . . . . . . . 419
17.11 Hazardous Substances Ordinance (GefStoffV) . . . . . . . . . . . . . . . . . . . . . . 419
17.12 The Toxics in Packaging Clearinghouse (CONEG) . . . . . . . . . . . . . . . . . . . 420

Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
1 Introduction

Colors play an important role in our everyday life. We react to colors intellectually,
for example, because we have learned to only cross the street when the crossing
light is green and to wait when it is red. But we also react to colors emotionally. The
color red is perceived as a warm color and stands for energy and warmth, joy, pas-
sion, and love among other things. On the other hand, the color blue belongs to the
cold colors and is seen in connection with ice, snow, and cold emotions. Uniform
objects can be supplied to different purposes by different colors.
This book discusses pigments, dyes, and fillers for plastics and their properties,
including the processing method. An indication of the classification at the Euro-
pean Chemical Agency (ECHA) [7] is given in the case of critical toxicological
­pigment properties. The nano pigments are also discussed in detail.
The present book sets out to convey that knowledge in a straightforward and
­understandable manner, without compromising scientific objectivity and rigor.
Special attention has been given to clear topical division and structuring to facili-
tate finding pertinent information quickly. That having been said, the gamut of
available colorants and fillers is so vast that there would be insufficient space to
cover all the materials out there, some of them quite exotic.
Instead, this book concentrates on colorants and fillers in regular current use, with
numerous figures and tables to illustrate their properties and applications. All the
same, this book cannot claim to be exhaustive in scope. Readers wishing to obtain
further information and details will be served by the extensive bibliographic refer-
ences provided.
This book is intended for anyone who is professionally involved with colorants and
fillers used in plastic materials. Beginners and students will gain a comprehensive
overview of the field, while experienced developers will find practical details of
immediate relevance to solving their everyday problems.
The colorants are listed according to the internationally used Color Index [1]. The
chemistry of the respective colorant cannot be recognized from this designation.
This knowledge is essential for the colorist because he/she can already recognize
2 1 Introduction

the essential properties of the respective colorant from chemistry. For this reason,
the chemistry of individual colorants is consciously dealt with. The formulas are
listed and, for organic pigments and dyes, the structural formulas are also pre-
sented. Additionally, the CAS (Chemical Abstracts Service) and EC (European Com-
mission) numbers are given, which are useful in everyday business.
As everywhere in daily life, a series of laws and regulations must be followed, also
in the coloring of plastics. The number of these regulations has increased signifi-
cantly in recent years due to intensive toxicological research into the effects of
substances on the human organism. Thus, the properties of colorants are being
re-evaluated. The consequence can be a limitation or ban on the use of substances.
Typical examples of this are the previously widely used cadmium and lead pig-
ments, and several specific azo colorants (keyword “disazodiaryl pigments”). The
discussion about nanoparticles, and the methods of how these are to be measured,
is not yet complete. The new classifications of pigments as nanoparticles by the
ECHA are still in process. Possible carcinogenic potentials of carbon black and tita-
nium dioxide are being discussed.
There have also been significant changes in the economy. Traditional European
pigment producers were taken over by other companies or outsourced from groups.
The cost pressure has risen sharply: Chinese and Indian pigment manufacturers
are entering the market – some with good qualities.
Except for two new inorganic orange pigments, completely new pigment bases
have not come onto the market in recent years. Pigment development focuses on
improving the pigments’ application properties, such as color strength, dispersibil-
ity, temperature resistance, and on variations in the effect pigments. Issues such
as thermal management have been added.
This book discusses also the physical basics of color formation, color perception,
and color measurement. Since there is already extensive literature in this area [2]
[3] [4] [5], this topic is only highlighted selectively.
The processing techniques for plastic coloring and the production of masterbatches
and preparations are also described [6].
References for Chapter 1 3

References for Chapter 1

[1] Color Index: https://colour-index.com, January 2018
[2] Etzrodt, G.: Die Farbenwelt der Kunststoffe, Verlag Moderne Industrie, Landsberg/Lech, 2003
[3] Kittel, H.: Lehrbuch der Lacke und Beschichtungen, Band 5: Pigmente, Füllstoffe und Farbmetrik,
Hirzel Verlag Stuttgart, Leipzig, 2003
[4] Huff, K.: Visuelle Abmusterung und praktische Farbmessung in der Kunststoffindustrie, Bayer AG,
Leverkusen 1993
[5] Dicke, B., Böttner, G.: Farbe als Qualitätskriterium – Mehr als ein Seherlebnis, BYK-Gardner, GDCh
Wochenschau – Chemie und Licht, 2016
[6] Farb- und Additiv-Masterbatches in der Praxis, zweite Auflage 2006, Masterbatch Verband im Ver-
band der Mineralfarben-Industrie e. V., Frankfurt am Main, 2006
[7] ECHA: https://echa.europa.eu/search for chemicals, January 2018
2 Color and Color
Measurement

Countless color variations surround us in everyday life. The term “color” is so evi-
dent that it is easy to overlook the role that color plays in everyday life. Although
color has a fundamental impact on our lives, our knowledge of “color” and how to
use it in a controlled manner is often not sufficient – which can lead to problems
when defining or communicating product colors. The assessment often takes place
under the influence of personal feelings and experience, making a uniform assess-
ment impossible.
The human eye perceives light in the visible range. However, “light” is not the
same as “color”, but, first of all, electromagnetic radiation, which triggers nerve
impulses on the retina and which makes “seeing” possible at all. The spectrally
sensitive sensory cells of the retina transmit their signals to the brain, where this
information creates the color impression. So, color is a sensory impression in the
human brain. Visible light is a small part of existing electromagnetic waves. Differ-
ent wavelengths are perceived as different colors. Color is, therefore, a perceptual
phenomenon that depends on the observer and the conditions under which the
color is observed. However, there is no physical quantity for the determination of
colors like for length or weight.
Three things are required to perceive colors [1]:
ƒ an object,
ƒ a light source (illuminant), and
ƒ an observer.
The human brain successfully uses the color impression for object tracking and
recognition. However, the color of an object changes when the color of the illumi-
nant changes or when the object is against a different colored background.
The energy in the form of light is required to see colors. To better understand the
“color” phenomenon, we need to recognize the origin of light. Light comes from a
variety of sources and consists of electromagnetic radiation, a form of energy that
propagates in a wave motion. All visible light consists of a mixture of colors that
are put together in different proportions to form every distinctive visible light. The
6 2 Color and Color Measurement

way we measure light is spectral energy distribution, in Figure 2.1 the visual color
spectrum begins at 400 nm and ends at 700 nm wavelength. Light with wave-
length below 400 nm is called ultraviolet (UV), and that above 700 nm is called
infrared (IR). The human eye cannot perceive ultraviolet or infrared light.

White light spectrum

U
l I
t n
r f
a r
a
V
i R
o e
l d
e
t

350 400 450 500 550 600 650 700 750

Wave length [nm]

Figure 2.1 White light spectrum

White light consists of a mixture of colors, which are characterized by a specific

wavelength range. These are the colors of the spectrum – red, orange, yellow,
green, blue, and violet.
Incandescent lamps and luminescence are two ways of generating light. The incan-
descent lamp generates light from thermal energy. Heating the filament of an in-
candescent lamp to a sufficiently high temperature will cause it to glow. Lumines-
cence, also known as cold light, is light from other energy sources. It can be
generated at room temperature or even lower temperatures. Quantum physics ex-
plains luminescence as the movement of electrons from their primary state (lowest
energy level) to a state of high energy. When they return to their primary state, the
electron releases the energy in the form of a light photon. If the time interval be-
tween the two steps is short (a few microseconds), the process is called fluores-
cence. If the interval is long (a few hours), the process is called phosphorescence.
 7

The combination of these wavelengths in the light can change according to the
light source. For this reason, colors can look different under the influence of day-
light, fluorescent light, or sodium vapor lamps. Natural sunlight varies widely. It
can be very blue, especially at noon in northern latitudes. Direct sunlight is usu-
ally seen as golden, but at sunset, it can be bright red. Artificial light from sodium
vapor lamps is yellow, from mercury vapor lamps blue-green, or from an incandes-
cent lamp more or less yellow.
Several phenomena can occur when the light hits an object. With transparent ob-
jects, the electromagnetic waves pass through the object. With colorless objects,
the light passes through the objects unchanged. With colored objects, part of the
light waves is absorbed. The unabsorbed light waves are perceived as color by the
human eye.
With more or less opaque objects, part of the light waves is absorbed, the remain-
ing part is reflected. With a blue object, for example, the red part of the color spec-
trum is absorbed. The human eye then perceives the reflected blue part as a blue
color. The reflection curve of white shows approximately the same intensities near
100% reflection in all wavelengths of the spectrum.
Refraction or scattering means that the light changes direction when it passes
from one medium to another, such as from the polymer to a pigment or filler parti-
cle in a plastic part. Scattering is influenced by the difference in refractive index
between a particle and its surroundings, the particle size, and the wavelength of
the light. An opaque color ensures high scattering. A translucent color shows a
combination of reflection and scattering. Absorption occurs when most of the
wavelengths in the visible spectrum are absorbed. Black objects absorb almost all
light.
An object appears in a particular color because the light reflected from its surface
is made up of precisely the wavelengths combined to produce the observed color.
The object absorbs all other wavelengths. For example, a blue object reflects the
blue light spectrum but absorbs red, orange, yellow, green, and violet, which are
most other wavelengths. A red object reflects the red part of the spectrum, but ab-
sorbs most of the orange, yellow, green, blue, and purple.
8 2 Color and Color Measurement

Figure 2.2 Reflection and absorption of colors

Black and white colors are different from other colors in terms of how they reflect
and absorb light. A white object reflects almost all colors, while a black object com-
pletely absorbs most colors.
Other significant influences on the color of an object are shape and surface effects.
For example, an object can be spherical or square, dull or glossy, transparent,
opaque, or translucent. It can also appear metallic, pearlescent, fluorescent, or
phosphorescent. Viewing angles also affect our color perception.
The human eye is the defining observer of color. An observer almost always bases
the acceptance of a color on visual judgment. For this reason, color matching can
become very subjective, since the color view varies greatly from person to person.
Characteristics such as age, gender, inherited characteristics, and even moods can
influence the color vision [2].

„ 2.1 Basics of Color Measurement

People who believe that the eye is the most important observer of color argue that
it is possible to judge color purely by referring to color cards through visual adjust-
ment. Since each person perceives the color differently, this method is very subjec-
tive and is not suitable for an objective assessment.
In addition to genetic abnormalities, color vision changes with age due to the
build-up of yellow macular pigmentation in the eye. For this reason, it is argued
that all original colors must be based on physical measurements. However, these
2.1 Basics of Color Measurement 9

measurements and their interpretation must be closely related to the reactions of

the visual observers.
The color control is, therefore, divided into two segments: visual and instrumental.
The color measurement method using the CIELAB method, including measure-
ment with a spectrophotometer, is described below [3].

2.1.1 Spectrophotometer
One method for color measurement is the spectrophotometric method. Spectro­
photometers measure the spectral characteristics of light and use them to calculate
the standard color values based on the CIE normal observer functions. In addition
to the numerical results in different color systems, spectrophotometers allow the
graphical representation of the spectral properties of the object color. Colors are
created by mixing the different wavelengths in certain proportions. A spectro­
photometer evaluates the light reflected by the object for different wavelengths or
wavelength ranges and can display the results as a graphic.
For the measurement, the visible spectrum is broken down into small, narrowly
defined wavelength ranges, each of which is evaluated by another segment of the
sensor (e.g., 39 segments). With this method, the smallest color differences can be
determined, which remain hidden from the human eye.

2.1.2 CIELAB Method

The Commission Internationale de l’Eclairage (CIE) has set certain standard values
that are used worldwide for color measurement.
The CIELAB system, which is widely used today, consists of the Cartesian coordi-
nates a*, b* (hue), and L* (lightness). Each color can be represented by the L*, a*,
and b* values. In certain cases, the polar coordinates L*, C* (chroma, chromatic-
ity), and h° (hue angle) are also used.
10 2 Color and Color Measurement

Figure 2.3 CIELAB coordinate system [1]

The Following Points Must Be Taken into Account when Measuring Color:
ƒ Is the measuring device calibrated (“adjusted”), white/black standard clean?
ƒ Are the values of the current standard correct?
ƒ Has the measuring device been calibrated with a colorful reference sample?
ƒ ISO 9001 requires test equipment monitoring!
ƒ Is the sample translucent? => Background!
ƒ Is the sample/background fluorescent?
ƒ Edge effects with thick plastic samples must be taken into account!
ƒ Should the pigmentation or the visual appearance of the plastic article be char-
acterized?
ƒ Is the sample matt/glossy?

The Following Must Be Taken into Account when Evaluating the Color:
ƒ Which light source/standard observer is available?
ƒ Which geometry of the measurement/gauge device is used?
ƒ L a b or L* a* b*?
ƒ DE* or, e.g., DE (CMC)?
ƒ Color strength calculation: which method (“equality criterion”)?
ƒ Hiding power: which method?
2.1 Basics of Color Measurement 11

2.1.3 I nfluences of Sample Quality and Temperature during

Color Measurement [3]

Powder/Granules
When measuring powders with a spectrophotometer, the measured value depends
on the compaction and the surface. In order to avoid mistakes, some points have to
be considered. The containers (e.g., glass cuvettes) must always be of the same
type, the fill level and compaction of the powder must be constant, and the surface
smooth and comparable. If the grain size is large, it is recommended to use a spec-
trophotometer with a large measuring aperture. The measurement surface is aver-
aged with the result of reproducible measurement values.

Semi-Transparent Materials
For semi-transparent materials, the light partly passes through the layer and is
more or less reflected by the background. It must be taken into account that the
background can have a major influence on the measurement result. This influence
can be minimized by increasing the layer thickness. An opaque white background
material also ensures constant results.

Materials with a Surface Structure

Surfaces with structure and patterns lead to poorly reproducible measurement re-
sults with a small measuring aperture. Therefore, the largest possible measuring
orifice should be used. The measurement accuracy can be significantly increased
by multiple measurements at different locations on the surface and subsequent
averaging.

Influence of Temperature
With some materials, a change in temperature also results in a change in color.
This phenomenon is called thermochroism. To carry out accurate color measure-
ments, the sample and measuring device must have a constant, defined tempera-
ture, ideally by storing them in a room with a constant climate.

Sample Preparation
ƒ The preparation will influence the results!
ƒ The sample should be uniform and homogeneous, without visible particles, air
bubbles, or fingerprints.
ƒ The sample to be measured must be of uniform thickness in the case of translu-
cent and transparent samples.
ƒ The backing must be specified in this case and must be uniform as well.
12 2 Color and Color Measurement

ƒ The samples should be as flat as possible.

ƒ In the case of transparent and translucent samples, the edge loss must be consid-
ered.
ƒ The measurement direction must keep constant in case of dichroism.
ƒ Measurements should be done at room temperature – thermochromism.
ƒ Better to start with new instead of using old samples (aging).

References for Chapter 2

[1] Dicke, B., Böttner, G.: Farbe als Qualitätskriterium – Mehr als ein Seherlebnis, BYK-Gardner, GDCh
Wochenschau Chemie und Licht, 2016
[2] Etzrodt, G.: Kompendium Pigmente und Harze, Pigments Consulting UG (haftungsbeschränkt),
Stuttgart 2011, unpublished
[3] https://www5.konicaminolta.eu/en/measuring-instruments/learning-centre/colour-measurement/
precise-colour-communication.html, 2017
3 Plastic Materials

„ 3.1 History of Development

The scientific and technical development of plastics began in 1838 with the discov-
ery of polyvinyl chloride (PVC) by Victor Regnault. The name of this new working
area was established by Ernst Richard Escales in 1911 with the first publication of
the magazine Kunststoffe. Hermann Staudinger introduced the term “macromole-
cule” in 1922. Table 3.1 gives a brief historical overview of the most important de-
velopment steps in the field of plastics research and technology. The most import-
ant synthetic plastics are listed in Table 3.3.
Polymers consist of chain molecules that are synthesized by linking of smaller
components, the monomers. These can be of natural origins, such as cellulose, or
are produced by chemical syntheses, such as polystyrene. The properties of poly-
mers are based both on the length of the molecular chains and on the chemical struc-
ture. The principle of building long molecular chains applies to both natural and
synthetic polymers. The molecular structures are shown exemplarily with the two
structural formulas shown in Figure 3.1 and Figure 3.2.

Figure 3.1 Cellulose is made from a monosaccharide

14 3 Plastic Materials

Figure 3.2 Polystyrene is made from styrene monomer through polymerization

When it comes to bonding monomers, a distinction is made between condensation

and addition polymerization. The number of repeating units in a macromolecule is
called the degree of polymerization.
Depending on the type of repeating unit, the polymers can be called homopoly-
mers, which are built up from only one type of repeating. The incorporation of
chemically different monomers leads to copolymers. If two different monomers are
present, alternating, random, or block-like structures are obtained. Besides linear
chains, there are also branched and cross-linked systems. The diversity of polymer
materials is based on these different molecular architectures.
Plastics can be divided into two important groups: thermoplastics that can be de-
formed by heat and thermosets that cannot be deformed by heat. The major differ-
ence is based on the behavior of the plastic during the forming process.
When a thermoplastic is heated and pressed into a mold, there is no chemical reac-
tion involved. After the polymer has cooled and hardened in the mold, it could be
brought back into a new shape by reheating it without changing the characteristics
of the plastic noticeably.
Thermosets, on the other hand, change chemically as they are brought into their
final shape. They react in a polycondensation reaction and form a network similar
to a spatial grid. This hardening through structural changes in the molecule is
­irreversible. Once a thermoset has been molded, it cannot be changed.
Figure 3.3 gives an overview of the synthetic polymers:
3.1 History of Development 15

Synthetic Polymers

Polycondensates Polymerizates Polyadducts

Thermosets Thermoplastics Thermoplastics Thermosets

Phenolic resin Polyamide Polyethylene Epoxy resin

Urea resin Polycarbonate Polypropylene crosslinked polyurethanes
Thiourea resin Polyester Poly-1-butenes
Melamine resin Polyphenylene oxide Poly-4-methyl-1-pentene Thermoplastics
unsat. polyester resin Polysulfone Ionomers
Alkyd resin Polyvinyl acetal Polyvinyl chloride linear polyurethanes
Allyl resin Polyvinylidene chloride chlorinated polyethers
Silicone Polymethyl methacrylate
Polyimide Polyacrylonitrile
Polybenzimidazole Polystyrene
Polyacetal
Fluoroplastics
Polyvinyl alcohol
Polyvinyl acetate
Poly-p-xylylene

Figure 3.3 Synthetic polymers

Table 3.1 The History of the Development of Plastics

Year Discoverer Discovery
1838 Victor Regnault Laboratory scale polyvinyl chloride
1839 Charles Nelson Crosslink-ability of rubber with sulfur
­Goodyear
1846 to 1900 Development of cellulosic plastics
1901 Otto Röhm First work on acrylic acid and
acrylic acid esters
1912 General Electric Patenting of the first alkyd resins
1928 Otto Röhm Production of polymethyl methacrylate
1928 Erich Konrad Development of Buna S, the first all-purpose
synthetic rubber
1928 Heinz Hopf Technical production of caprolactam
1930 to 1933 IG-Farbenindustrie Start of production of polystyrene,
­ olyacrylonitrile, polyisobutylene, polyvinyl
p
chloride, and polyethylene oxide
1933 Eric W. Fawcett and High-pressure polymerization of ethylene to
Reginald O. Gibson produce LDPE
16 3 Plastic Materials

Year Discoverer Discovery

1933 to 1939 ICI Elaboration of the technical basis for the
large-scale production of polyethylene
1935 to 1938 Wallace Hume Production of the first polyamide 66 (Nylon),
­Carothers production of Nylon begins
Du Pont
1938 Paul Schlack Production of the first polyamide 6 (Perlon),
IG-Farbenindustrie Start of production of Perlon
1940 Otto Bayer Process for the production of polyurethane
1946 John R. Winfield and Discovery of saturated polyester as a fiber
James T. Dickson raw material, production at ICI and Du Pont
1946 US-Rubber Co. First ABS plastics
1953 Karl Ziegler Low-pressure polymerization of ethylene with
organometallic catalysts
1953 Hermann Schnell Discovery of polycarbonates
1957 Hoechst AG Start of production of polypropylene
1965 Shell Block copolymers made from styrene and
polyolefins
1967 Dynamit Nobel AG Technical production of crystal-clear
­polyamide
1973 Dynamit Nobel AG Production of polyvinylidene fluoride begins
From 1973 Development of special plastics such as
­polyaryl ethers, polyaryl sulfones, poly­
phenylene sulfide, polyether sulfone, poly-
etherimide, polyimide sulfone and, above all,
thermoplastic copolymers

„ 3.2 Thermoplastic Polymers

In plastics processing, thermoplastic polymers play the most considerable eco-
nomic role, as they can be melted and deformed at higher temperatures without
significant decomposition. Although they have most of the required material prop-
erties after their production, coloring is advantageous for many purposes or is
­necessary for identification. The thermoplastic polymers show the following prop-
erties:
3.2 Thermoplastic Polymers 17

Table 3.2 Properties of Thermoplastic Polymers

Natural state ƒ Transparent to beige opaque
ƒ Material properties largely available
Coloring Depending on the use, advantageous to absolutely
­ ecessary (e.g., electrical cables)
n
Typical characteristics ƒ Highly viscous consistency above the softening point
ƒ Decrease in viscosity up to the decomposition point
ƒ Hardening after cooling
Thermoplasticity Is used to process plastics through injection molding,
e­ xtrusion, blow molding and welding
Damage With every machining process, the material is damaged to a
greater or lesser extent

Under unfavorable processing conditions, crystallization effects can occur after the
reshaping of polymers. Crystallization nuclei can also be pigments. This can
change the shape of the finished plastic article (“warpage”). The consequence can
be, for example, that beverage crates can no longer be stacked or that the lid of
garbage cans no longer fits on the can.
The thermoplasticity of plastics is used to process them by injection molding, ex-
trusion, blow molding, or welding.
The advantages of polymer materials are:
ƒ low specific weight
ƒ high resistance to corrosion and rotting
ƒ high electrical insulation properties
ƒ thermal insulation and sound insulation
ƒ easy shaping
ƒ ideal material for mass production because of its economic processability
ƒ easy to color, print, and metalize
ƒ wide range of inexpensive raw materials
These favorable properties are offset by the following disadvantages:
ƒ usually low mechanical strength
ƒ low heat resistance
ƒ deterioration of the physical properties under the action of light and heat
ƒ most polymers are flammable
ƒ expensive waste disposal
ƒ uneconomical reparability
ƒ limited dimensional accuracy, a tendency to post-shrinkage and creep
18 3 Plastic Materials

3.2.1 Chemical Composition and Material Properties

3.2.1.1 Polyvinyl Chloride

Polyvinyl chloride (PVC) is produced on an industrial scale using emulsion, sus-
pension, and bulk polymerization processes. PVC is flame-retardant and very
­resistant to chemicals. Its softening point is between 75 °C and 80 °C. Processing
is relatively easy by calendering, extrusion, and blow molding, whereby the PVC
usually needs to be stabilized, e.g. by environmentally friendly calcium-zinc stabi-
lizers. For injection molding, PVC with low molar mass (low K-value, easy flowing)
must be used.
PVC can be produced as PVC-u (unplasticized), PVC-p (plasticized), a copolymer of
vinyl chloride with vinyl acetate, and as an impact-resistant molding compound by
mixing PVC with rubber-like components. PVC-u can be bonded and welded and is
processed into pipes, fittings, window frames, and façade coverings, among others.
PVC-p is used as a base material for films, floor coverings, hoses, cable insulation,
artificial leather, or similar things, and is particularly suitable for high-frequency
welding.

3.2.1.2 Polyolefins
Polyolefins are all polymers made from olefins, such as polyethylene, polypropyl-
ene, polybutene-1 and polyisobutylene. They have good mechanical properties, are
easy to process, resistant to chemicals, and versatile, and have a good price-perfor-
mance ratio.

3.2.1.2.1 Polyethylene
Polyethylene is produced by polymerizing ethylene using various processes. Its
properties are mainly determined by the molar mass, the molar mass distribution,
and the degree of branching. The density and the melting point increase with the
crystalline portion of the polyethylene, whereby the lower the degree of branching
of the molecular chains, the higher this portion is. The traded polyethylene is dif-
ferentiated according to its density in LDPE, LLDPE, and HDPE, whereby the over-
all density ranges between 0.91 g/cm3 and 0.97 g/cm3.
Low-density polyethylenes can be manufactured in high-pressure processes (LDPE)
or low-pressure processes (LLDPE). The use of metallocene catalysts in recent
years has brought about a further improvement in the product properties in both
process variants.
3.2 Thermoplastic Polymers 19

3.2.1.2.2 Polypropylene
Most of the polypropylene (PP) is produced by the gas phase process using metal-
locene catalysts, which are tailored to the desired product properties. PP is used in
the packaging sector (films), in the textile sector for fibers and tapes and the indus-
trial sector (vehicle construction, electrical engineering/electronics, semi-finished
products). There is a large number of PP products on the market that differ in their
flowability, transparency, scratch resistance, flexural modulus, flexibility, weather
resistance, heat resistance, rigidity, hardness, toughness, and melting point,
among other things. Highly crystalline PP products (HCPP) close the gap between
unreinforced PP and PP reinforced with mineral fibers or platelets.

3.2.1.3 Styrene Polymers and Copolymers

Polystyrene (PS) is the thermoplastic polymer of styrene (C6H5-CHCH2) and is tech-
nically predominantly polymerized by free radicals in suspension. PS is crystal
clear, stiff, quite brittle, and resistant to acids, alkalis, alcohol, and mineral oil, but
not resistant to, or soluble in, most solvents. It is inexpensive, easy to process, and
versatile. To improve the brittleness, the impact resistance, and the light sensitiv-
ity of the standard PS, before the polymerization, the styrene is added to a solution
of polybutadiene. Since the two polymers are immiscible, a polystyrene phase is
formed when the reaction is carried out appropriately, in which small particles of
the grafted rubber are embedded. The amount of rubber used, as well as the struc-
ture and size of the particles of the graft polymer, are decisive for the mechanical
properties of impact-resistant polystyrene (HIPS, High-Impact PS).
Another change in properties can be achieved by copolymerizing styrene with
­acrylonitrile (SAN), with acrylonitrile and butadiene (ABS), or with acrylonitrile
and acrylic ester (ASA). SAN has high strength and hardness, as well as excellent
heat resistance. ABS is particularly impact-resistant, but due to the butadiene con-
tent only has limited aging resistance. ASA is also particularly impact-resistant,
but more weather-resistant than ABS. The products are used in household and
consumer goods as well as in sophisticated technical parts.

3.2.1.4 Acrylic Resins

Acrylic resins are the collective name for polymers of acrylic acid and methacrylic
acid, as well as the corresponding nitriles, esters, amides, and similar. The best-
known type of acrylic resin is thermoplastic poly(methyl methacrylate) (PMMA). It
is produced using free radical polymerization in bulk, solution, suspension, and
emulsion processes. Methacrylates have a wide range of properties. The excellent
light transmission, combined with low weight and high flexibility in processing, as
well as particularly excellent weather resistance, contributes significantly to the
fact that this material can be used in many ways, e.g., in building glazing, the illu-
20 3 Plastic Materials

minated advertising sector, and automotive engineering. In addition to standard

PMMA, impact-resistant molding compounds are also produced.

3.2.1.5 Polyamide
Silk and wool are natural polyamides (PA) while technical thermoplastic PAs are
best known as “Nylon” (PA 66) and as “Perlon” (PA 6). PAs are designated accord-
ing to the number of carbon atoms in their monomers: PA 6 = polycaprolactam;
PA 66 = polycondensation product of hexamethylenediamine and adipic acid (DIN
16773 T1). PAs are semi-crystalline, and conventional PAs melt between 200 °C
and 260 °C. The narrow melting and solidification range is also characteristic.
Polyamides are mainly processed into fibers and used for technical parts in the
electrical industry and vehicle construction. The impact strength is increased by
adding elastomers; glass fibers and mineral fillers increase strength and reduce
thermal expansion. PAs are resistant to alkalis, many solvents, fuels, and oil, but
are attacked by acids. Partly aromatic polyamides (PPA) are suitable for the highest
mechanical, thermal, and environmental stress.

3.2.1.6 Polycarbonate
Polycarbonates (PC) are linear thermoplastic polyesters and polycondensation
products of carbonic acid with diols, e.g., dioxydiphenylalkanes. Starting products
are bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and phosgene. PCs are very
translucent, mechanically stable, heat-resistant, and have excellent electrical insu-
lation properties. In addition to areas of application in electrical engineering and
the automotive sector (headlights), considerable quantities are processed into
­laser-optically readable data carriers (e.g., CDs). For technical applications in the
automotive sector, PCs are also processed into blends (e.g., ASA/PC or ABS/PC).

3.2.1.7 Other Thermoplastics

Since a detailed treatment of all plastics would go beyond the scope of this book, a
few more important plastics should be mentioned at this point:
ƒ ABS – acrylonitrile-butadiene-styrene copolymers
ƒ ASA – acrylonitrile-styrene-acrylic ester
ƒ SAN – styrene-acrylonitrile copolymers
ƒ PET – polyethylene terephthalate
ƒ PBT – polybutylene terephthalate
ƒ POM – polyoxymethylene
ƒ PUR – polyurethane
3.2 Thermoplastic Polymers 21

Table 3.3 Uses of Commercially Available Plastics

PE (polyethylene) ƒ Films (carrier bags, sacks, etc.)
ƒ Hollow bodies
ƒ Bottle crates
ƒ Toys
ƒ Cables
ƒ Pipes
PP (polypropylene) ƒ Household items (mixing bowls)
ƒ Toys
ƒ Bottle crates
ƒ Stretched woven tapes (bags, nets)
ƒ Fibers
PS (polystyrene) ƒ Electrical industry (spools, light covers, tape and film
reels)
ƒ Household items (stay-fresh cups, party dishes,
­refrigerators)
ƒ Toys
ƒ Office supplies
ƒ Parts without much mechanical stress
SB (styrene butadiene) ƒ Electrical industry (TV rear panels, junction boxes, phone
housings)
ƒ Coat hangers
ƒ Thermoformed packaging for dairy products
ƒ Packaging for eggs
ƒ Drinking cups for vending machines
ƒ Machine housings
ƒ Toys
SAN (styrene acrylic ƒ Electrical industry (covers, household machines)
­nitrile) ƒ Containers, coffee filters
ƒ Headlight housings
ƒ Indicator and taillight covers
ABS (acrylic butadiene ƒ Machine housings
­styrene) ƒ Vacuum cleaner housings, food processors, telephone
housings
ƒ Automotive industry (front spoilers, radiator grilles, glove
boxes)
ASA (acrylonitrile styrene ƒ Traffic lights
acrylic rubber) ƒ Information signs
ƒ Hot water drainage pipes
ƒ Garden furniture, boat hulls
PPO (polyphenylene ƒ High-temperature-resistant plastic parts (> 200 °C)
­oxide)
PA (polyamide) ƒ Fibers
ƒ Technical articles (gears, bobbins)
ƒ Machine housings
22 3 Plastic Materials

PAN (polyacrylonitrile) ƒ Fibers

PC (polycarbonate) ƒ Baby bottles
ƒ Medical equipment
ƒ Dimensionally stable, high-strength technical devices
PMMA (polymethyl ƒ Glass replacement
­methacrylate) Plexiglas ƒ Vehicle glazing
ƒ Shower stalls
ƒ Magnifying glasses
ƒ Sunglass lenses
POM (polyoxymethylene) ƒ for mechanically stressed parts (bearings, gears)
polyacetal ƒ Disadvantage: some formaldehyde can be split off
CAB (cellulose ƒ Eyeglass frames
­acetobutyrate) ƒ Case handles
ƒ Parts that are exposed to the weather (billboards)
CA cellulose acetate ƒ Cable sheathing
(acetyl cellulose) ƒ Molded parts (glasses)
ƒ Films, photo films, Rayon (acetate silk)
ƒ Pipes, bottles
ƒ Skylights
PTFE ƒ Pan coating
(polytetrafluoroethylene) ƒ Metal coating (low coefficient of friction)
PUR (polyurethane) ƒ Ski boots
– thermoplastic ƒ Technical parts
PUR (polyurethane) ƒ Coatings
– physically drying ƒ Paint
ƒ Synthetic leather
PUR (polyurethane) foam ƒ Seats
ƒ Mattresses
ƒ Armrests
ƒ Neck supports
UP (unsaturated ƒ Boatbuilding
­polyester) ƒ Bodywork
resins ƒ Containers, tanks
ƒ Furniture (seat shells)
PET (polyethylene ƒ Fibers (Diolen, Trevira)
­terephthalate) ƒ Beverage bottles
PVC (polyvinyl chloride) ƒ Profiles, cable ducts, gutters
hard ƒ Cups (packaging for food)
ƒ Bottles (oil, vinegar)
PVC (polyvinyl chloride) ƒ Decorative films, furniture films (veneer replacement)
flexible ƒ Hoses
ƒ Floor coverings
ƒ Ring binders, folders, covers
3.3 Bioplastics 23

An essential criterion in the coloring of plastics is the processing temperature of

the respective plastic. The processing temperatures for injection molding or blow
molding range from approximately 160 to 200 °C for PVC, over approximately 200
to 250 °C for PE, and 250 to 290 °C for PA 6, up to approximately 320 to 340 °C for
PSU.
The thermal stability of the inorganic pigments currently on the market is, with
certain exceptions, outstanding, especially when they are produced by calcination
at temperatures above 700 to 1200 °C. The thermal stability of the organic colo-
rant is more or less limited, and there are two main reasons for the limited thermal
stability. On the one hand, this is the thermal stability of the molecule itself and,
on the other hand, the stability of the crystal modification present in pigments. It
should be noted that with increasing processing temperature, the number of still
usable organic coloring agents decreases rapidly. This inevitably means that not
every arbitrary color nuance can be set. To make matters worse, the thermal stabil-
ity of organic colorants is plastic-dependent.

„ 3.3 Bioplastics
The term “bioplastics” encompasses two different groups of products, the “bio-
based” and the “biodegradable” plastics.
Bio-based materials are obtained entirely or partially from renewable resources.
These include, for example, polylactic acid, polyhydroxy fatty acids, starch, cellu-
lose, chitin, and gelatin. Bio-based plastics can be biodegradable – but not always.
The bio-based but non-biodegradable plastics include natural fiber-reinforced plas-
tics and composite materials made of wood and plastic.
Biodegradable means: Specific bacteria release enzymes that break down the long
polymer chains of the material into small molecules. The bacteria then digest
these, and what remains is water, carbon dioxide, and biomass. For the material to
be able to be called “biodegradable,” according to the European standard DIN EN
13432, it must be 90% degraded after at most 180 days under certain conditions.
Biodegradable plastics do not have to be made from renewable raw materials; they
can also be petroleum-based. The biodegradability does not depend on the raw
material, but solely on the chemical structure of the plastic [1] [2].
Bioplastics are both those polymers that consist of renewable raw materials (bio-
based) and petroleum-based ones that are biodegradable [1].
24 3 Plastic Materials

Figure 3.4 Biopolymers

A biopolymer should have at least one of the following properties:

a) consists of bio-based (renewable) raw materials and/or
b) is degradable by biological means
Accordingly, the following three primary biopolymer groups exist:
1. Degradable petro-based biopolymers
2. Degradable (predominantly) bio-based biopolymers
3. Non-degradable bio-based biopolymers
This means that bioplastics do not necessarily have to consist exclusively of renew-
able raw materials. Biodegradable biopolymers based on petrochemical raw mate-
rials can also be produced, such as polyvinyl alcohols, polycaprolactones, copoly­
esters, or polyester amides. Conversely, not all biopolymers based on renewable
raw materials are necessarily biodegradable, such as highly substituted cellulose
acetates, vulcanized rubber, casein plastics, or linoleum.
Bio-based means that the material or product is (partially) produced from biomass
(plants or animals). Biomasses used for bioplastics are corn, sugar cane, or cellu-
lose.
The bioplastics with the highest potential are polylactides and starch blends. Poly-
lactide (PLA) is a non-naturally occurring polyester that is produced from sugar
through a multi-stage synthesis: sugar is fermented into lactic acid and polymer-
ized into PLA.
3.3 Bioplastics 25

PLA is transparent, crystalline, rigid, has high mechanical strength, and can be
processed using conventional thermoplastic processes [1].
The packaging sector (e.g., hollow bodies, films, carrier bags), horticulture (e.g.,
films, flower pots), and agriculture (e.g., agricultural films) come into question as
potential areas of application. By using biodegradable plastics, it was hoped, on the
one hand, to save valuable landfill space; on the other hand, in agriculture, this
type of film should make mechanical removal before harvest superfluous. The film
should be disposed of in an environmentally friendly way by simply plowing under
it.
Due to their thermoplastic processing, the biodegradable plastics can be colored in
bulk. It should be noted, however, that the degradable plastics based on cellulose/
starch derivatives necessarily contain plasticizers (usually higher alcohols and
­water). Excessive brittleness of the finished parts can only be avoided through the
content of plasticizers. Since thermoplastic processing takes place at temperatures
above the boiling point of water, appropriate precautionary measures must be
taken to prevent unwanted embrittlement caused by processing.
The requirement for biodegradability naturally applies to the entire system and
does not only apply to the plastic only. This means that not only the additives but
also the colorants should be biodegradable, creating an exceptional problem:
ƒ The natural, biodegradable colorants cannot be used simply because of their in-
adequate thermal stability for thermoplastic processing. Further weak points are
their low authenticity values.
ƒ In the case of organic, synthetic colorants, it must be assumed that they are not
biodegradable or that degradation products that are relevant to the environment
may arise. Detailed studies on this topic have not yet been published.
ƒ Due to their chemistry, the inorganic pigments are not biodegradable. As a com-
promise, however, individual inorganic pigments are used to color the biodegrad-
able plastics. Various inorganic pigments occur in nature either as a pure sub-
stance in the form of minerals or, due to their absolute insolubility, they would
not pose any risk to the environment.
Although most inorganic pigments are produced by calcination at high tempera-
tures and, as corresponding studies show, are totally insoluble, various inorganic
pigments cannot be used. This results from the required quality standard for com-
post because composting is the prescribed route for the disposal of biodegradable
objects.
These quality standards describe the requirements, including the test methods for
recognition as biodegradable products, and the content of certain heavy metals in
the compost is also precisely defined. The insolubility of the inorganic pigment is
irrelevant; the heavy metal content, as such in the humus, based on 1 kg of dry
matter, is decisive.
26 3 Plastic Materials

There are no general advantages or disadvantages of fossil or renewable raw mate-

rials. For each specific application, environmental compatibility, economic effi-
ciency, and social impact over the entire life cycle of a product must be examined.
The eco-efficiency analysis shows that plastics based on plants are not generally
more eco-efficient than those based on petrochemicals. If the need for water and
fertilizer is relatively low and the transport routes are short, the use of vegetable
raw materials can be ecologically beneficial. However, if energy-intensive pro-
cesses are used during processing, the ecological effect can easily be reversed.
Biodegradable plastics are not generally more environmentally friendly than
­others. But they are the best solution for certain applications – for example, for
plowable agricultural films, compostable food packaging, or carrier bags.

References for Chapter 3

[1] Endres, H., Siebert-Raths, A.: Technische Biopolymere – Rahmbedingungen, Marktsituation,
Herstellung, Aufbau und Eigenschaften, Munich, 2009, Carl Hanser Verlag
[2] https://www.basf.com/de/company/news-and-media/science-around-us/tear-resistent-waste-bags-for-
compost.html, September 2017
[3] Etzrodt, G., Müller, A.: Kunststoffeinfärbung, Munich, 2018, Carl Hanser Verlag
4 Basics of Colorants

„ 4.1 General Characteristics

Colorants is the collective term for all coloring substances (dyes and pigments).
Pigments are very fine colored or achromatic solids that absorb and scatter light.
In contrast to dyes, they are practically insoluble in the application medium. Pig-
ments not only have the task of giving the plastic a decorative appearance, but
they also have a significant influence on the light and weather resistance.
Dyes are light-absorbing organic compounds that are soluble in the application
medium.
ISO 18451 defines terms that are used in the field of colorants, dyes, and fillers:
DIN ISO 18451-1: 2016-06 - Pigments, dyes, and fillers - Terms - Part 1: General
terms (ISO 18451-1: 2015) [2].

Table 4.1 Properties of Classical Pigments

Particle size 1 µm = 10–3 mm
1 nm = 10–6 mm
Transparent pigments Up to about 0.15 µm (half the wavelength of visible light)
Opaque pigments From about 0.2 to about 2.5 µm
Platelet-shaped pigments From approx. 8 µm up to 25 µm, in extreme cases up to
200 µm
Density 1 g/ml up to 6 g/ml
Conductivity Up to 600 µS
Surface area (BET) From 1 m2/g up to 200 m2/g

Colorants are divided into inorganic and organic colorants according to DIN ISO
18451-2:2016-06 - Pigments, dyes and fillers - Terminology - Part 2: Classification
according to coloristic and chemical aspects. The following list shows the classifi-
cation according to coloristic aspects in accordance with DIN ISO 18451.
28 4 Basics of Colorants

This classification is based on optical effects, the causes of which are given below:
White pigments The optical effect is based on wavelength-dependent light
­scattering.
Colored pigments The optical effect is based on wavelength-dependent light
­absorption, combined with light scattering.
Dyes The optical effect is based on wavelength-dependent light
­absorption.
Black pigments The optical effect is based on wavelength-independent light
­absorption in the visible range of light.
Effect pigments The optical effect is based on at least one of the following three
effects:
ƒ in the case of metallic effect pigments, on the directional
­reflection on metallic pigment particles, which are
­predominantly formed and aligned over a wide area
ƒ in the case of pearlescent pigments, on the directional reflection
from predominantly flat and aligned transparent platelets
ƒ in the case of interference pigments, on the phenomenon of
light interference

„ 4.2 Colorants
Inorganic Pigments
ƒ Inorganic white pigment
ƒ Inorganic colored pigments
ƒ Inorganic black pigments
ƒ Inorganic effect pigments
ƒ Inorganic luminous pigments
ƒ IR-reflective pigments
ƒ IR-absorbing pigments

Organic Pigments
ƒ Organic colored pigments
ƒ Organic black pigments
ƒ Organic effect pigments
ƒ Organic luminous pigments
4.2 Colorants 29

Organic Dyes
ƒ Organic colored dyes
ƒ Organic black dyes
ƒ Organic luminous dyes
From a chemical point of view, the colorants, according to DIN ISO 18451, are
­divided as follows:

Inorganic Pigments
ƒ Pigments made from chemical elements
ƒ Oxide/oxide hydroxide pigments
ƒ Complex inorganic colored pigments (CICP)
ƒ Sulfide/sulfoselenide pigments
ƒ Chromate/chromate molybdate pigments
ƒ Silicate pigments
ƒ Other pigments

Organic Pigments
ƒ Azo pigments
ƒ Polycyclic pigments: copper phthalocyanines
ƒ Polycyclic pigments: diketo-pyrrolo-pyrroles
ƒ Polycyclic pigments: quinacridones
ƒ Polycyclic pigments: isoindolines and isoindolinones
ƒ Polycyclic pigments: perylenes and perynones
ƒ Other polycyclic pigments

Organic Dyes
ƒ Ionic dyes
ƒ Cationic dyes
ƒ Anionic dyes
ƒ Nonionic dyes
In the delivery state, pigments are present both as primary particles and as aggre-
gates and agglomerates. A description is given in DIN ISO 18451-3: 2014-07 – Pig-
ments, dyes, and fillers – Terms – Part 3: Particle size [2].
According to DIN ISO 18451-3, aggregates are an intergrown association of pri-
mary particles arranged flat against each other, the surface area of which is smaller
30 4 Basics of Colorants

than the sum of the surfaces of the primary particles. Agglomerates are a non-­
intergrown association of primary particles and/or aggregates, e.g. at corners and
edges, whose total surface area does not deviate significantly from the sum of the
individual surfaces.

Figure 4.1 Aggregates, agglomerates

A comparison of the properties of organic and inorganic pigments shows the

strengths and weaknesses of the respective pigment groups (Figure 4.2).

Figure 4.2 Comparison of the properties of organic and inorganic pigments

Further information can be found in refs. [3] and [4].

Another random document with
no related content on Scribd:
1917 Adkins Geo Cav 6D June
14
July
3991 Andrews E L “ 6K
26
76 July
4270 Anderson D
E 29
40 Aug
5680 Ault J W
D 14
93 Aug
6921 Alexander S
D 26
Aug
7124 Alexander J D Cav 5K
28
65 Sept
9292 Auburn C
H 19
Sept
9445 Atkins J F Cav 2H
21
35 Sept
9584 Adams H
A 23
29 Sept
9643 Allen D B, S’t
- 24
117 Sept
9759 Alfred W J
K 25
88 Oct
10473 Allyn D
K 7
32 Oct
10793 Atland C
C 12
89 Oct
11186 Albin I
D 19
Nov
12183 Austin Alfred 5K
27
93 Jan
12513 Amick W 65
B 23
313 Bash David 117 Apr 64
C 2
Apr
576 Bee Thomas Cav - -
16
75 Apr
596 Bock Samuel
I 17
66 May
838 Brown T
D 1
84 May
1514 Barry Henry
D 31
66 June
1603 Boley A J
C 4
65 June
1759 Barra John
H 9
June
2016 Burnett Wm Cav 6G
15
27 June
2191 Buckhart E
F 19
19 June
2222 Brasier S, Mus
I 20
44 June
2299 Bumgardner
D 22
42 June
2458 Barrett E
I 25
42 July
2874 Bowman John
C 4
July
3044 Bruce J W Cav 5M
8
July
3359 Broughton D 7K
15
68 July
3366 Bricker J
C 15
52 July
4027 Barton J F
G 26
4035 Ballinger Robert 39 July
I 26
81 July
4251 Bonly James
C 29
Aug
4479 Baker J 9G
1
13 Aug
4563 Baker D W
B 2
129 Aug
4948 Bayer F
H 7
29 Aug
5089 Brenton J W
I 8
53 Aug
5093 Bowlin Wm
G 8
Aug
5220 Barton E Cav 2G
10
101 Aug
2275 Busick W A, Cor
F 10
81 Aug
5442 Bryer P
K 12
79 Aug
5590 Bohems Philip
A 14
Aug
5690 Baker J P Cav 7H
15
31 Aug
5794 Boom W P
F 15
130 Aug
5981 Barton George
F 17
112 Aug
6163 Brookers J M
E 19
66 Aug
6410 Brown J M
F 22
6518 Bartholomew I 99 Aug
A 22
101 Aug
7370 Bamgroover J A
H 31
Sept
7794 Barnes T M Cav 5C
4
29 Sept
8314 Babbitt W H
I 10
14 Sept
8397 Bassinger H
C 10
125 Sept
8519 Boyd W F
F 12
88 Sept
9098 Bortley S
I 18
79 Sept
9548 Bray T E 64
K 23
Sept
9708 Brown J, S’t Cav 1A
24
58 Sept
9777 Birch T A
L 26
40 Sept
9793 Bozell J F
B 26
Sept
9846 Bixter D 5B
27
Blackaber Wm 42 Oct
10350
H I 5
30 Oct
10939 Benton L
H 14
72 Oct
11559 Bennett R N
D 27
87 Oct
11604 Bemis J M, Cor
F 28
128 Nov
11919 Brown D
B 8
11930 Bailey George 72 Nov
A 8
29 Nov
12019 Bennet A
G 15
32 Nov
12128 Booth J
E 22
Dec
12294 Bennett C 6H
15
66 Jan
12486 Barrey H 65
I 19
93 Jan
12504 Balstrum J
F 22
57 Feb
12596 Branson E
A 6
Apr
301 Charles James 6G 64
1
Apr
625 Connell P Cav 6M
19
Claycome S A, 66 Apr
634
S’t G 20
42 May
1117 Cox Joseph, S’t
B 15
May
1146 Carter Henry 2C
16
30 May
1172 Curry J W
F 17
87 May
1463 Currier Wm
K 30
31 May
1523 Crest J D
F 31
Carpenter O C, 29 June
2254
Cor D 21
2307 Cottrell M, S’t Cav 6G June
22
38 July
2776 Cooley A
C 2
82 July
3043 Clark W
C 8
July
3922 Connolley D 9 I
25
66 July
4192 Cox S
E 28
Aug
4917 Clifford H C Cav 7 I
6
Aug
5262 Courtney J F “ 2L
10
130 Aug
5654 Collar E
G 14
Aug
5660 Crews E M Cav 5A
14
54 Aug
5901 Clark A
A 16
93 Aug
6208 Chrichfula S
A 19
22 Aug
6477 Croane J J
C 22
58 Aug
6646 Cornelius E
B 23
Carnahan A W, Aug
6926 6E
S’t 26
66 Aug
7383 Carpenter S
I 31
120 Sept
7726 Callings W
F 3
30 Sept
7737 Cramer A
H 3
7899 Cheny James Cav 7 I Sept
5
101 Sept
8051 Cramton R
I 6
53 Sept
8108 Crazen J
G 7
13 Sept
8133 Crager J
C 8
80 Sept
8144 Cooper J
E 8
Sept
9294 Christman J E Cav 6G
19
56 Sept
9535 Collins G
F 22
130 Sept
9980 Connett Daniel
F 28
13 Sept
10084 Conel J
D 30
35 Oct
10905 Callan M
B 13
87 Oct
11423 Cafer J H
K 24
93 Oct
11631 Cummings J W
F 28
101 Nov
12062 Clark M
B 17
42 Nov
12173 Cannon A
F 26
Dec
12213 Cregs Wm Cav 5E
3
Jan
12415 Collins W A, S’t 5G 65
8
12559 Calvert G F Cav 8 I Jan
30
July
4234 Curry W F “ 4 I 64
29
65 Apr
426 Dummond J H
F 7
66 Apr
508 Davis J M
I 12
12 May
964 Darker Wm
C 8
44 June
2205 Denny John
E 19
29 July
3157 Detrich C
K 11
July
3419 Dusan J 6D
16
35 July
4021 Develin E 64
B 26
32 July
4029 Decer P
K 26
42 July
4124 Dill C P
F 27
13 Aug
5255 Davis K
D 10
36 Aug
5367 Dunben M
E 11
13 Aug
5420 Delup Z S
D 12
38 Aug
5681 Dallinger W C
E 14
81 Aug
6147 Denton Philip
D 19
116 Aug
6934 Downey S M
I 25
6944 Dowell W L 6C Aug
26
30 Sept
9638 Dunlap W
A 24
Sept
10010 Downs J R Cav 5 I
29
36 Oct
10435 Dane Andrew
I 6
35 Oct
10446 Dignon L
B 7
29 Oct
10916 Dawson L F
I 14
Oct
10954 Dial R 1B
14
58 Nov
12087 Daffendall P H
D 18
Nov
12172 Davenport J Cav 6 I
24
Delashment F, 14 Dec
12236
S’t B 6
85 Jan
12533 Duckworth J 65
F 27
73 Jan
12545 Dawley J
I 27
124 Feb
12580 Dawson J
D 3
19 Sept
9236 Diver O 64
F 19
May
916 Evans G H Cav 1A
6
Edwards G H, May
917 6G
Mus 7
1083 Ellis H C Cav 6D May
14
75 May
1279 Evans W
I 22
29 May
1346 Eskridge Oakley
D 24
38 June
1994 Edwards J W
G 15
June
2481 Esenthal F Cav 5D
25
58 July
4075 Eaton W H
B 27
39 Aug
4953 Ecker J
I 17
Aug
5076 Evans J Cav 6 I
8
20 Sept
7917 Ells D
I 5
Oct
11320 Elston F 9B
22
Oct
11429 Estelle E W, S’t Cav 2L
24
38 Nov
11712 Eldridge E
- 1
Nov
11774 Earl D, Cor Cav 2B
3
Dec
12285 Emmons W 5D
14
35 May
1482 Frecks F
D 30
66 June
1808 Fitter B
I 10
30 June
2143 Fike Tobias
D 18
3014 Fitzgerald I 30 July
D 7
32 July
3453 Fescher D
E 17
July
3637 Fuget W Cav 3C
20
Sept
8379 Fields N “ 6F
10
72 Sept
8547 Fenton I
D 12
Sept
8766 Forward S Cav 8 I
14
25 Sept
9847 Forshua W
H 27
Farmingham W 14 Oct
10509 Cav
C K 8
Oct
11311 Fanier F Cav 6 I
22
Oct
11626 Fish C “ 2H
26
93 Nov
12012 Falkerson J, S’t
B 14
93 Nov
12144 Francis F, Mus
- 24
Dec
12320 Fross John, S’t Cav 5D
24
10 Mar
12728 Felnick H 65
F 4
Mar
98 Graham Wm 6G 64
22
110 Apr
322 Gladman H
B 2
1048 Goodwin Wm Cav 2M May
12
66 May
1165 Grimes F O
I 17
29 May
1215 Garver John
F 19
May
1312 Gullsen Wm Cav 7L
23
June
1594 Griffin William “ 6 I
3
22 June
2337 Gray D L
I 22
80 June
2386 Guthrie W B
C 24
120 June
2418 Gillard Wm
C 24
128 July
3573 Gibbons W T
I 19
66 July
4179 Gould Wm 64
E 28
July
4273 Gilbert H A, S’t Cav 2K
29
July
4847 Galliger Wm 7B
31
35 Aug
4901 Gerard H
G 6
20 Aug
6189 Goodwin I
F 19
74 Aug
6398 Gordon W M
G 21
Goodridge E, 94 Aug
6493
Cor H 22
32 Aug
7298 Grass C
H 30
7321 Gray H F Cav 2H Aug
30
30 Sept
7698 Gerber I
C 3
58 Sept
8546 Galliger P
C 12
35 Sept
8791 Gagham Wm
K 14
72 Sept
9112 Green S
E 18
29 Sept
9114 Gillan J
F 18
Griswold Oct
10782 2F
Thomas 12
13 Oct
11409 Gordon J W
D 24
Oct
11581 Greenwood W 3C
28
Dec
12216 Grant H G 5G
3
Jan
12398 Garnet T 6E 65
5
39 Jan
12483 Green Wm
E 19
Apr
630 Hollar John Cav 5 I 64
19
30 May
879 Henick Wm
F 4
117 June
1953 Hall L S
C 14
116 June
2118 Hilliard J
D 17
2130 Hodges J 7C June
18
74 June
2379 Hustin James
B 23
June
2392 Hodges S 9F
24
June
2629 Humphrey I 3C
28
July
2768 Hendricks J Cav 2C
2
July
2768 Higgins M P “ 3C
2
July
2793 Hodges W J 5F
2
65 July
2812 Hillman H
G 3
July
2974 Hamilton James 7K
7
68 July
3289 Hine S
A 14
80 July
3507 Hodgen J W
G 18
65 July
4487 Hanger L S
A 1
88 Aug
5362 Hart J R
H 11
Aug
5678 Hittle B Cav 6L
14
20 Aug
5695 Helville N C
F 15
20 Aug
5872 Heah Jacob
G 16
Aug
6076 Hearne John Cav 5F
18
6198 Hershton A 4M Aug
19
129 Aug
6491 Hendricks I
H 22
30 Aug
7031 Hartsock I
A 27
42 Sept
7790 Hunter J M
F 4
Hammond G W, 65 Sept
7837
Cor D 4
32 Sept
7903 Halfree J A
A 5
Sept
7971 Hamilton P S 7E
6
Hughes W H, 81 Sept
8091
Cor D 7
Sept
8347 Hart A 7A
10
Sept
8541 Haff M Bat 4 -
12
42 Sept
8681 Hunter H
F 13
30 Sept
8778 Haynes W
G 14
Sept
8836 Higgins J W Cav 3C
15
Sept
8967 Holloway J “ 5M
16
Sept
9003 Hubbner F “ 4E
18
36 Sept
9329 Hurst R V, Cor
B 20
9429 Higgins W E 53 Sept
H 21
Sept
9911 Haghton J 2D
28
30 Sept
9933 Harrington O
I 28
80 Oct
10123 Hoffman J
C 1
Hunstler W H, 38 Oct
10293
S’t E 4
39 Oct
10522 Hoagler N C
E 8
13 Oct
10613 Harris W C
D 10
13 Oct
10820 Hector E
D 12
99 Oct
11231 Haskins H
A 20
Oct
11243 Hasfle J, Mus 1F
21
14 Nov
11790 Hill R 64
D 4
13 Dec
12249 Hamilton D
B 9
Jan
12536 Hall H H 2E 65
27
129 Aug
6444 Ihn C 64
B 22
Sept
8963 Igo T, Cor 4E
16
Apr
670 Johnson Isaac 5C
22
June
1931 Jennings C, Cor Cav 6 I
14
2212 Jackson John 22 June
C 20
63 June
2353 Jones Wm M
D 23
38 July
3311 Jasper Wm
I 10
Aug
5245 Judd Henry, S’t 2D
10
Aug
6172 Julerso H Cav 2D
19
Aug
6811 Jones H C 5C
20
88 Aug
7100 Jones A
I 28
Sept
9948 Johnson J Cav 7A
28
120 Jan
12517 Jones J 65
C 24
40 Mar
12799 Johnson H
C 19
42 Apr
417 Kistner George 64
B 7
56 Apr
618 Kinnan A
G 18
Ketchum G W, May
858 Cav 5 I
S’t 3
June
2036 Kelly John, S’t Cav 5 -
15
June
2407 Kennedy Amos 2H
24
June
1908 Kelso E O Cav 3C
13
2527 Kanga J 74 June
E 26
Kennedy J W, July
3047 3 I
Cor 8
72 July
4024 Keys Wm
E 26
Aug
5149 Keiler W J, S’t Cav 4H
9
29 Aug
5253 Kocher T
I 10
25 Aug
5722 Kern W
H 15
32 Aug
6596 Kelly John
C 23
128 Aug
7085 Kames J
F 28
81 Sept
8621 King D
A 13
49 Oct
10689 Keller I
B 11
79 Dec
12278 Kuling I
A 12
10 Feb
12587 Keef P, Cor Cav 65
C 4
May
1041 Lewis J 6H 64
12
30 May
1239 Lawrence R J
G 20
116 May
1261 Lower N G
I 21
65 June
2615 Lewis James
F 28
58 July
2745 Luff C
I 1
3029 Lewis J Cav 3C July
7
128 July
3767 Lannon J S
F 22
80 July
3890 Lawrence D
A 24
35 Aug
4548 Lyons Wm
A 2
Aug
5014 Lee John Cav 3C
8
75 Aug
5585 Lawson William
A 14
80 Aug
5616 Lawyer James
B 14
Aug
6775 Lyons Wm 1E
25
Aug
7162 Lowery D Cav 2G
29
Sept
8607 Lunger A “ 7M
12
52 Sept
9256 Liggett
G 10
Oct
10508 Lewis R Cav 7C
8
101 Oct
11152 Lash J
B 18
Nov
11715 Lakin A Cav 7 -
1
42 Dec
12250 Lawrence B T
D 9
66 Mar
130 McCarty John
D 23
631 Mullen James Cav 6G Apr
19
65 Apr
746 Masters Wm
G 26
18 May
841 Milton John
C 1
117 May
903 Mytinger Wm
F 5
May
954 Milburn J 6K
8
May
1090 Moore Peter 6 I
14
74 May
1405 Miller Jacob
E 27
May
1516 Martin Geo, S’t Cav 3C
31
30 June
1860 Merritt H
G 12
30 June
2240 Mitchell J J
D 20
June
2397 Milliken S L Cav 1G
24
38 June
2511 Moneyhon B 64
D 26
88 June
2608 Marsh J
D 28
119 Mar
5 Moodie Z
K 31
80 July
3387 Mank E
E 16
80 July
3633 Marlit J
H 20
35 July
3884 Mulchy J
A 24