Handbook of Antiblocking, Release, and Slip Additives

343 Pages·2005·3.642 MB·English

by  Wypych, George

HANDBOOK OF
Antiblocking,
Release, and
Slip Additives
George Wypych
ChemTecPublishing
Toronto 2005
PublishedbyChemTecPublishing
38EarswickDrive,Toronto,OntarioM1E1C6,Canada
©ChemTecPublishing,2005
ISBN1-895198-31-3
All rights reserved. No part of this publication may be reproduced, stored or
transmitted in any form or by any means without written permission of copyright
owner.NoresponsibilityisassumedbytheAuthorandthePublisherforanyinjury
or/anddamagetopersonsorpropertiesasamatterofproductsliability,negligence,
use, or operation of any methods, product ideas, or instructions published or
suggestedinthisbook.
CanadianCataloguinginPublicationData
Wypych,George
Handbookofantiblocking,release,andslipadditives/GeorgeWypych.--1sted.
Includesbibliographicalreferencesandindex.
ISBN1-895198-31-3
1.Polymers--Additives.2.Polymers--Additives--Healthaspects.
3.Polymers--Additives--Environmentalaspects. I.Title.
TP1142.W9642004 668.9 C2004-906653-6
PrintedinCanadabyTranscontinentalPrintingInc.,505ConsumersRd.
Toronto,OntarioM2J4V8
Table of Contents i
Table of Contents
1 INTRODUCTION 1
1.1 Historical developments 1
1.2 Expectations from commercial additives 2
1.3 Definitions 3
1.4 Classification 4
References 6
2 GENERIC TYPES 7
2.1 Introduction 7
2.2 Characteristic properties of commercial additives 7
2.2.1 Antiblocking agents 7
2.2.1.1 Inorganic 7
2.2.1.1.1 Calcium carbonate 8
2.2.1.1.2 Carbon nanotubes, fibers, graphite 9
2.2.1.1.3 Ceramic and glass spheres and fly ash 10
2.2.1.1.4 Diatomaceous earth and other natural silicas 11
2.2.1.1.5 Synthetic silica 12
2.2.1.1.6 Synthetic clay (laponite) 13
2.2.1.1.7 Talc 14
2.2.1.1.8 Zeolite 15
2.2.1.2 Organic 16
2.2.1.2.1 Microparticles 16
2.2.2 Mold release agents 17
2.2.2.1 Fluorocompounds 17
2.2.2.2 Polydimethylsiloxanes 18
2.2.2.3 Polymeric waxes 19
2.2.2.4 Other chemical compounds 20
2.2.3 Slip agents 21
2.2.3.1 Acids 21
2.2.3.2 Esters 22
2.2.3.3 Fatty acid amides 23
2.2.3.4 Natural wax and its substitutes 24
2.2.3.5 Salts 25
References 25
ii Table of Contents
3 STANDARD METHODS OF CONTROL 27
3.1 Adhesives 27
3.2 Floor coverings 28
3.3 Footwear and walkway surfaces 28
3.4 Geosynthetics 29
3.5 Leather and coated fabrics 29
3.6 Lubricants 30
3.7 Medical 31
3.8 Paints and coatings 31
3.9 Paper 31
3.10 Plastics and rubber 32
3.11 Roads and pavement 33
3.12 Sport equipment 34
3.13 Textiles 35
References 35
4 TRANSPORTATION AND STORAGE 41
4.1 Transportation 41
4.2 Storage 42
References 43

5 MECHANISMS OF ACTION 45
5.1 Antiblocking agents 45
5.2 Slip agents 53
5.3 Release agents 56
References 58

6 COMPATIBILITY AND PERFORMANCE 61
References 64
7 DIFFUSION AND MIGRATION 67
7.1 Diffusion 67
7.2 Distribution of additive in bulk and on surface 69
7.3 How mobility affects additive selection? 72
7.4 Additive transfer to material in contact 73
7.5 Additive loss 74
References 75
Table of Contents iii
8 INTERACTION WITH OTHER COMPONENTS
OF FORMULATION 77
8.1 Fillers 77
8.2 Other components of formulation 79
8.3 Synergy between surface additives 80
8.4 Other properties 82
References 82
9 PROCESSING AND ADDITIVE PERFORMANCE 85
References 87
10 EFFECT ON PRODUCT PROPERTIES 89
10.1 Mechanical properties 89
10.2 Mar and abrasion 91
10.3 Shrinkage and warpage 92
10.4 Blocking force 93
10.5 Adhesion to mold and demolding 95
10.6 Coefficient of friction 99
10.7 Residues on molds 104
10.8 Residues on molded parts 105
10.9 Optical properties 105
10.10 Rheological properties 108
10.11 Electrical properties 111
10.12 Structure and orientation 111
10.13 Thermal aging 113
10.14 UV radiation 115
10.15 Effect on other properties 115
References 117
11 USE IN SPECIFIC POLYMERS 121
11.1 ABS 121
11.2 Acrylics 123
11.3 Bromobutyl rubber 125
11.4 Cellulose acetate 126
11.5 Cellulose, acetate, butyrate and propionate 127
11.6 Cellulose nitrate 128
11.7 Chlorinated polyvinylchloride 129
11.8 Chlorosulfonated polyethylene 129
iv Table of Contents
11.9 Copolymers 130
11.10 Cyanoacrylates 133
11.11 Ethyl cellulose 133
11.12 Ethylene-propylene-diene copolymer, EPDM 134
11.13 Ethylene-propylene rubber, EPR 136
11.14 Epoxy resin 137
11.15 Ethylene-vinyl acetate copolymer, EVA 138
11.16 Ionomers 140
11.17 Nitrile rubber 141
11.18 Polyamide 141
11.19 Polybutadiene 142
11.20 Polycarbonate 143
11.21 Polyester 145
11.22 Polyetherimide 147
11.23 Polyethylene 148
11.24 Polyimide 155
11.25 Polylactide 156
11.26 Polymethylmethacrylate 157
11.27 Polyoxymethylene 159
11.28 Poly(N-vinylcarbazole) 159
11.29 Polyphenylene ether 160
11.30 Polypropylene 161
11.31 Polystyrene 164
11.32 Polysulfone 166
11.33 Poly(phenylene sulfide) 166
11.34 Polyvinylacetate 167
11.35 Polyvinylalcohol 167
11.36 Polyvinylbutyral 168
11.37 Polyvinylchloride 168
11.38 Polyurethanes 170
11.39 Proteins 173
11.40 Rubber, natural 174
11.41 Silicone 174
11.42 Styrene-butadiene rubber 176
11.43 Styrene-butadiene-styrene 176
11.44 Starch 177
References 178
12 USE IN INDUSTRIAL PRODUCTS 187
12.1 Adhesives and sealants 187
12.2 Aerospace 189
Table of Contents v
12.3 Agriculture 190
12.4 Automotive applications 192
12.5 Bottles 194
12.6 Ceramic materials 196
12.7 Composites 197
12.8 Coated fabrics 197
12.9 Cosmetics 199
12.10 Dental materials 199
12.11 Electronics 200
12.12 Fibers 202
12.11 Film 203
12.12 Food 212
12.13 Foams 213
12.14 Gaskets 215
12.15 Inks, varnishes, and lacquers 215
12.16 Medical devices 216
12.17 Membranes 217
12.18 Paints and coatings 217
12.19 Pharmaceutical products 218
12.20 Photographic materials 220
12.21 Pipes 222
12.22 Roofing materials 222
12.23 Tires 223
12.24 Toys 225
12.25 Wire & cable 225
References 225
13 VARIOUS PROCESSING METHODS 231
13.1 Blow molding 231
13.2 Calendering 233
13.3 Coextrusion 233
13.4 Compression molding 234
13.5 Compounding (mixing) 237
13.6 Dip coating 238
13.7 Dryblending 240
13.8 Extrusion 241
13.9 Extrusion blow molding 244
13.10 Injection molding 246
13.11 Printing 249
13.12 Reaction injection molding 252
13.13 Rotational molding 253
vi Table of Contents
13.14 Rubber processing 254
13.15 Slip casting 255
13.16 Thermoforming 256
13.17 Transfer molding 257
References 257
14 SPECIALIZED ANALYTICAL METHODS 261
14.1 Identification 261
14.2 Determination of concentration 262
14.3 Determination of volatility and molecular motion 263
14.4 Study of materials containing additives 265
References 267
15 MATHEMATICAL MODELLING 269
References 271
16 HEALTH, SAFETY AND ENVIRONMENTAL 273
16.1 Antiblocking agents 273
16.1.1 Inorganic 273
16.1.1.1 Calcium carbonate 273
16.1.1.2 Carbon related materials 274
16.1.1.3 Ceramic and glass spheres and fly ash 274
16.1.1.4 Diatomaceous earth and natural silicas 274
16.1.1.5 Synthetic silica 275
16.1.1.6 Synthetic clay (laponite) 275
16.1.1.7 Talc 275
16.1.2 Organic 276
16.1.2.1 Microparticles 276
16.2 Release agents 276
16.2.1 Fluorocompounds 276
16.2.2 Polydimethylsiloxane 276
16.2.3 Polymeric waxes 277
16.2.4 Other chemical compounds 277
16.3 Slip agents 278
16.3.1 Acids 278
16.3.2 Esters 278
16.3.3 Fatty acid amides 278
16.3.4 Natural wax 279
16.3.5 Salts 279
Table of Contents vii
17 REGULATIONS AND DATA 281
17.1 Toxic substance control 281
17.2. Carcinogenic effect 283
17.3 Workplace exposure limits 284
17.4 Food regulatory acts 286
References 288
18 PERSONAL PROTECTION 289
18.1 Clothing 289
18.2 Gloves 290
18.3 Eye protection 292
18.4 Respiratory protection 293
References 297
INDEX 299
1
Introduction
1.1 HISTORICAL DEVELOPMENTS
Surface blocking was a technological hurdle for as long as humans began to pro-
cess materials. In ancient times natural products were used to improve technologi-
cal output and quality. These included beeswax, plant waxes, natural resins, oils,
etc. They were used advantageously in cosmetics (e.g., creams used by Cleopatra
in Egypt), plasters (e.g., wall plasters in Pompei, Italy), molds, etc.
The priority of application of modern additives is not documented in research
publications but the use of antiblocking, release, and slip agents is rather recent
advancements of technological processes. This is easy to predict knowing the ori-
gin of several materials involved in their production. Stearic acid is the oldest syn-
thetic material used in material processing. It was first obtained by French chemist
Chevreul who began studies of soaps and isolated the most common fatty acids. In
1825, together with Gay-Lussac, Chevreul patented use of stearic acid in candle
manufacturing. It took about a century to apply stearic acid in polymer processing.
Calcium stearate was first used for commercial purposes by Harrison in 1924.1
Crambe abyssinica, which is a cool-season oilseed containing large concen-
trations of erucic acid, was introduced in the United States of America in 1940 by
the Connecticut Agricultural Experiment Station.2 About 39% of high-erucic-acid
oils are now used for production of erucamide, which is a common slip agent.2
The first major paper on mold release was published in 1946 by Ziegler.3 It
contained a thorough analysis of the influence of mold material on release proper-
ties. Even more important, the paper3 contained a proposal for a new method of
mold release testing, which gave the fundamental tool for rational analysis of the
problem. More than twenty of the so-called “mold lubricants” were tested by the
newly developed pull-out force method. In addition, the effect of “lubricant” on
product clarity was observed − both results being considered in the final selection.
In the best cases, the decrease of up to 80% of pull-out force was obtained with
these tested “lubricants”. Plasticizers and pigments were also found to facilitate
mold release properties in combination with mold release agents.
Film wrapping and handling characteristics were of major concern for film
producers and these prompted studies of slip agents. The first major paper on
improvement of friction coefficient of polypropylene film was published in 19664