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Thermoset Resins

Market Report
Ken L. Forsdyke and Trevor F. Starr
Thermoset Resins

A Rapra Market Report

by

Ken L. Forsdyke and Trevor F. Starr

November 2002

Rapra Technology Limited


Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
Tel: +44 (0)1939 250383 Fax: +44 (0)1939 251118 http://www.rapra.net
The right of K.L. Forsdyke and T.F. Starr to be identified as the authors of this work has been
asserted by them in accordance with Sections 77 and 78 of the Copyright, Designs and Patents Act
1988.

© 2002, Rapra Technology Limited

ISBN: 1-85957-355-X

All rights reserved. No part of this publication may be reproduced, stored in a retrieval system, or
transmitted in any form or by any means—electronic, mechanical, photocopying, recording or
otherwise—without the prior permission of the publisher, Rapra Technology Limited, Shawbury,
Shrewsbury, Shropshire, SY4 4NR, UK.

Typeset, printed and bound by Rapra Technology Limited.


Contents

1 About This Report ..........................................................................................................1


1.1 Introduction ................................................................................................................1
1.2 Scope of the Report ...................................................................................................1
1.3 Geographical Focus...................................................................................................1
1.4 Methodology ..............................................................................................................1
1.5 Units and Terms Used in the Report ..........................................................................1
1.6 Authorship..................................................................................................................2
2 Executive Summary .......................................................................................................3
2.1 Market Share .............................................................................................................3
2.2 Production Capacity and Operating Rates .................................................................4
2.3 Developments............................................................................................................4
2.4 Material Substitution ..................................................................................................4
2.5 Environmental Issues.................................................................................................5
2.6 Recycling ...................................................................................................................5
3 Thermoset Resin Types – Production Outline .............................................................7
3.1 Acrylics ......................................................................................................................7
3.2 Alkyds ........................................................................................................................7
3.3 Amino Resins.............................................................................................................8
3.4 Bismaleimides............................................................................................................8
3.5 Epoxy.........................................................................................................................9
3.6 Furane .....................................................................................................................10
3.7 Hybrids ....................................................................................................................11
3.8 Phenolics .................................................................................................................11
3.9 Polyimides ...............................................................................................................12
3.10 Unsaturated Polyester............................................................................................12
3.11 Polyurethanes........................................................................................................15
3.12 Vinyl Esters............................................................................................................15
3.13 Other Thermosetting Resins ..................................................................................17
3.13.1 Cyanate Esters................................................................................................17
3.13.2 Silicone-Based ................................................................................................17
3.13.3 Resins Under Development .............................................................................18
References ....................................................................................................................19
4 Applications..................................................................................................................21
4.1 Introduction ..............................................................................................................21
4.2 Adhesives ................................................................................................................21
4.2.1 Epoxy ................................................................................................................22
4.2.2 Unsaturated Polyesters .....................................................................................23
4.2.3 Phenolic ............................................................................................................23
4.2.4 Others ...............................................................................................................24
4.3 Buttons ....................................................................................................................24
4.4 Casting and ‘Solid Surface’ Applications ..................................................................24
4.5 Coatings ..................................................................................................................25
4.5.1 Arylzene Resins ................................................................................................25
4.5.2 Blocked Isocyanates..........................................................................................25
4.5.3 Epoxies .............................................................................................................26
4.5.4 Melamine Resins ...............................................................................................27
4.5.5 Phenolic ............................................................................................................27
4.5.6 Polyesters .........................................................................................................27
4.5.7 Polyurethanes ...................................................................................................27
4.5.8 Powder Coating.................................................................................................28
4.5.9 Vinyl Esters .......................................................................................................29
4.5.10 Others ............................................................................................................. 30
4.5.11 Ultraviolet Cure ............................................................................................... 30
4.6 Composite Matrices................................................................................................. 30
4.6.1 Processing and Fabrication............................................................................... 31
4.6.1.1 Autoclave Moulding .................................................................................... 31
4.6.1.2 Contact-Moulding (Hand Lay) and Spray Deposition .................................. 31
4.6.1.3 Cold-Press and Vacuum Bag Moulding ...................................................... 31
4.6.1.3 Filament Winding........................................................................................ 32
4.6.1.4 Continuous Lamination ............................................................................... 32
4.6.1.5 Hot-Press Moulding .................................................................................... 32
4.6.1.6 Pultrusion ................................................................................................... 33
4.6.1.7 Resin Injection (Transfer) or Resin Infusion Moulding................................. 34
4.6.2 Fire Retardant Composite Applications ............................................................. 34
4.6.3 Matrices for Composites.................................................................................... 35
4.6.3.1 Acrylics ....................................................................................................... 35
4.6.3.2 Bismaleimides ............................................................................................ 36
4.6.3.3 Epoxy ......................................................................................................... 36
4.6.3.4 Furanes ...................................................................................................... 37
4.6.3.5 Hybrids ....................................................................................................... 37
4.6.3.6 Melamine and Urea Formaldehyde Resins (Aminos) .................................. 37
4.6.3.7 Phenolic...................................................................................................... 37
4.6.3.8 Polyimides .................................................................................................. 38
4.6.3.9 Modified Polyimides.................................................................................... 39
4.6.3.10 Unsaturated Polyesters ............................................................................ 39
4.6.3.11 Urethanes................................................................................................. 39
4.6.3.12 Vinyl Esters .............................................................................................. 40
4.6.4 Composite Applications..................................................................................... 40
4.6.4.1 Aerospace .................................................................................................. 40
4.6.4.2 Chemical and Corrosion ............................................................................. 40
4.6.4.3 Energy Generation ..................................................................................... 41
4.6.4.4 Infrastructure .............................................................................................. 41
4.6.4.5 Marine ........................................................................................................ 42
4.6.4.6 Transport .................................................................................................... 42
4.7 Encapsulation.......................................................................................................... 43
4.7.1 Epoxies ............................................................................................................. 43
4.7.2 Hybrids.............................................................................................................. 43
4.7.3 Others ............................................................................................................... 44
4.8 Flooring ................................................................................................................... 44
4.8.1 Epoxies ............................................................................................................. 44
4.8.2 Polyesters and Vinyl Esters............................................................................... 44
4.8.3 Phenolic and Furane ......................................................................................... 45
4.9 Gelcoats and Pigment Pastes.................................................................................. 45
4.10 Paints and Lacquers.............................................................................................. 45
4.11 Pastes and Putties................................................................................................. 46
4.12 Polymer Concrete.................................................................................................. 47
4.13 Printing Inks and Associated Applications.............................................................. 47
4.14 Tooling .................................................................................................................. 48
4.15 Friction Materials ................................................................................................... 48
4.16 Foundry and Refractory Products .......................................................................... 48
4.17 Wood Products...................................................................................................... 49
4.18 Foams ................................................................................................................... 49
4.19 Mineral Wool Insulation ......................................................................................... 50
4.20 Moulding Compounds............................................................................................ 50
4.21 Abrasives............................................................................................................... 50
4.22 Rubber Compounding Resins................................................................................ 51
4.23 High Pressure Laminates.......................................................................................51
4.24 Sports Goods.........................................................................................................52
4.25 Others....................................................................................................................52
References ....................................................................................................................52
5 Market Development ....................................................................................................53
5.1 Introduction ..............................................................................................................53
5.2 Market Issues ..........................................................................................................53
5.3 Epoxy Based Resins................................................................................................55
5.4 Epoxy Vinyl Ester Based Resins ..............................................................................55
5.5 Phenolic Resins .......................................................................................................56
5.6 Polyimide Based Resins ..........................................................................................56
5.7 Polyurethane Based Resins.....................................................................................57
5.8 Unsaturated Polyester Resin Systems .....................................................................57
5.9 Conclusions .............................................................................................................57
6 Consumption – Current and Future ............................................................................59
6.1 Composites Matrices ...............................................................................................59
6.1.1 North America ...................................................................................................60
6.1.1.1 Market Size.................................................................................................60
6.1.1.2 Comment ....................................................................................................62
6.1.2 Western Europe ................................................................................................63
6.1.2.1 Market Size.................................................................................................63
6.1.2.2 Comment ....................................................................................................63
6.1.3 Eastern Europe .................................................................................................65
6.1.3.1 Market Size.................................................................................................65
6.1.3.2 Comment ....................................................................................................65
6.1.4 Asia-Pacific........................................................................................................66
6.1.4.1 Market Size.................................................................................................66
6.1.4.2 Comment ....................................................................................................67
6.1.5 Latin America ....................................................................................................67
6.1.5.1 Market Size.................................................................................................67
6.1.5.2 Comment ....................................................................................................68
6.1.6 Rest of the World...............................................................................................68
6.1.7 Summary and Analysis ......................................................................................69
6.2 Unreinforced Unsaturated Polyester Resin: Applications .........................................70
6.2.1 North America ...................................................................................................70
6.2.2 Western Europe ................................................................................................71
6.2.3 Eastern Europe .................................................................................................71
6.2.4 Asia-Pacific........................................................................................................71
6.2.5 Latin America ....................................................................................................72
6.2.6 Rest of World.....................................................................................................72
6.2.7 Summary...........................................................................................................72
6.3 Value: Thermoset Resins for Composites and Associated Applications ...................73
6.4 Adhesives ................................................................................................................73
6.5 Encapsulation ..........................................................................................................75
6.6 Coatings, Flooring and Allied ...................................................................................76
6.7 Polyurethanes..........................................................................................................77
6.8 Other Thermosets – North America .........................................................................77
6.9 Overall Summary, Analysis and Conclusions ...........................................................77
References ....................................................................................................................80
7 Major Players and Company Profiles..........................................................................81
7.1 Acquisitions and Related Information .......................................................................81
7.2 Companies’ Directory...............................................................................................83
7.3 Company Profiles.....................................................................................................97
7.3.1 AOC ..................................................................................................................97
7.3.2 ASHLAND SPECIALTY CHEMICAL COMPANY ...............................................97
7.3.3 BAKELITE AG................................................................................................... 98
7.3.4 BOYTEK ........................................................................................................... 99
7.3.5 BÜFA POLYURETHANE GmbH & Co. KG ..................................................... 100
7.3.6 CRAY VALLEY ............................................................................................... 100
7.3.7 DSM COMPOSITE RESINS ........................................................................... 100
7.3.8 DOW CHEMICAL COMPANY ......................................................................... 101
7.3.9 HENKEL TEROSON GmbH............................................................................ 102
7.3.10 ITW PLEXUS ................................................................................................ 102
7.3.11 KÖMMERLING CHEMISCHE FABRIK GMBH & CO .................................... 103
7.3.12 LLEWELLYN RYLAND LTD.......................................................................... 103
7.3.13 LORD CORPORATION................................................................................. 104
7.3.14 LOCTITE CORPORATION ........................................................................... 104
7.3.15 REICHHOLD................................................................................................. 104
7.3.16 SCOTT BADER............................................................................................. 106
7.3.17 SIKA AG ....................................................................................................... 106
7.3.18 SP SYSTEMS ............................................................................................... 107
7.3.19 VANTICO LIMITED ....................................................................................... 108
8 Standards and Legislation ........................................................................................ 109
8.1 Standards.............................................................................................................. 109
8.2 Legislative Matters................................................................................................. 113
8.2.1 Chemical Emissions........................................................................................ 114
8.2.2 Fire Hazards ................................................................................................... 115
9 Environment and Recycling ...................................................................................... 117
9.1 Introduction............................................................................................................ 117
9.2 Composites Recycling ........................................................................................... 117
9.2.1 The Japanese Approach ................................................................................. 118
9.2.2 The French/German Approach........................................................................ 119
9.2.3 The Canadian Approach ................................................................................. 120
9.3 Recycling of Polyurethane ..................................................................................... 120
References.................................................................................................................. 120
Glossary of Terms ........................................................................................................ 121
Abbreviations and Acronyms ...................................................................................... 123
Thermoset Resins Market Report

1 About This Report

1.1 Introduction

Although the oldest is now well over 100 years old, the majority of thermoset resins are much
younger, typically little more than 60. They are man-made materials forming part of the plastics or,
more correctly, polymer family. It is interesting to see that, after nearly 110 years, phenolic resins,
the oldest truly man-made resins, retain the largest production volume of all thermosets. These
resins, both resol and novolak, solid, liquid and solution grades provide man with a wide spectrum
of highly viable, useable and economic thermosetting materials which satisfy the requirements of a
wide range of applications. Breadth of application is common to many thermosetting resins.

1.2 Scope of the Report

It is the purpose of this study to examine the different types of thermosets, to outline their
respective methods of manufacture and conversion into finished products, to detail their many
applications and, finally, to quantify their current and predict their future market status. The
emphasis in this report is on materials where key developments are taking place or consumption is
significant. Thus, the use of thermoset resins in the manufacture of fibre-reinforced composites
well exceeds, in these pages what may be other, equally important applications for some readers.

This study looks primarily at those thermosetting materials which have made a significant market
penetration. There are literally dozens of developmental or very specialist materials which, by
virtue of their very small production quantity, have been deemed to have no real bearing on the
market, about which this report is written.

Like other market reports published by Rapra Technology, the overall aim is to provide the reader
with a summary of commercially relevant information. It is written for readers from all sectors of
the thermoset resin industry.

1.3 Geographical Focus

The aim of this study has been to encompass the worldwide thermoset resin market place.
However, data is more readily available on both the current and future Western European and
North American situations, hence there is a greater emphasis on these areas. Nevertheless, as
indicated in Chapter 6, which considers world statistics, the regions of Eastern Europe, Asia-Pacific
and Latin America are not overlooked. As their industrialisation and/or economies improve, all
three areas can be expected to play an increasing part in the development, manufacture and sales of
all thermoset resin systems.

1.4 Methodology

An extensive but selective database has been employed in the preparation of this report. This has
ranged from the examination of the relevant published material, as found in journals, textbooks and
conference proceedings, as well as in technical and publicity literature, through both telephone
and/or written, company and private interviews, and, finally, e-mails and traditional
correspondence. The assistance of all those who have helped with the preparation of this study is
acknowledged gratefully.

1.5 Units and Terms Used in the Report

Unless noted separately, the following statistical attributes apply throughout the study:

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Thermoset Resins Market Report

• Monetary values are based on the US dollar value as at the time of publication and where
necessary take into account inflation running at a typical average of 2.0% per annum;

• All tonnage output or consumption values employ the same unit, metric ktonnes, and accepting
that this introduces some minor error, all final summary totals either by country or
geographical region, are rounded to the nearest 5,000 tonnes.

A directory of company web addresses is supported by a carefully selected number of company


profiles, summarised from Internet searching, or through interview or correspondence.

Finally, to supplement or explain any technical or industrial terms used, a short glossary and an
abbreviations and acronyms section conclude the report.

1.6 Authorship

The authors of this report are consultants for Fortech, which specialises in fibre reinforced plastics
(FRP) and was founded by Ken Forsdyke in 1990. This practice has clients worldwide and is
involved in production processes for composites, expert witness work on composite products,
applications of phenolic resins from friction materials to foundries, and composites marketing. Ken
Forsdyke and Trevor Starr are also members of the group which founded the UK Composites
Processing Association.

Kenneth L. Forsdyke is a Chartered Chemist, Fellow of the Institute of Materials, Minerals and
Mining (IOM3) and Member of the Royal Society of Chemistry. He has spent forty years in the
polymer industry. Since the 1970s he has worked on phenolic resins for wet lay composites,
polyesters and other thermosetting resin materials. Ken has had over thirty papers published, is
named as inventor on six patents and is currently Chairman of the South Wales Polymer Group of
the IOM3.

Trevor F. Starr graduated in metallurgy and is a Chartered Engineer and Fellow of the Institute of
Materials, Minerals and Mining. He has worked for over 30 years with the worldwide composites
industry, particularly through his UK-based consultancy practice, Technolex, which became part of
Fortech in 1999. Trevor has worked on several directories and data books covering the raw
materials, such as thermoset resins, employed by the composites industry, including a profile of the
global composites industry for Elsevier Advanced Technology. In 2000 he published Pultrusion for
Engineers with Woodhead Publishing.

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Thermoset Resins Market Report

2 Executive Summary

2.1 Market Share

Worldwide the current consumption of thermoset resins across the whole industrial spectrum totals
a massive 27 million tonnes. Collectively, that industry continues to grow at a rate forecast to
average marginally over 2.5% per annum. Taking that estimate, some five years from now the
consumption will have risen to 31 million tonnes. For reasons discussed in this study, it has not
been possible to put an exact value on this industry. If, however, an average price of US$1,250 per
tonne is used, the value of the industry to the world economy is around US$34 billion, rising within
five years to in excess of US$39 billion.

In other words, thermosets comprise a raw material output totalling virtually 25% of the world’s
total plastics production. Polyurethanes (PU) at 34% comprise the major sector of that current
consumption, with urea-formaldehyde (UF) at 32%, phenol-formaldehyde (PF) at 15%, unsaturated
polyesters (UP) at 9%, epoxies at 5%, melamine-formaldehyde (MF) at 4% and the furanes (plus
other unclassifieds) at 1% taking up the remainder. This is depicted in Figure 2.1. These percentage
breakdowns are not expected to change significantly by 2007, although some resins, for example
the epoxies, are expected to see growth in excess of the forecast 2.5% over the next five years at
the expense of other thermosets.

Other
MF
Epoxy 1%
4%
5%
UP
9% PU
34%

PF
15%

UF
32%

Figure 2.1 Estimated market share of world thermoset resin production by material, 2002

Although, maybe in comparison to, e.g., the electronics industry, these consumption figures are not
very impressive, they are an achievement for an industry which, with some exceptions, did not
really exist until the Second World War. It is the same basic chemistry of those early phenolics,
epoxies, polyesters and polyurethanes, that has spawned a growth industry manufacturing an ever
increasing range of adhesives, sealants, coatings, composite matrices, refractories and an enormous
range of other materials. All have become essential to the life of modern man and whether raw

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Thermoset Resins Market Report

material or finished product, all remain open to further development and even greater
commercialisation.

This worldwide industry is both thriving and growing and in a cost-effective manner continues to
supply high performance, high quality products for an ever expanding range of applications and
markets. Many industries now depend on the thermoset resin industry’s output and continued
success and the future can only be summarised as both bright and exciting.

2.2 Production Capacity and Operating Rates

Production capacity and operating rates would be impossible to obtain for the high tonnage
thermosets. Whilst there may be ten high density polyethylene (HDPE) plants in the world (or
fewer) there are thousands of, e.g., polyester plants. In China for example, many moulders produce
their own resins! There are some larger manufacturers but the total tonnage of all the small ones is
probably as great. For example, the world capacity for polyester resins is probably about 3.0
million tonnes. The European industry is currently thought to be operating at ca. 70-75% capacity.

2.3 Developments

Progress has been rapid in this field. For example, adhesives used to be restricted to relatively low-
performance applications, while today the range of formulations makes it possible to assemble
aircraft and automotive components in situations where, formerly, welding or mechanical fixing
was the only practical answer. Sealants have equally changed beyond all recognition from a few
simple filler-like grades to a vast range of sophisticated products, whose cost and ease of
application permits their use in highly critical industrial applications. Similar advances have been
made in paints, lacquers and other coating materials, whether for application to timber, metal,
concrete or other substrate. All have been developed to be more resistant to the environmental
conditions to which they are subjected in use.

All of these advances illustrate the enormous progress which has been made in thermosetting resin
chemistry. Probably the greatest and most visible growth application for thermosetting resins over
the last thirty to forty years has been as matrix resins for composite materials. The tremendous
growth in the acceptance of composites as first class, true engineering materials is arguably the
main thermoset resin success story.

The high strength to weight ratio of engineered composites and the great improvements which have
taken place in manufacturing techniques, allowing greater reproducibility and, therefore, greater
confidence in mechanical and physical properties of finished components, has seen the advance of
thermoset resins from heavy industry, such as foundries and friction materials to major mechanical
components for industries such as aerospace.

2.4 Material Substitution

Thermosetting resins may be used in such a wide range of applications that almost any traditional
material may be substituted by a thermoset, often to technical advantage. The principal limiting
factor is usually temperature. Thermosetting resins are based on organic backbones and the
toughest of these begin to degrade at around 300 °C, although some will take short-term exposure
well above this. Metals operating at temperatures within the limits for the resin are often replaced
to advantage by thermosetting composites offering weight saving, corrosion resistance, better
specific stiffness and durability. Some thermosetting structures actually perform better in fire than
metal equivalents. Natural products such as marble and other stone may be replaced by
conglomerate stone or stone effect solid surfaces, which offer improved chemical resistance,
improved impact resistance and better hygienic cleaning. Timber is limited as a structural material
by natural faults and maximum sizes. Thermosetting resins may be used to laminate timber to sizes

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Thermoset Resins Market Report

not seen in natural lumber, to increase strength and minimise the effects of natural weak spots. The
ability of thermosetting resins to replace more traditional materials is endless. There is even woven
phenolic cloth which unlike 'polyester' cloth which is thermoplastic, is fully thermoset.

2.5 Environmental Issues

The thermoset industry has not been remote from environmental issues. The need to reduce VOC
emissions has had its effect on the whole range of applications from prepreg production to hand-lay
composites manufacture or in the use of adhesives and sealants. This report shows that the
manufacturers of thermoset resins are making rapid advances to improve where technically
possible. One example of this would be the paints industry where water dispersed systems have
taken over from solvent based in several areas and powder coating technology, using a whole range
of resins, is growing rapidly.

2.6 Recycling

Although thermosets, by their irreversible chemical nature, pose much greater recycling problems
when compared with some other materials, many thermosets can be used a ‘second’ time. This
second use may well be entirely different from the first, but this provides an answer to
environmental concerns. Thermoset-based composites cannot be remelted and reworked like a
thermoplastic but production waste and redundant components may readily be granulated and
reused. Applications include road surfacing products and traditional concrete, as well as use as
fillers in other thermoset based materials for the production of building blocks, polymer concrete
and moulding compounds. There is also energy to be recovered from redundant thermosets and use
has been made of this in Japan.

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Thermoset Resins Market Report

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Thermoset Resins Market Report

3 Thermoset Resin Types – Production Outline

Several textbooks have been written describing thermoset resins in general [1, 2, 3]. It is important
to recognise that the twelve classifications employed below as a means of aiding this essentially
technological description of the variety of thermoset resins are limited and far from definitive. With
both the past and current rapidity of resin development, there is an increasing chemical inter-
relationship, one resin type to the next. As a consequence, there is a high potential for serious
formulation confusion. This is suitably exemplified by the difficulty of accurately and thoroughly
differentiating between say, epoxy, vinyl and epoxy vinyl ester resins, and polyurethanes and
polyisocyanurates, where the latter two have simply been treated as polyurethanes. However, in a
report which is market, rather than chemically orientated, the use of such a generalised outline
grouping is considered justified.

Application examples outlined within each resin description are indicative of some of the areas in
which the particular resin type may be used. A more comprehensive description is provided under
respective application headings later in this study.

Examples of manufacturers of different resins are included in the text. The list is not definitive, nor
does it aim to be, there are simply too many companies worldwide now involved in the
manufacture of thermoset resins.

3.1 Acrylics

Polymers of the acrylic acids and their esters such as polymethylmethacrylate are thermoplastics
and well-known materials. However, as a result of their acid and ester side groups, the monomers
may be modified to produce molecules in which there is more than one reactive site. These in turn
can be made into crosslinkable polymers and hence thermosetting materials. Typical of these are
the urethane-acrylics marketed by Ashland Chemicals as ‘Modar’ resins, Dow ‘Derakane’ vinyl
esters and Akzo ‘Spilac’ all of which are designed as laminating resins for the production of
composites.

Companies which manufacture acrylics include:

Advanced Composites Pty Ltd


Atofina
Barentz N V
BF Goodrich
Euroresins UK Ltd
FVH Polyester
LV Lomas Ltd
Singapore Highpolymer Chemical Products Pte Ltd

3.2 Alkyds

Alkyd resins are made by the reaction of a polyhydric alcohol such as glycerol with a polybasic
acid such as phthalic acid or the fatty acids of natural oils such as linseed oil. The oils are
triglycerides and have long chain unsaturated groups as part of their make-up. It is these groups
which can air-oxidise and, in the presence of a suitable catalyst or ‘drier’ produce a crosslinked
product. Because the crosslinking process is air oxidation, alkyds of this type are only satisfactory
as thin coatings and hence their use in paints. Alkyds are in fact a specific type of polyester. Types
crosslinking by addition polymerisation through unsaturation rather than air oxidation, have been
used to produce moulding compounds.

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Thermoset Resins Market Report

Alkyds are manufactured by the following companies:

Bayrakli (Dewilux)
Dar-Tech Inc
Eastech Chemical
Eternal Chemical Co Ltd
Lilly Industries Inc
Nuplex Industries Ltd
Resana S/A

3.3 Amino Resins

Amino resins is the collective term applied to urea- and melamine-formaldehyde resins. These
materials are made by the condensation of the appropriate amine with formaldehyde in a two-stage
reaction process.

Urea, CO(NH2)2, a white crystalline solid, is made by the reaction of liquid CO2 with ammonia
under high pressure (100-200 atmospheres) at 135-195 °C. It is condensed with formaldehyde
under neutral or slightly alkaline conditions to produce mono- and di-methylol ureas. This first
stage product is then reacted further under acid conditions, with heating, to produce viscous syrup.
The reaction is stopped before crosslinking occurs by changing the pH to a slightly alkaline one.
The syrup can be used to impregnate paper for the production of decorative laminates.

Urea-formaldehyde moulding materials are made from the second stage product by the addition of
fillers such as wood flour (often bleached for best colour), pigments, stabilisers (e.g.,
hexamethylenetetramine), hardeners (a latent acid which decomposes at moulding temperature to
yield an acid) and other ingredients to aid processing.

Manufacturers such as BIP Limited supply urea-formaldehyde resins. Very large quantities of UF
resins are made in-house be users such as particle board manufacturers.

Melamine (a six membered ring structure of alternating nitrogen and carbon atoms having -NH2
groups attached to the carbons) is prepared from urea at high pressure and temperature. Yields are
low (30-35%) but the major by-product, ammonium carbamate, can be recycled to urea.

The resins are produced by condensation with formaldehyde under mildly alkaline conditions, the
first stage being the production of methylolmelamines which can have from one to six methylol
groups per melamine molecule. It is normal to use a molar ratio of formaldehyde to melamine of
ca. 3:1. The resulting resin may be impregnated to paper or converted to moulding powder.
Melamine resins may also be spray dried to extend their limited shelf-life in solution.

Manufacturers of melamine resins include Applied Polymer Systems Inc, BIP Ltd, CECA, Eternal
Chemical Co. Ltd. and Helios.

3.4 Bismaleimides

Bismaleimides are the condensation products of a diamine with maleic anhydride. Typical
diamines include methylene dianiline and methylene diamine. The products are very high
temperature resistant materials which are used for heat resistant coatings, high performance printed
circuit boards and as composite matrices in aerospace applications.

Bismaleimides are produced by Siber Hegner Ltd., CBC Europe Limited and HOS-Technik GmbH.

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Thermoset Resins Market Report

3.5 Epoxy

Developed largely as a result of the Second World War, but only available commercially from
around 1950, the very versatile family of thermosetting epoxy resins offer high-performance under
raised temperature and corrosive environments. In other words, the epoxies are, in comparison to
most other thermosets, sophisticated resin systems. They have, as a result of their wide molecular
weight spectrum, a considerable application latitude, whether for adhesives, encapsulation, flooring
or as composite matrices.

Epoxy resins are manufactured by the condensation of an epoxy containing molecule, such as
epichlorohydrin, with a diphenol such as bisphenol-A (diphenylol propane) in the presence of an
alkaline catalyst. The resulting molecule, the epoxy resin, is an alternating copolymer with
secondary hydroxyl groups along the chain and epoxy terminal groupings. Depending on molecular
weight, this can be a viscous liquid or a brittle, low melting solid. A typical structure for such a
resin is shown in Figure 3.1.

O CH3 CH3 O

H2C HC H2C O C O CH2 CH CH2 O C O CH2 CH CH2

CH3 OH n CH3

Figure 3.1 Bisphenol-A based epoxy, general molecular structure

Consequently, an epoxy resin can be denoted by both its functionality value as well as by its
molecular weight. When an epoxy resin contains two epoxy groups per molecule it is referred to as
a ‘di’-functional resin, but if more than two, then as a multifunctional resin. The total concentration
of epoxy groups can be expressed on a molecule weight basis known as the ‘weight per epoxy’
(WPE), i.e., the weight of resin in grams to provide one molar equivalent of epoxy. Other
expressions such as ‘epoxy equivalent weight’ (EEW) or ‘epoxy molar mass’ (EMM) are also used.

The resins may be crosslinked or ‘cured’ in many ways using both the terminal epoxy groups and
the secondary hydroxyl groups on the polymer chain.

Table 3.1 indicates the range of bisphenol-A-based epoxy resins available in the market place. The
description solid simply means that the resin is of sufficient molecular weight to be solid at room
temperature and not that it is already crosslinked. Such resins are used at elevated temperatures as
melts or as solutions.

Table 3.1 Properties of typical commercial grades of bisphenol-A-based epoxy resins [4]
Viscosity
Molecular weight WPE ‘n’
Pas @ 25 °C
350 182 0 8
380 188 0.12 14
600 310 0.9 Semi-solid
900 475 2.0 Solid
1400 900 3.7 Solid
2900 1750 9.0 Solid
3750 3200 11.9 Solid

There are many, alternative starting materials for the production of epoxy resins, epichlorohydrin
and bisphenol-A is simply a common example. If the eventual epoxy resin was required to offer a
degree of fire retardancy, then a halogenated starting material could be used such as tetra-
bromobisphenol A. Equally, phenolic or alkylated phenolic novolaks, can be glycidated in an
identical manner to bisphenol-A-based resins, to provide multifunctional epoxy resins. Many other

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Thermoset Resins Market Report

starting materials are possible yielding a wide range of crosslinked resin properties which are
reflected in the wide application range of these resins.

Applications range from structural composites for aircraft, yachts and sports equipment to coating
of metals for industrial corrosion prevention and electronic encapsulation. Hence the need for the
wide variety of properties which can be obtained from the multiplicity of possible chemistry.

The wide range of chemical compositions of commercial epoxy resins leads to an equally wide
range of chemical co-reactants, catalysts or modifiers which may be used with them. In thermosets
which crosslink principally by an addition reaction, a suitable weight proportion of a ‘free radical’
catalyst is added to the desired quantity of resin, usually containing an accelerator, immediately
before use. In epoxy resins, amine, acid anhydride or Lewis acids, are typically supplied
compounded into one part of a two-part system. The correct weight or volume ratios of the two
parts are brought together and mixed ready for use. It is also worth mentioning that the cure
conditions are a sound indicator of the temperature performance of the final, crosslinked resin;
room temperature cure systems are rarely, if ever, suitable for other than low-to-moderate in-
service temperatures, whilst cure at say 120 °C or more indicates a resin exhibiting a much higher
temperature resistance, sometimes above the cure temperature.

Epoxy resins in particular, allow the use of other non-chemical procedures to promote cure and
these are finding increasing importance in a number of applications. For example, microwave
energy, with or without the addition of a chemical promoter, can be employed successfully to
enhance the cure of composite mouldings and cationic, ultraviolet photocure, is already well-
established for those epoxies used in both dentistry and adhesive formulations. Powder coating as
an alternative to spray-painting, with its associated VOC emission problem, is yet another major
and from the view-point of reducing VOC emissions, a very important market sector where epoxy
formulated systems are gaining ground.

There are many manufacturers of epoxy resins as illustrated by the following list:

Abatron Inc
AdTech Plastic Systems Corp
Amber Composites
Chemres
Gaches Chimie
Gougen Brothers Inc
Hexcel Composites Ltd
Lonza Inc
Resolution Performance Products LLC
Vantico

3.6 Furane

Furane (or furan) resins are the product of the condensation of furfuryl alcohol and/or
furfurylaldehyde (furfural). Furfural occurs in many plants and is extracted commercially from
products such as oat husks and corn cobs. The alcohol is made by the catalytic hydrogenation of the
aldehyde. The polymerisation reaction is carried out under acid conditions but is extremely
exothermic and is stopped by neutralisation. Crosslinking, which can also be acid induced, is not
fully understood but appears to be by an addition polymerisation reaction. This has been
determined by detectable loss of unsaturation. The cured resins are used for heat resistant
applications and are very resistant to chemical attack. They were used for tank lining in chemical
plant but are somewhat brittle and have been replaced in many, but not all, applications by
materials such as vinyl esters.

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Thermoset Resins Market Report

Furanes are produced by a number of companies:

Ashland Italia SpA


Beetle Plastics Inc
Brace
Exaton Composites (Pty) Ltd
Univar plc
Vidropol SA

3.7 Hybrids

Commercially the term ‘hybrid’ resins has been applied principally to urethane modified
polyesters. These materials have been marketed heavily in the United States claiming to give
benefits of toughness to polyester resin systems.

3.8 Phenolics

Phenolic resins [4] are the oldest completely man-made resins having been commercialised before
the turn of the nineteenth century. Phenol was originally extracted from coal but is today made by
the oxidation of cumene. In 1997 only 2% of the world’s phenol came from coal. Formaldehyde is
manufactured from methanol over a silver catalyst. The methanol is made from CO and hydrogen,
the latter from natural gas in today’s economy.

The term phenolic resin is used to describe a very large range of materials. In simple terms
phenolic resins are the condensation product of a phenol with an aldehyde. The most common of
these is the condensation product of phenol with formaldehyde. Phenol-formaldehyde resins are
manufactured in two chemical groups, resol (also spelt resole) and novolak (also spelt novolac).

The resol resins are manufactured with a formaldehyde to phenol molar ratio greater than one,
normally in the range 1.4 to 1.6. The resulting resin has more than one methylol group attached to
each aromatic ring and these can be used for crosslinking. Hence the resin is a true thermoset as
manufactured. Resol resins are made by the simple condensation of the starting materials in a
stainless steel or glass lined vessel fitted with a condenser arranged both to reflux and distil. The
usual catalyst is an alkaline material and may be caustic soda, ammonia, an amine, sodium
carbonate, etc. Whilst the reaction will take place under either acid or alkaline conditions, acid
catalysis is generally too violent for commercial resol production. Temperatures used are up to
boiling, much of the heat of reaction being taken away by the condensers as well as a jacket on the
reactor. The final product may be liquid, a solution in an added solvent (ketones and alcohols are
most common) or, occasionally a solid. The production of solid resols is a hazardous business since
the point at which the molecular weight is sufficiently high for the product to be solid and that at
which it is effectively crosslinked and intractable are very close. Solid resols are emptied from the
reactor in the molten state into a box filled with chilled plates, or a similar shock cooling device,
where it freezes rapidly and the reaction stops.

Novolak resins, in which the formaldehyde to phenol molar ratio is less than one, may be made
using an acid catalyst although even then the acid would be a weak organic acid and not a mineral
acid. Because there is insufficient formaldehyde present to crosslink the product, the resulting
polymer is a thermoplastic and usually solid, although, as with resols, it may be supplied as a
solution directly from the plant. If solid, the resin is poured from the reactor as a melt, either via
small holes to form ‘pastilles’ on a moving, cooled belt or as a continuous stream from whence it is
broken up into crude lumps. Either way the resin is ground in a fine grinding plant usually with the
addition of a formaldehyde donor such as hexamethylenetetramine (hexa). The resin, packed in
bags or supplied as bulk powder in tankers, is then ready for use. The hexa provides the extra

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Thermoset Resins Market Report

methylene bridges needed to complete the crosslinking reaction when the powder is heated to a
melt again in processing.

In the great majority of phenolic resin applications, these polymers are cured by heat alone,
although there are often traces of the original alkaline catalyst in resols, which, on heating, speeds
the crosslink reaction. Typical cure temperatures are 120-170 °C. Suitably formulated resol resins
can also be cured by the addition of an acid catalyst at room temperature. The reaction is highly
exothermic but is used for the production of composites by both manual and machine techniques
and for the production of phenolic foams. In most cases the application of some heat (40-70 °C) as
a post cure or during cure is needed to ensure complete crosslinking.

Chemically modified phenolic resins are too numerous to list here. Typical modifications include
the use of alkyl phenols, cresol, resorcinol, aryl phenols, urea, melamine, natural phenols such as
cashew nut shell liquid, rubbers, other polymers as additive and co-reactants (e.g.,
polyvinylbutyral, polyvinylacetal), furfuraldehyde and other aldehydes, etc. Each modification has
its own purpose and the range of materials which can be produced is very large indeed.

Phenolics are manufactured by many companies including:

AD Vershure VVK
Bakelite AG
Borden Chemical
Chem-Materials Co
Georgia-Pacific Resins Inc
Huntsman Chemical Co
TCR Composites

3.9 Polyimides

The first polyimides were made by the condensation of pyromellitic dianhydride with aromatic
amines such as m-phenylenediamine. More recently the range of monomers used has broadened but
all remain complex chemicals and hence the resins are expensive materials. As a commercial
example, Du Pont’s ‘Kapton’ material is the condensation product of pyromellitic dianhydride and
di-(4-aminophenyl)ether. These materials are moulded at high temperatures (ca. 300 °C) and post
cured at 400 °C.

Polyimides are supplied by Algram Engineering Co Ltd, Applied Polymer Systems, Esspee and
Stochem Inc.

3.10 Unsaturated Polyester

There is little doubt that the vast range of unsaturated polyester resins must be the best known of
any commercial thermosetting resin system because of their association with the general purpose
range of polyester/glass composites, usually known to the general public as ‘fibreglass’. This
popularity stems from their relative ease of manufacture, their economics, their ease of processing
or conversion into a finished product, their tolerance of processing, their range of ‘reactivity’ and
‘flexibility’ and moreover, their ability to be readily modified to answer specific use and finished
product performance demands.

The term polyester resins is deemed, for the purposes of this study, to mean unsaturated polyesters.
Polyesters are made by the condensation of a di-acid, or di-acid anhydride with a glycol. The most
commonly used saturated acids are ortho-phthalic acid (normally in the form of phthalic anhydride)
and iso-phthalic acid, and the commonest unsaturated acid is maleic acid. The most popular glycol
is 1,2-propylene glycol. The purpose of the saturated acid is to spread the unsaturation in the

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Thermoset Resins Market Report

molecule and hence prevent excessive crosslinking in the final product. The aromatic structures
also impart stiffness to the chain and that stiffness is modified by the maleic acid. Polyesters are
made to a very large number of formulations determined by the ultimate application. A typical
formulation for a general purpose resin would be propylene glycol 145 parts, maleic anhydride 115
parts and phthalic anhydride 85 parts.

In principle manufacture begins by reacting either an unsaturated dibasic anhydride (e.g., maleic
anhydride) or acid (e.g., fumaric acid) and a dibasic saturated anhydride (e.g., ortho-phthalic,
chlorendic or tetrachlorophthalic anhydride) or acid (e.g., iso-phthalic, adipic or sebacic acid) with
a suitable glycol (e.g., propylene, dipropylene or diethylene glycol). If fire retardancy is required in
the finished resin, halogenated monomers have been used but, owing to the toxicity of the smoke
generated when these materials are involved in fires, other methods of achieving improved fire
properties, such as adding additives to the finished resin, are assuming greater importance. The
ensuing, unsaturated polyester is then blended with a suitable active diluent, typically styrene but
many others are possible, in the desired weight proportion, to provide a resin with the viscosity and
reactivity suitable for the final application. The respective properties offered by each of these
‘building blocks’ is summarised in Table 3.2.

Table 3.2 The building blocks for unsaturated polyester resins [5]
Building block Raw material Characteristics
Unsaturated anhydrides Maleic anhydride Low cost, and provides a resin with a
and dibasic acids moderately high heat deflection
temperature (HDT)
Fumaric acid Imparts the highest reactivity (molecular
crosslinking), a higher HDT, and more
rigidity, but is a slower forming polyester
Saturated anhydrides and Phthalic (orthophthalic) Lowest cost, moderately high HDT;
dibasic acids anhydride provides stiffness, high flexibility and
tensile strength
Isophthalic acid Provides high tensile and flexural strength,
better chemical and weather resistance and
high HDT
Adipic, azelaic and sebacic Imparts flexibility (i.e., toughness,
acid resilience and impact strength). Adipic
acid is the lowest in cost of the
flexibilising acids
Chlorendic anhydride Employed where flame retardance is
demanded of the polyester resin
Terephthalic anhydride High heat deflection and high strength
Tetrachlorophthalic Confers flame retardancy to the polyester
anhydride resin
Glycols Polypropylene glycol A low cost glycol, provides a resin with
good water resistance and flexibility, plus
compatibility with styrene
Dipropylene glycol Used where flexibility and toughness are
required
Diethylene glycol Imparts greater toughness, impact strength
and flexibility
Hydrogenated bisphenol-A Provides a resin with better corrosion
resistance, a high HDT, high flexibility
and tensile strength
Tetrabromobisphenol-A For flame resistance

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Thermoset Resins Market Report

Manufacture involves a simple, stainless steel reaction vessel fitted with an agitator, a temperature
controlled heater, gas and raw material inlet/outlet ports and condensers, all connected to a final
blending tank. In principle, the chemical reaction, which takes place between the respective raw
materials in producing a polyester resin, is a reversible condensation reaction known as
polyesterification. Water is produced as a by-product and the rate of this polyesterification is
controlled by the reaction temperature and the rate at which the water is removed by the
condensers. The use of an agitator and a slow bleed of inert gas through the vessels contents as the
reaction proceeds, prevents the formation of hot-spots (which could cause pockets of differently
reacted resin) and the development of colour-producing oxidation reactions. The process is
carefully monitored throughout a number of distinct stages to ensure, commensurate with the raw
materials introduced initially to the reaction vessel, that a polyester resin of the desired molecular
weight, viscosity, acid and hydroxyl number results.

The simpler, orthophthalic resins employing both maleic and phthalic anhydride are single stage
reaction products, whereas a two-stage process is essential in the manufacture of isophthalic resins.

With the last traces of water removed, and with polyesterification complete, the hot resin is passed
to the blending tank for dilution with active monomer, which will be used in the crosslinking or
curing process. Whilst styrene remains the most common of these, vinyl toluene, methyl
methacrylate and many others may also be used. The unsaturated polyester resin industry has taken
major steps over recent years to reduce the styrene level as a means of limiting volatile emissions
during subsequent product manufacture. The increasing introduction by the industry of
dicyclopentadiene (DCPD) containing resins, has a similar purpose.

As supplied to the fabricator, unsaturated polyester resins usually contain an accelerator. A low
percentage addition of, e.g., a cobalt or zinc salt, is added to the resin to enhance or accelerate the
production of free radicals when the organic peroxide initiator (catalyst) is added to cure the resina).
Curing takes place by the linking of the unsaturation in one molecular chain of the polyester to that
in another with a small number of molecules of the chosen active diluent (e.g., styrene), using free
radical activated, addition polymerisation. The careful selection and use of accelerators and
catalysts, to ensure the optimum mechanical and physical properties from the chosen unsaturated
polyester resin, cannot be too highly stressed. The crosslinking process is highly time/temperature
sensitive with cure being achieved over a range of temperatures from room ambient to >100 °C,
depending on the process used and the product manufactured.

Unsaturated polyester resins can be tailored further by the use of non-reactive additives such as
mineral fillers, to adjust the physical properties to those required for fabrication into products. For
example, these additions can alter the viscosity and/or thixotropy of the resin, the cure rate and, by
counteracting moulding shrinkage, the eventual surface appearance of the finished component.
Pigments, opaque, translucent or transparent, can provide colour, and additions of ultraviolet
absorbers offer marked improvement in the resistance to outdoor environment exposure.

There are many suppliers of unsaturated polyester as illustrated by the following list:

APOC Hawk Ltd


Ashland Specialty Chemical Co
Composites One
Cray Valley Ltd
De Yssel Coatings BV
DSM Composite Resins

a)
The term ‘catalyst’ is chemically incorrect when applied to an organic peroxide used to initiate addition
polymerisation. ‘Initiator’ is the preferred chemical terminology for such a material. However, owing to the
industry having, in general, adopted the term ‘catalyst’, it is used in this study to avoid confusion.

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Thermoset Resins Market Report

Dulux-Resins
Interplastic Corporation
Lonza Spa Internmediates & Additives
NCS Resins
Neste Polyester
Reichhold Inc
Resinous Chemicals
Scott Bader Co Ltd
SIR Industriale
Vianova Resins

3.11 Polyurethanes

Polyurethanes are probably unique among thermosetting resins in that there is no such thing as a
‘polyurethane resin’. The producer of urethane products purchases what are basically the chemicals
from which the resin and the crosslinked thermoset will be made in one chemical process. A
‘urethane’ is the chemical group which results when an isocyanate is reacted with an alcohol.

R.NCO + HOR1 Æ R.NH.COOR1


isocyanate alcohol urethane

Polyhydroxy materials (polyols) will react with polyisocyanates to form polyurethanes with a large
variety of degrees of crosslinking from a very large variety of possible starting materials. The
commercially important isocyanates are: 2,4-tolylene di-isocyanate and 2,6-tolylene di-isocyanate
in an 80:20 or 65:35 mixture (TDI), diphenylmethane di-isocyanate (MDI), naphthylene di-
isocyanate, hexamethylene di-isocyanate and triphenylmethane tri-isocyanate. MDI and TDI are
the most important. All of these materials are liquids and all are toxic in nature to varying degrees.
Their handling in the production of polyurethanes must be very carefully controlled.

The nature of the polyurethane produced, rigid or flexible, is a function of the starting materials.
There are a very wide range of polyols both polymeric and monomeric from which to choose. By
careful selection of the polyol/isocyanate combination, the exclusion or otherwise of water, the
choice of catalyst, etc., these thermosetting materials may be used to produce a range of products
from rubbers to soft foams and from rigid insulation foams to rigid castings.

Many manufacturers supply polyurethanes including:

Ashland Distribution Co
Dar-Tech Inc
Elastogran
Hutchinson
Polymer Technologies
Resin Systems Inc
Technology Marketing Inc
Vianova

3.12 Vinyl Esters

Many of the introductory remarks for the unsaturated polyesters also apply here, the major
differences being the higher cost of vinyl ester raw materials and, hence, the resins. Vinyl esters
provide improved toughness and greatly improved chemical resistance compared to polyesters.

Vinyl esters were commercialised in the early 1970s and the two major types are both based on an
epoxy resin reacted with an acrylic monomer to form an unsaturated system capable of being

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Thermoset Resins Market Report

crosslinked. The first is formed by the reaction of a diglycidyl ether bisphenol-A epoxy resin with
methacrylic acid, followed by dilution in styrene monomer, whilst the second involves epoxy
novolak resins, again reacted with methacrylic acid and diluted with styrene monomer. Two further
types, polyester and urethane vinyl esters, are also manufactured but in much smaller quantities and
only for specialist application. The structure of a typical bisphenol-A based vinyl ester is shown in
Figure 3.2.

CH3 O OH CH3 OH CH3 OH O CH3

CH2 C C O CH2 CH CH2 O C O CH2 CH CH2 O C O CH2 CH CH2 O C C CH2

CH3 CH3
n

Figure 3.2 Typical bisphenol-A vinyl ester resin, general structure

The production equipment is very similar to that for unsaturated polyesters, although, because no
water or indeed other condensation product is formed during the reaction, the condensers are not
required. However, a much higher level of production control is essential. If for example, the
epoxy/acid reaction is not properly cooled on completion, then a gelation of the unfinished resin
can result. Further, the vinyl esters are more reactive than the unsaturated polyesters and, as self-
polymerisation can readily occur, cure inhibitors are added in conjunction with the styrene or other
monomer diluent.

This whole range of resins can be considered as a combination of the optimum characteristics of
unsaturated polyesters and epoxies (Table 3.3). Like the unsaturated polyesters, the basic resins can
be modified and one example, rubber-modified epoxy vinyl ester offers increased adhesive strength
with superior resistance to abrasion and severe mechanical stress, combined with greater toughness
and elongation at break.

Table 3.3 Cured resin property comparison, vinyl ester versus unsaturated polyesters [1]
Vinyl esters Unsaturated polyesters
Property Unit
Standard Modified Orthophthalic Isophthalic
Density g.cm-3 1.12 1.13 1.19 1.19
Tensile strength MPa 80 72 55 65
Elongation at break % 5 8 1.8 3.5
Tensile modulus MPa 3300 3000 4300 3600
Flexural strength MPa 145 135 100 125
Flexural modulus MPa 3100 2900 4000 3300
Heat distortion temperature °C 102 80 67 100
Water absorption, 28 days mg/test
60 75 90 95
seawater piece

The polymerisation of vinyl esters is achieved using accelerators, and peroxide catalysts in a
similar manner to polyesters.

Dow Composite Resins has announced the introduction of a new range of chemically resistant
Atlac E-Nova resins based on a completely new vinyl ester urethane chemistry.

Vinyl ester resins are supplied by a variety of companies among them are:

Alchemie Ltd
AOC
Dow Chemical
DSM Composite

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Thermoset Resins Market Report

Euroresins Italia Srl


Gwill Industries
Lonza SpA
Nippon Shokubai Co Ltd
Reichhold

3.13 Other Thermosetting Resins

The demand for higher and higher performance characteristics from thermosetting resins,
particularly in their application as matrices for aerospace composites, has led to the development of
a wide range of high performance, low tonnage, usually high cost materials over the years. Some of
these materials are discussed briefly below.

3.13.1 Cyanate Esters

Early development work of these materials by Bayer was based on bisphenol-A or phenolic
novolaks reacted with cyanogen chloride (ClCN). The reaction gives high yields of bisphenol-A
dicyanate ester, which trimerises into a cyanurate ring structure at elevated temperatures. The early
work was aimed at applications in aircraft brake friction components and electrical laminates. The
ownership of the technology passed to Mitsubishi Gas Chemicals and Celanese and the former has
commercialised a variant of the resin, known as the BT range. The Celanese activity was
eventually acquired by Ciba (now Vantico), which has extended the range. Allied Signal also has a
range of cyanate ester resins, known as Primaset PT, and these are based on phenolic novalaks.

Cyanate esters are used in high performance electrical applications with high Tg (>250 °C). They
may be toughened with some high performance thermoplastic resins such as polyethersulphone
(PES), polysulphone (PSF), polyphenylene oxide (PPO), etc., without loss of Tg.

Cyanate ester resins are supplied by Lonza, Ciba and Mitsubishi Chemical.

3.13.2 Silicone-Based

Renowned for their heat stability compared to their completely organic counterparts, silicone resins
are relatively expensive and generally less strong mechanically. They are made by the hydrolysis of
a mixture of chlorosilanes which, for the final product to be crosslinkable, must contain a
proportion of trichlorosilane. Typically the R/Si ratio has to be in the region of 1.2-1.6:1 where R is
the number of organic groups. These are most commonly methyl but may also be phenyl and the
methyl:phenyl ratio is another important defining parameter for the resins.

In commercial preparation the chlorosilanes are dissolved in a suitable solvent and blended with
water. Methyl silanes hydrolyse rapidly and with a high exotherm whereas phenyl silane may need
to be heated to achieve complete hydrolysis. At the end of the reaction the polymer solution is
separated from the aqueous layer and distilled to the required solids content. The polymer may be
further polymerised by heating with an organic salt such as zinc octoate until the required
molecular weight is achieved. The final crosslinking is carried out, when required, by heating in the
presence of a suitable catalyst such as triethanolamine or zinc octoate.

The properties of the cured material are dependent largely on the nature of the chlorosilanes chosen
initially. The largest uses are for high temperature electrical insulation often in the form of
impregnated glass cloth.

Silicone manufacturers include Bayer, Dow Corning, Rhone Poulenc, Wacker-Chemie, Toshiba,
Toray and Shinetsu.

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Thermoset Resins Market Report

3.13.3 Resins Under Development

During October 2000 the Mitsubishi Chemical Corporation of Japan announced in ‘Japan
Chemical Weekly’, the development of a crosslinked polyolefin, provisionally named TRC
Polymer, with the aim of commencing full-scale market development by the end of 2001. In spite
of exhibiting thermosetting properties, this marvellous, heat reversible and recyclable, crosslinked
polyolefin converts itself from a crosslinked resin to a heat reversible resin when heated at specific
temperatures, a property said to be possible by grafting two kinds of functional groups onto the
main polyethylene molecular chain. Ester bond reaction points transform themselves from
crosslinking to dissociation, a reaction which occurs reversibly between 160-200 °C, enabling the
resin to be moulded and recycled by melting at 250 °C. To the general-purpose, low specific
gravity, bending and chemical characteristic properties of polyethylene, are therefore added those
of crosslinked resins, such as improved heat, shock and creep resistance. Owing to the high degree
of moulding flexibility and obvious heat-sealing properties, there is hope that even though costing
several times more than polyethylene, there will be a respectable market demand for wire sheaths,
under-floor heating pipes and automotive components.

Dow Automotive has entered into an alliance with the Cyclics Corporation to develop cyclic
butylene terephthalate (CBT) resins for structural automotive applications. It is claimed that the
material has the processing advantages of a thermoset (e.g., low viscosity) and the material
properties of a thermoplastic when polymerised.

In other work, there is the potential for manufacturing rigid crosslinked thermosetting polymers
from plant triglycerides (e.g., a modified acrylated epoxidised soy oil resin, epoxy and urethane
resins from rape oil, etc.). These ‘natural’ resins are claimed to exhibit respectable mechanical
properties and water resistance as well as being highly suitable to employ with flax or hemp fibre
reinforcement in the resin transfer moulding of low-cost, high volume products. Mechanical
properties have still some way to go to compare with traditional polyester/glass composites but
could find application in motor vehicle interiors, for example, if the cost is economically
acceptable. These developments demonstrate the beginning of longer term investigations into
sustainable composites. This effort is receiving considerable research attention at the time of
writing, both in the US and Europe. In Europe a group of researchers and other interested parties
has founded SusCompNet (the Network for Sustainable Composites) based at The University of
Wales, Bangor.

The requirements of the advanced sector of the composites industry are far from being overlooked.
Phenylethnyl resins containing imide oliogomers, are under active development and
commercialisation for the cost-effective resin transfer and resin infusion manufacture of composite
components for high-performance aerospace application. Of particular interest is the Mach 2.4 civil
transport development requiring long-term performance at 177 °C and resins of this type with their
low viscosity, high melt stability, high Tg, acceptable toughness and good mechanical properties
are showing excellent promise in meeting demands of that order. The American company,
Raytheon Missile Systems is one advanced composites manufacturer hopeful of exploiting this type
of thermoset resin advance in applications which are, and will increasingly be, beyond the
capability of traditional metallic materials. Concepts under active discussion include fuselages,
wings, fins, control surfaces and radomes. It is equally worth note that for reasons of both
environmental protection and productivity, manufacturing methods are being aimed at reduced
solvent use and the use of ultraviolet radiation or electron-beam curing. As has happened in the
past, technological spin-off downwards is expected to eventually be of benefit to the more
commercial sectors of the worldwide composites industry.

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Thermoset Resins Market Report

References

1. J. Murphy, Reinforced Plastics Handbook, Second Edition, Elsevier Advanced Technology,


1998.

2. J.A. Brydson, Plastics Materials, Fifth Edition, Butterworth Heinemann, 1989.

3. T.F. Starr, Thermoset Resins for Composites, Second Edition, Woodhead Publishing Ltd.,
1998.

4. A. Gardziella, L.A. Pilato and A. Knop, Phenolic Resins, 2nd Revised Edition, Springer
Verlag, 1999.

5. T.F. Starr (Ed.), Pultrusion for Engineers, Woodhead Publishing Ltd., 2000.

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Thermoset Resins Market Report

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Thermoset Resins Market Report

4 Applications

4.1 Introduction

Table 4.1 indicates how phenolic and unsaturated polyester resins dominate in the wide-range of
uses to which thermosetting polymer systems are applied. The majority are used as a matrix for
fibre-reinforced composite materials, whether these be structural composites or composites with a
very different function such as a friction element. Several resins grouped as ‘others’ at the start of
this study, do not appear in this table but are discussed later in the text. It is also true to say that, for
some applications, many different chemical species of thermoset resin may be employed to the
same ultimate result. Some of the headings that follow refer to materials, some to the manner or
application in which those materials are employed, an arrangement found preferable owing to the
complex interrelationships which exist in this area.

Table 4.1 Summary of applications for thermoset resins


Resin Application
Acrylics Composites, sheeting, casting, paints
Alkyds Paints
Bismaleimide Composites
Epoxy Adhesives, encapsulation, flooring compounds, castings,
coating materials - liquid and powder, advanced composites,
polymer concrete, tooling
Furane Tooling
Hybrids Composites
Melamines and urea- Moulding materials, laminate surfacing materials, foams
formaldehydes
Phenolic Advanced composites, composites, moulding materials,
rubber reinforcing, refractory, foundry, adhesives, coatings,
friction elements, polymer concrete, insulation foam, floral
foam, mineral wool binding, felt bonding, electrical
insulation, abrasives, sealants, printing inks, fibre boards,
plywood, timber laminates, etc.
Orthophthalic and isophthalic Adhesives, buttons, castings, composites, encapsulation,
unsaturated polyester flooring materials, gelcoats, filler pastes, pigment pastes,
polymer concrete, putties, tooling, etc.
Urethane and isocyanurate Composites, paints, flexible foam, rigid foam, self-skinned
mouldings
Vinyl ester Adhesives, coatings, composites, flooring materials, tooling

4.2 Adhesives

Of all the uses to which thermoset resins are now put, one of the most significant in respect of
technological advance, has been adhesives. Whereas, not many years ago, welding or some form of
mechanical fixture such as a simple nut, bolt and washer sufficed, today there is an increasing
move towards the use of adhesives based on epoxy, phenolic, unsaturated polyester,
polyisocyanates, vinyl ester resins or another thermosetting resin. Even rubber based ‘contact’
adhesives nearly always include a phenolic resin as a tackifier. Whilst needing very careful
selection and use, each has its place in joining carefully prepared and often primed surfaces to
create the optimum bond, capable of uniformly distributing any load applied between those
surfaces even under what may be severe environmental conditions. Cost-effective structural
component assembly is thus enhanced in a technology which, in many ways, can be considered to
have begun with the use of epoxy adhesive bonding in the joining of the Comet airframes. Much

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Thermoset Resins Market Report

has obviously been learnt since then, a statement confirmed through the many disparate examples,
grouped by adhesive type, which follow.

Major players in the adhesive manufacturing market include Ashland Chemicals, Vantico Limited,
Scott-Bader Co. Limited, Permabond Limited, SP Systems Limited, Hexcel Composites,
Vosschemie GmbH, Loctite Aerospace, ITW Plexus, Henkel, Nihon Handa, etc.

4.2.1 Epoxy

The Araldite series of epoxy adhesives manufactured by Vantico, are perhaps the most well known,
typically two-part, systems. There are numerous specialist grades of epoxy adhesives and their
application can range from simple use in the art world, to the sophisticated bonding of Kevlar
fabric to ceramic body armour. In the former and in a process known as glass appliqué, large
‘stained glass’ panels are formed by the bonding, with a special clear adhesive, of two layers of
glass, one clear, and the other constructed from interlocking and carefully tailored coloured glass
pieces.

However, it is the aerospace industry which has always made great and successful use of epoxy
resins not just as composite matrices, but also for adhesive bonding. The US Air Force and the
University of Illinois are among the institutions working on this. In a still new development, the
repair of composite aircraft panels and structures is being facilitated by the use of ‘patches’ of
suitably pre-formed reinforcement pre-impregnated with selectively formulated epoxies. One
problem retarding the increased use of this effective repair procedure, has been the difficulty of
accurately securing these patches in place while the resin cures. Although obviously demanding the
use of ‘keepers’ against the aircraft structure, it is a problem overcome by the addition of magnetic
particles to both the adhesive and the pre-impregnated resin. These particles have a double
advantage in that the adhesive can also be cured electromagnetically by exciting them with
microwave energy. It is a development with clear spin-off potential into other application areas.

Such repairs, or indeed any aircraft structure repair, must retain 100% long-term effectiveness. The
United States Air Force is developing an integrated system encompassing the design, analysis,
surface preparation, installation, inspection, training and certification, covering the complete life
cycle of a bonded repair.

Indeed the previously suggested spin-off is growing. A range of electrically conductive adhesives
based on a silver-filled epoxy (for example, Tra-Duct 2902 from Tra-Con Inc. (USA) and Dohdent
NH-070A and NH-041A-2 from Nihon Handa (Japan)) is becoming popular for electronic bonding
and sealing applications where a combination of mechanical, electrical and/or thermal properties is
required. Adhesive bonds offer high resistance to humidity and continuous service temperatures to
140 °C, completely replacing welded joints in that service scenario and being faster to manufacture
than mechanical bonding. Such adhesives can be equally applicable whether bonding metals, glass,
ceramics or plastics and many, such as Emcast 1505 or 1507 from Electronic Materilas Inc. (USA),
have been developed for very specific purposes such as the joining of fibre optic
telecommunication connections, a sector of rapidly growing interest.

However, many sophisticated aerospace and corrosion-resistant applications demand from the
structural epoxy-based adhesive, a continuous temperature resistance of up to 200 °C. Here systems
such as Permabond’s ESP 4582, which is also capable of induction cure within 30 seconds, come
into their own. A specially formulated, room-temperature curing instrumentation ceramic-based
epoxy adhesive from the UK company, Symonds Adhesives (Cotronics E 098), suitable for
cementing, insulation and embedding applications, is reported as being resistant to 1650 °C.
Cotronics E 098 can be employed for metals, glass, ceramics and a range of plastics and offers high
bond strength, good thermal conductivity and electrical resistance as well as good chemical and
solvent resistance.

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Thermoset Resins Market Report

Recent developments by EIC Laboratories include ElectRelease, an ingenious high-strength epoxy


adhesive which debonds from a metal surface when an electric current is passed across the epoxy-
metal interface. It is therefore a preferred replacement to the use of mechanical fasteners in those
situations, such as the increasing use of aluminium for automotive application, where temporary
bonding is an essential part of an assembly process. This suggests a new assembly technique with
wider applications and a development therefore that can be expected to promote the formulation of
perhaps a number of competitive systems.

As a result of the ultra-thin oxide always present on the surface, aluminium is both difficult to weld
and to adhesive bond, and this has caused Permabond to develop their 6050 system which contains
an adhesive promoter. It is equally suitable for other metals and also composites. No surface
preparation is needed and bonding can take place in between 5 and 10 minutes.

In the automotive industry, sheet moulding compound (SMC) door and body panels, spoilers,
tailgates and instrument panels, continue to employ adhesive bonding to other SMC/bulk moulding
compound (BMC) components, or electro-coated and galvanised metal surfaces. One typical
example needing no surface preparation or primer, is Pliogrip 5000/5020 from the Specialty
Polymers & Adhesives Division of Ashland Specialty Chemicals. This is an area where there is
increasing competition from long fibre, glass-reinforced thermoplastics, but adhesives based on
thermoset resins will probably be used with these also.

The infrastructure in the civil engineering market, both new build or repair, is another sector
reaping positive benefits from the use of epoxy adhesives. The secure bonding of composite
structures to existing concrete is one area of particular importance. Concrete consists of sand and
aggregate in calcium silicate hydrate cement and suitable adhesives need, in addition to respectable
mechanical properties, the ability to bond with hydroxyl groups on the surface of the concrete.
Equally they need a degree of water resistance and the ability to cure at low temperature. Specially
formulated amine curing systems achieve this and the market for reinforcement of existing and new
concrete structures is growing rapidly.

4.2.2 Unsaturated Polyesters

Whilst relatively little use of unsaturated polyester resins as adhesives can be reported, there is one
important application for a fast-curing system. Employed as an alternative to timber for the
shoring-up of mine roofs, Sandvik Rock Tools, Mine Bolt & Resin System (MBR) and similar
systems are thin capsules consisting of two chambers separated by a polyester film barrier. One
portion, the larger, contains the resin dissolved in a monomer, whilst a peroxide catalyst fills the
other. After inserting a capsule into a previously drilled hole, a steel bolt is driven home and
immediately rotated, rupturing both chambers and causing the two materials to mix together and
cure to form an irremovable bonding grout. The resin and catalyst can also be mechanically
blended together with coarse aggregate fillers, where a more putty-like grout is required. This
market is also open to epoxy based systems and acid cure phenolic resins have been investigated
for the same application.

4.2.3 Phenolic

Many of the very diverse applications of phenolic resins may be regarded, in the broadest sense, as
adhesive applications. However, here, just a few of the more obvious adhesive uses will be
mentioned.

Phenolic resins have been used as bonding agents since the earliest days. Resorcinol modified
adhesives are the preferred structural timber adhesives and are used in the production of laminated
timber structural members for building and construction purposes. Phenol/formaldehyde resols are
also used as the bonding agent in external and high quality plywood production.

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Thermoset Resins Market Report

Phenolic resins, modified with polyvinyl acetal or polyvinyl butyral or similar materials, are used
for the high temperature bonding of steel to steel and have American military approval as metal to
metal adhesives in aircraft and other structures. Phenolic resins are also used in the formulation of
contact and other flexible adhesives based on, e.g., polychloroprene, and in nitrile rubber
adhesives. Their use as tackifiers in rubber formulations, especially tyre stock, where they help to
improve the adhesion of rubber to steel, may be regarded as an adhesive application also. Pressure
sensitive adhesives frequently contain phenolic resin tackifiers.

4.2.4 Others

There are many other thermosetting resin based or containing adhesive systems. Blocked
isocyanates, polyurethanes and many others have been developed in recent years as the advantages
of adhesive bonding over traditional joining methods have become better appreciated in production
engineering.

A typical example of a recent development is a still relatively new family of high-adhesion


thermoplastic epoxy Blox polymers from Dow Chemical for hot-melt adhesives. These combine
the adhesion and durability of epoxies with the flexibility and processability of thermoplastics. It is
anticipated that these materials will find application as coatings, adhesion promoters and polymer
additives.

Sika unveiled two new adhesive systems at the April 2002 JEC Composites Exhibition in Paris.
Sikafast® is a new fast-setting flexible structural adhesive needing little or no surface preparation,
whilst Sikaflex 660WM® is a one-component polyurethane adhesive intended for semi-structural
and structural applications within the automotive industry.

The US based IPS Corporation has introduced several new Weld-On® structural methacrylate
adhesives specifically designed for the bonding of structural assemblies.

4.3 Buttons

Often overlooked as a thermoset resin application, is the manufacture of a wide range of decorative
buttons for clothing. Manufactured using a low reactivity orthophthalic or, occasionally, isophthalic
grade of unsaturated polyester and casting rods of the required diameter, these systems allow for
the introduction of colour or texture swirls and other effects. Resins of different viscosities or
thixotropies are used to reduce mixing on pouring and curing. The buttons are then machined from
the cast rods so produced, revealing the colours, etc., in the various resins used. The introduction of
polyester buttons is one of several alternative technologies which have displaced, over the years,
early versions of other plastics such casein, phenolic and cellulose acetate. These had themselves
displaced hand-crafted bone, ivory, wood, etc. Like every material which, after commercialisation,
peaks to a steady plateau before falling out of favour following the introduction of an improved
competitor, polyester-based buttons are declining in favour of moulded thermoplastic, often highly
decorated alternatives.

4.4 Casting and ‘Solid Surface’ Applications

Casting and encapsulation (Section 4.7) are clearly similar applications, somewhat difficult to
differentiate. Here, the former is taken to concern larger objects rather than the smaller castings
encapsulating electrical and electronic components for insulation and easier assembly purposes.
The latter most commonly uses epoxy resins.

Slow-curing unsaturated polyesters can be employed for cast sculptured shapes and the use of a
wide range of mineral fillers can produce artificial versions of natural minerals such as marble,
onyx and granite. The use of such materials for the production of sinks, wash basins, counter tops,

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Thermoset Resins Market Report

etc., in recent years has seen the advent of the ‘solid surface’ industry which this type of product
describes. Cultured onyx is perhaps the upper end of such material in that it is possible, by careful
formulation and chemistry, to produce lamps, vases and other decorative wear with the same
translucency as the real material at a fraction of the cost. This ability to add opaque and translucent
pigmentation and to create a high, glass-like readily polished surface finish offers particular
attraction in many applications. Solid surface kitchen surfaces may also be produced with acrylic
resin systems and others are under development.

There is also the extensive, worldwide use of ‘water-white’, long gel time, low exotherm, low
shrinkage, polyesters in the manufacture of decorative shapes encapsulating and in turn protecting,
some artefact ranging from a watch component, through coins, flowers, leaves, to medals, stamps
and model cars. Such items are generally sold as paperweights to the gift-wear and business
promotion industries. Although small in size, the overall number produced annually consumes a
not inconsiderable tonnage of resin.

The use of, usually polyester based, highly filled material for the casting of decorative objects and
statuary for internal and external use has grown rapidly in the last decade. New systems such as
those based on water-soluble acrylic systems have also been introduced and will doubtless grow as
the demand for lower VOC emissions in production increases. These types of materials are also a
common feature of theme parks.

4.5 Coatings

The term coatings now covers a multitude of applications from paints for car bodies or timber,
brick and stonework protection and decoration, through flooring and high performance and
corrosion-protection uses, to say nothing of finishing treatments for paper and cardboard and a
whole range of both domestic and industrial items. Very few of the diverse range of components
that man now requires to employ on a daily basis, escape some form of finishing or coating
treatment.

As a consequence there is an equally large range of finishing or coating materials and many of
these are based on thermoset resin chemistry. Paints and lacquers, although also capable of
classification as coating materials, are considered under a separate heading, as is encapsulation,
which in some instances as explained later, could equally be classed as a coating.

Many manufacturers are active in this field, among them Ashland Chemicals, Hawkeye Industries,
Lonza SpA, Chemval SRL, BUFS Polyurethane, Rust-Oleum, Fosroc International, Trimite
Limited, E. Wood Limited, etc.

4.5.1 Arylzene Resins

As well as finding application in the formulation of air-drying coatings, arylzene resins such as
those manufactured by Georgia Pacific Resins, find numerous other applications such as
crosslinkable additives for melamine, phenolic resol and urea-formaldehyde based systems. They
can also be used as building blocks for alkyds, epoxies, polyesters, powder coatings, uralkyds,
urethanes, UV curable resins and waterborne coatings. As noted later the development of high-
quality, viable and cost-effective UV curing resins and waterborne systems is becoming
increasingly important as replacements for coatings and other applications exhibiting high VOC
emission loss.

4.5.2 Blocked Isocyanates

Blocked isocyanates, which are designed to be compatible with hydroxy-terminated acrylates,


epoxy, phenolic, polyester and polyether-based resins, are under active development by, for

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Thermoset Resins Market Report

example, the Specialty Division of Baxenden Chemicals. Their application in the manufacture of
high performance coatings is appreciated for their ability to withstand severe environmental
conditions, including wear and abrasion. These materials also find use in adhesive systems.

4.5.3 Epoxies

Low viscosity epoxy resins are employed in a wide-range of surface coating formulations,
worldwide. The ambient cure segment uses standard liquid diglycidyl ethers of bisphenol A (DGE-
BA) and bisphenol F (DGE-BF), liquid epoxy novolaks (EPN), aliphatic and cycloaliphatic epoxy
resins. Recent developments are indicating better performance is obtained by the use of
trimethylpropaneglycidyl ether and polyoxpropylenediglycidyl ethers.

However, perhaps the most important epoxy coating development is the rapidity with which
waterborne, organic solvent free systems, often designed for ambient temperature cure, are
becoming increasingly commercialised. Although first introduced some thirty years ago, the reason
for their current rise in importance is the increase in demand for reduction in VOC emissions
during processing and cure. A wide range of solventless systems is available for most applications.

For example, low viscosity, solventless epoxy-based resins, curing agents and modifiers, were
developed several years ago by Shell Chemical (now Resolution Performance Products)
specifically for railway wagons, a particularly severe application both in the context of the initial
coating condition and the eventual use of the wagon.

In another steel-based substrate situation, Tohpe has announced the use of a specially modified
waterborne epoxy containing carefully selected additives and rust preventers, to provide a heavy
duty, thin but pinhole free, anti-corrosive coating system for industrial structures and bridges.

Other work by the Shell Chemical Company has shown that waterborne, two-component, ambient
cure systems formulated from non-ionic stabilised dispersions of a solid epoxy resin and an amine
curing agent, have shown superior water and salt spray resistance in comparison to the former, still
competitive, solvent-based coatings. Formulations at optimum amine-to-epoxy stoichiometry, have
lower VOC emissions, faster hardness development, better gloss and impact resistance.

As one resin system example taken from many, the long-term enhancement of the chemical
resistance of concrete floors, is benefiting from the commercialisation of water-based epoxy
coatings, as typified by Waterpoxy 751, from the Coating & Inks Division of the Italian company,
Cognis, which also offers good compression properties under load.

The use of UV radiation or electron beam curing is also gaining ground, not just for epoxy
coatings, now that the necessary equipment and production procedures are being simplified.

In the automotive industry, although composites continue to find greater use, lightweight, high-
strength aluminium alloys are also finding favour in competition to steel; reduced weight can result
in considerable fuel consumption and therefore environmental benefits. However, there is a
potentially serious corrosion problem with high copper content aluminium alloys when used
adjacent to steel items. Consequently, a possible answer appears to lie with the use of an
anticorrosive ‘double-strand’ conductive polymer additive in a waterborne epoxy system. Such a
combination would enhance the primer’s ability for inhibiting corrosion of the aluminium alloy,
without compromising its ability to protect the steel, but equally is capable of being applied using
the currently dominant electrophoretic technology.

Although having a relatively high cost, epoxy-based coatings offer a viable and economic answer
to some infrastructure rehabilitation requirements. This is demonstrated by an amine-based curing
system found suitable for the rehabilitation of potable water pipes and tanks. One such ‘turnkey’
system, Nitoline WP was announced in 1998 by the UK company, Fosroc International and

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Thermoset Resins Market Report

included the necessary coating and ancillary equipment. Further epoxy-based coatings receive
comment under the powder-coating heading (Section 4.5.8).

4.5.4 Melamine Resins

Unlike the other coating resins considered under this heading, melamine is not applied as a liquid.
It is used as a pigmentable powder for high-pressure moulding, and is noted for its high skin
hardness, strong arc and abrasion resistance in the manufacture of household and tableware and in
decorative laminates onto a variety of substrates. Melamine surfaces are the most common on
decorative laminates for use in domestic kitchens where products with well known names such as
‘Formica’, consist largely of phenolic resin impregnated paper with surface layers of urea-
formaldehyde paper containing the colour or pattern and melamine-formaldehyde as the ultimate,
wearing surface layer.

4.5.5 Phenolic

Another coating application of major importance is the coil coating of steel for food packaging, an
elevated temperature (or baked) application which demands the production of a thin barrier film
exhibiting a balance between flexibility and chemical resistance. Here crosslinking phenolic resins,
such as the GPRI 7500 series produced by Georgia Pacific, come into their own, because of their
ability to be blended with a wide range of polymers to answer numerous coating requirements.
Initially developed as crosslinkers for high molecular weight, linear epoxy resins, this type of
phenolic also finds use with other hydroxyl-containing polymers, such as polyesters, vinyls and
acrylics.

Other traditional coating uses for phenolic resins include the coating of copper wire for coil
winding, a process that remains a very large user.

4.5.6 Polyesters

Ortho- and isophthalic unsaturated polyesters are employed in the production of coating materials,
and are often manufactured by those companies who are majors in the development, manufacture
and sale of traditional composite matrix systems. Polyester coatings are used in many applications
including paints.

All grades of unsaturated polyester are used as a pigmented or unpigmented resin-rich flow or
finishing coat, onto the reverse or non-exposed face of contact or spray deposited composite
mouldings. Such coatings, which often contain a small addition of wax to prevent ‘air-inhibition’
on polymerisation, are applied to enhance the appearance and environmental resistance, or seal any
porosity and/or exposed fibres from the reinforcement, present on the surface.

There is a wide range of unsaturated polyester gelcoats, which form the outer, decorative and
protective exposed-face film of contact, spray deposited, cold-press, resin transfer moulded and
pultrusion moulded composites. These are considered further under gelcoat and pigment paste
(Section 4.9).

4.5.7 Polyurethanes

Polyurethane coatings, for example from Bayer AG, for use on plastic substrates for automotive
application, can be solvent borne, high solids, or waterborne, to suit specific circumstances, with
the latter obviously affording a high reduction in VOC emissions. Further, low temperature curing
polyurethane systems also offer a real alternative to pure thermoset acrylic systems because of the
resulting improvement in the properties of the film coat.

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Thermoset Resins Market Report

Another company supplying a wide-range of polyurethane dispersions and urethane-acrylic hydrids


for resins and additives in the formulation of architectural and industrial coatings, is the Hauthaway
Corporation. These are claimed to offer enhanced abrasion and impact resistance as well as
improving the toughness of most acrylic emulsion formulations.

Work has also shown that in competition to, e.g., epoxy mastic formulations, high-build moisture
curing urethane protective coatings are preferable on steel structures exposed to marine
environments. Trials were undertaken on both alternatives, applied over ‘near white’ blasted steel
first treated with a water-based inorganic, zinc-rich primer. The urethane system is more user
friendly and offers a faster cure with low VOC emissions.

As a final example, following work by BASF and Polycon, waterborne coatings based on urethane
linkages created from polyol and isocyanate reactants, provided the solution for a flexible, cost-
effective, easily colour-matched coating required to protect and glamorise a large, complex-shaped,
engineered thermoset fascia employed by General Motors for their F-car line.

4.5.8 Powder Coating

Any review in the context of thermoset resin systems and their use as a coating system, will clearly
indicate that powder coating is increasingly usurping other application techniques [1]. As a result
there are commensurate developments in both the equipment and the processing conditions
employed, in the substrates that can now be successfully and economically powder coated as well
as in the materials now suitable for the process.

However, it is important to recognise that although powder coating systems demonstrate several
major advantages in competition with other, more environmentally friendly coatings and,
moreover, can be considered a major success story of the last decade, there are downsides.
Complicated formulations, poor coating wet-out, and the high level of energy and resource
consumption have predominated but, as already suggested, alternative powder manufacturing
routes, new powder formulations and radiation curing are already providing viable answers. In fact
powder coating systems generally are being considered increasingly as engineered materials.
Although both thermosetting- and thermoplastic-based powders are available, the former (at >90%)
is the major portion of the market.

Initially, the process was material limited to basic epoxy and epoxy-polyester systems, whereas
today, materials specific to customer applications are becoming increasingly common. These
include pigmentable carboxyl-terminated polyester resins, crosslinked with either a triglycidyl
isocyanurate or hydroxyalkylamide type hardener, offering excellent flexibility and outstanding
external durability. As a result, the process has gained an ever-greater share of the general
industrial coatings market particularly in Europe, where Scott-Bader is a major player.

Some systems suitable for general metal coating are based on glycidyl methacrylate (GMA)
acrylic-cured polyester hydroid technology as a replacement for triglycidyl isocyanurate (TGIC)-
cured polyester powders.

In other work to broaden the commercial viability and acceptance of powder coating for coil
coating and in the production of food containers, DSM Resins and Michel Huber of Munich,
Germany, have developed a new high speed metal coating process, known as Electro-Magnetic
Brush (EMB) Technology.

During 2000, Dow Chemical introduced what they called a new family of Blox polymers, claimed
to combine the adhesion and durability of epoxies with the flexibility and processability of
thermoplastics. There are two types, high-adhesion barrier resins and adhesive resins, with the
latter suitable for powder coating applications, plus other coating applications. Dow also lists
several new epoxy or acrylated epoxy powder coating resins. As another example, Resolution

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Thermoset Resins Market Report

Performance Products offer a high molecular weight polyamine adduct having a target solids level
of 57%.

The external corrosion protection of steel pipes, even those exposed to severe conditions, high
service temperatures, hot and damp environments, is understood to be enhanced by the use of a
new epoxy powder primer, Eurokote 7988 from Eurocoat. This primer, owing to its special
chemistry, behaves differently in its application parameters from conventional powder primers but
can also be employed on conventional coating lines. Another primer, 716, offers a solution to
certain application constraints, such as reduced energy costs and the preservation of substrates that
could be damaged by excess heat, plus a better operating flexibility when the substrate is heated in
a non-homogeneous manner.

The problem of reducing the damaging effects of heat during the cure of any surface coating, or
indeed during the exothermic polymerisation of any thermoset resin, is resulting in an increasing
availability of low-temperature and UV curable systems. These systems are also being developed to
be free from the VOC emission disadvantages that plague otherwise traditional coatings. The
decorative powder coating of composites, high pressure laminates and medium density fibreboard
(MDF) are particular applications susceptible to heat damage.

Whilst environmental considerations generally predominate, other applications, such the


automotive sector, are driving the development of powder coating technology in another important
direction, namely the need for improved performance and productivity or, in other words, better
process economics. As recently as 1997, BMW began applying heat-cured powder clearcoats and
PPG has since introduced a new ‘wet’ system, Powder-Prime that allows motor manufacturers to
apply both first and second coats in dip tanks.

Powder coating applied by spray, is increasingly finding application for the in-mould coating of
hot, compression-moulded composite components. Not only is complete part coverage better
guaranteed but, as a result of a chemical reaction between the coating and the fibre reinforced
composite substrate, an extremely durable finish is obtained. Both conductive and paintable grades
are available, with the latter specifically designed to fill any surface porosity that may be present,
as well as providing an excellent interfacial bond between the subsequent paint finish and the
component surface. Following the development of coating systems that cure at 105 °C rather than
the former 150 °C, new coating opportunities for low pressure and temperature moulded
composites have also been created.

Finally, commensurate with advances in powder coating resins, comes alternative and improved
‘de-binding’ devices used to ‘unbind’ agglomeration in powders for powder coating. These are
based on a combination of ultrasound and conventional vibration, during the sieving of electrostatic
powder coatings, particularly those employed for automotive clearcoat application. Typical is
Russell Finex’s Vibtrasonic technology which employs an acoustically developed titanium
transducer or probe which applies an ultrasonic frequency to the separator mesh of the sieve, via a
velocity transfer plate. This breaks down the surface tension, effectively making the stainless steel
wires of the mesh, friction-free.

4.5.9 Vinyl Esters

Vinyl esters can be considered as offering a combination of the best properties of both unsaturated
polyester and epoxy resins and are best considered as coating materials under the heading of
gelcoats (Section 4.9). They can be employed as resin-rich flowcoats, applied as a final surface coat
to composite mouldings, but this use is less typical than for the unsaturated polyesters.

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Thermoset Resins Market Report

4.5.10 Others

Blocked isocyanates, designed to be compatible with hydroxyl-terminated acrylates, epoxy,


phenolic, polyester and polyether resins to provide high performance coatings, are under active
development. The Specialty Division of Baxenden Chemicals is one company understood to be
involved.

4.5.11 Ultraviolet Cure

Although not a material for coating, UV curing is a development of major and growing importance
for the coatings industry. However, the wide availability and realisation of a truly commercial UV
cured coating process applicable to all substrates, awaits further development. Even so, it is already
clear that the combination of an environmentally friendly system and UV cure could offer
advantages over current thermosetting powders. Current disadvantages include complicated
formulations, (e.g., acrylic, cationic and free radical resins, solid unsaturated polyester, solid
urethane acrylate hardener and maleate-vinyl ether systems), poor wetting and finally, of major
importance, problems in ensuring an even distribution of the UV radiation particularly for highly
complex shapes.

Nevertheless development proceeds apace because, given optimum solutions, the result can be
much better process economics and thinner and more consistent coatings, with superior weathering
properties. Much of the work is being concentrated on photoinitiators (e.g., bisacylphosphine
oxide) and light stabilised additives and also on the application of the process to externally exposed
timber. In this instance epoxy acrylate resins are claimed as ideal. A typical formulation for a
transparent system would have a primer consisting of a water-soluble, bifunctional, aliphatic
polyurethane acrylate and a topcoat of a bifunctional, aliphatic polyurethane acrylate. The latter
would contain a UV absorber such as 2-hydroxyphenyltriazine (Tinuvin 400 from Ciba-Geigy AG)
and a hindered amine light stabiliser (e.g., Tinuvin 292), combined with a light converting dye.

Among the companies involved are Ciba Specialty Chemicals (initiators), Fusion UV Limited (UV
lamps and source systems) and UCB Specialty Chemicals Division (Belgium).

4.6 Composite Matrices

A large percentage of the world’s thermoset resin production is consumed by the multinational and
steadily growing composites industry. The relative global consumption in different applications is
shown in Table 4.2. Three subheadings, processing and fabrication, matrix type and applications
have been employed in this section.

Table 4.2 Relative global consumption of composites in different applications


GLOBAL EUROPE JAPAN
(1998 Figures) (1998 Figures) (1997 Figures)
Construction/building 30% 30% 56%
Electrical 13% 17% 12%
Marine 10% 10% 6%
Pipes & silos 11% 10% 5%
Transportation 24% 24% 5%
Unclassified 12% 9% 16%

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Thermoset Resins Market Report

4.6.1 Processing and Fabrication

4.6.1.1 Autoclave Moulding

This process is the preferred route for the processing of very high reinforcement fraction
components to mouldings. It is most popular with the aerospace sector and the principal resins used
are epoxy and phenolic. Reinforcement material (glass, carbon, aramid) which has been pre-
impregnated with resin and the resin allowed to partially cure (‘B’-stage) is termed ‘prepreg’ by the
industry. This material is cut to shape and laid on an open mould to the required thickness and
reinforcement pattern, before being covered with a flexible bag and placed in a heated, pressurised
autoclave to consolidate the laminate and flow and cure the resin. The method is capital intensive
and fairly labour intensive but the highest mechanical properties for a moulded composite are
normally achieved in this manner.

4.6.1.2 Contact-Moulding (Hand Lay) and Spray Deposition

The last ten years have seen these two labour-intensive composites moulding processes begin to
lose some favour with competition from the low-capital entry techniques such as resin infusion
processes resin injection or resin transfer moulding (RTM). Nevertheless, there is no expectation
that either will, even in the long-term future, be totally usurped. Both techniques, although
suffering from the vagaries always present in any labour-intensive manufacturing operation, are in
many respects ideal for prototypes, short-run production and the massive type of one-piece
moulded constructions not open to any other means of fabrication. Contact-moulding (also known
as hand-lay) is the process on which the whole of the now worldwide composites industry was
founded.

In the same way, there is no reduction in the number or range of thermoset resins formulated for
both. Indeed, with the urgent need to reduce VOC emissions markedly in some countries, their
number has increased with the development and commercialisation of low styrene and
dicyclopentadiene (DCPD)-based unsaturated polyesters, still the principal resin type for both
processes.

Processing machinery, such as that available from R.W. Rolf Wolfangel GmbH (Germany) and
others around the developed world, has made the conversion to closed mould techniques easier for
those wishing to take this course. At the same time the same manufacturers have modified and
updated spray machinery to reduce the emissions from that equipment during use and Venus-
Gusmer (USA) have been very much involved with this. Process machines such as roller
impregnators are also available to reduce emissions during hand lay.

Phenolic resins may be both hand-laid and spray deposited. Vinyl esters are sometimes hand laid as
are epoxy resins but these two systems are more commonly used in other processes.

4.6.1.3 Cold-Press and Vacuum Bag Moulding

The last five years have seen cold-press moulding diminish somewhat in importance as a process.

The popularity of vacuum bagging may explain the rapid growth of resin infusion processes as
hand-lay has declined. However, vacuum bagging, in which it remains necessary to wet out the
reinforcement with the resin before the application of the vacuum bag, only saves emissions on the
cure part of the cycle. This is a relatively low emission part of the process and cold-press moulding,
in which the compression of the press onto the resin and reinforcement achieves consolidation, is
cleaner in this respect. The capital cost for cold-press, or low pressure press as it is more accurately
known, is greater than with vacuum bagging because the latter needs only one tool, usually female,

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Thermoset Resins Market Report

coupled with suitable vacuum bagging materials. Depending on the number of items to be
manufactured and the materials used, some vacuum bagging films are reusable.

In the case of cold-press moulding a product with two good faces is produced from a two part tool.
However, although cycle times can be shorter, tooling costs are higher and there may be little or no
advantage over resin-injection/transfer techniques.

The most frequently used resin systems for these processes are the polyesters but phenolic, vinyl
esters, epoxy and acrylic urethanes can be processed in this manner also.

4.6.1.3 Filament Winding

This selective process for the manufacture of closed or open-ended cylindrical components can be
considered a highly capital-intensive composites fabrication technique. Consequently products
made by filament winding should either be required in large quantities, e.g., pressure pipe,
sewerage pipe, ventilation ducting, etc., or be of a design nature such that filament winding is the
only practical manufacturing technique. Under that latter category would be found a wide range of
vessels from very large liquid bulk storage tanks to LPG cylinders. There are also specialist
military applications for filament winding such as hand-held rocket launchers and rocket engine
components.

For the construction of simple tanks and low performance pipe and tube, isophthalic polyesters are
the most common resins. Where chemical resistance is required vinyl esters are used and for high
mechanical performance, such as pressure pipe and pressure vessels, epoxy resins are the most
popular. Phenolic resins can be filament wound using acid catalysis and these resins are used where
fire performance is of importance such as mining ducting and some factory exhaust systems.

4.6.1.4 Continuous Lamination

Continuous lamination, most commonly applied to polyester resins but also possible with phenolic
and vinyl esters, is, as the name suggests, a method for the continuous production of laminated
sheet products. The most common application for such products are truck side panels and roofing
sheets, profiled or flat, opaque or transparent. Capital costs are relatively high for the plant for this
process but output is high and continuous, one of the very few composites manufacturing processes
which is.

4.6.1.5 Hot-Press Moulding

Hot-press compression moulding (between relatively massive and expensive matched metal tool-
sets), has been used successfully for many years. It is used for quantity applications demanding
good mechanical performance, complex shapes with critical dimensions and good chemical and
corrosion resistance. Applications range from electrical ‘white goods’ mouldings, through modular
panels for liquid storage tank construction to automotive and truck bodywork. The continued
development of the generally unsaturated polyester based BMC/DMC (bulk or dough moulding
compounds) and SMC (sheet moulding compounds) used in this process, owes much to the ever-
growing customer demands. Today, SMC mouldings, particularly those used for automotive
applications, cost less than their steel or aluminium counterparts and, to further advantage in a
world of mobile phones and GPS location systems, are virtually invisible to radio waves.

DMC/BMC are short fibre (4-8 mm) compounds, supplied as a lump or ‘sausage’ of dough from
which an appropriate quantity is cut for the moulding to be made. They flow well and deep draw
parts are easily moulded.

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Thermoset Resins Market Report

SMC has much longer (40-50 mm) glass reinforcement. It is made and supplied as sheets between
non-adhering films. The possible draw of a moulding is far less than that available with
DMC/BMC and the flow is less in the tool. However, the mechanical properties of SMC products
are considerably better than those of the doughs.

Developments include new next-generation UV-stable, pigmentable Ekadure 2001 polyesters


developed by the Specialty Polymers & Adhesives Division of Ashland Chemical in co-operation
with Plasticolors and Union Carbide. The resulting SMCs eliminate the need for post-moulding
painting on structural and exterior application mouldings. Then for bath and vanitory, as well as
traditional SMC end-use mouldings, comes the recent development of the world’s first thermoset-
modified acrylic resin from Mitsubishi Rayon. Enhanced weatherability, hot-water resistance, gloss
retention and transparency is claimed, when compared to polyester versions.

The development of the fuel cell, particularly that using hydrogen as fuel, is a potential application
for a very large amount of thermoset materials. DMC/BMC bipolar plates and end plates could be
an essential part of any fuel cell powered vehicles on a large scale. Although not expected to have
major impact until the end of the present decade, this application could give a new meaning to
volume in hot press moulding.

Through improved mould design, better processing techniques and improved thermosets, BMC
mouldings (well-known for their creep resistance at elevated temperature (100 °C and above), fire
retardancy and dielectric strength), are now being seen as low-cost and better alternatives to high
temperature/engineering thermoplastics that often demand secondary coating and other operations.
This is typified, for such applications as circuit breaker housings, headlamp reflectors and many
other automotive components, by BIP’s new range of flexible polyester based moulding
compounds (called FMCs), which exhibit flexural moduli as much as 42% lower than conventional
grades but without detriment to other recognised properties.

Hot-press moulding is normally a high pressure process with pressures of up to 15 MPa (1 ton.in-2).
This brief assessment would not be complete without some mention of low pressure moulding
compounds (LPMC), a largely National Chemical, Scott Bader development. This composition,
around 15 years old, seeks to marry the advantages of SMC with a much reduced equipment cost
and better process economics. The lower moulding pressure employed (typically 500 kPa
compared to 3 MPa and above), allows the use of much less expensive, sometimes even composites
tooling operating at a lower temperature (90 °C, compared to 150 °C) and requiring lower tonnage
presses for a given platen size. Although both SMC and LPMC are pre-compounded materials,
typically employing unsaturated polyester resin, they differ in that the first relies on a chemical
thickening process whereas the latter on a physical thickening process. Vinyl ester and phenolic
based moulding compounds complete the material selection available.

4.6.1.6 Pultrusion

The technique for the continuous manufacture of composite moulded sections, or profiles, by
means of a process known as pultrusion has, arguably, been the fastest growing sector of the
composites industry in recent years [2]. In this process, reinforcement, in a range of formats, is
pulled through a die with the cross-section of the finished profile. The reinforcement ‘bundle’ is
either pre-impregnated with resin by dipping in a bath prior to entering the die or the resin is
pumped under pressure into the die a short distance from the start. In either case, the resin is cured
as it travels through the heated die and is pulled from the back of the die and sawn to length. With
the growing use of ‘standard’ (i.e., ‘off the shelf’) or ‘custom-moulded’ profiles for the civil
engineering/infrastructure, as well as other markets, the growth situation is very unlikely to change
in the near future. As a consequence, every manufacturer of epoxy, phenolic, urethane-
methacrylate, or principally, unsaturated polyester resin, is able to offer grades specifically
formulated for pultrusion.

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Thermoset Resins Market Report

Until recently, one of the problems with the use of epoxy when compared to any unsaturated
polyester, was the reduced line-speed of the pultrusion machine to allow for the slower cure
reactivity. Reichhold claim to have introduced a new epoxy for pultruded profile manufacture that
fully resolves this problem whilst remaining stable at room temperature.

From the specifier point of view, standard pultruded profiles can be ordered and treated as for
metal profiles using the definitions laid down in prEN 13706 (Reinforced plastic composites.
Specification for pultruded profiles).

4.6.1.7 Resin Injection (Transfer) or Resin Infusion Moulding

Over recent years, the worldwide composites industry has begun to realise the potential for
introducing, by means of an injection procedure, the requisite thermoset resin matrix into a
reinforcement ‘pack’ held within a closed male/female tool set.

Resin transfer moulding, employing a variety of injection pressure systems, sometimes aided by the
creation of a partial vacuum within the tool set, was among the first. Since then, there has been a
multitude of minor or major ‘liquid-moulding’ process developments. These have included, for
example, SCRIMPTM (Seeman Composites Resin Infusion Moulding Process), which has patent
protection, Resin Infusion under Flexible Tooling (RIFT) and many others which are very similar
and are simply termed ‘resin infusion processes’. All are claimed to offer particular advantages but,
naturally, also disadvantages. The principal difference between resin transfer moulding (RTM) and
the infusion processes is in the tooling set-up. For RTM a matched pair of rigid tools is required to
resist the positive injection pressure of the liquid resin, whereas in the infusion processes only one
rigid tool is required, the other face being a flexible film or semi-flexible thin moulding. The mould
‘cavity’ is below atmospheric pressure when moulding. RTM produces two ‘good’ surfaces. The
reverse surface on infusion moulded products is ‘fair’.

As a consequence, there has been the commensurate development of a wide-range of thermoset


resins, principally based on unsaturated polyester chemistry, specifically formulated in terms
largely of viscosity and reactivity, to uniquely satisfy each of these liquid moulding processes.
Indeed there is one class of thermosets, the acrylic-urethanes, now well known by the trade name
Modar that, although now used largely for the manufacture of pultruded profiles, was initially
developed and fully commercialised for resin transfer moulding.

Although a low initial viscosity resin is obviously important in any injection or infusion moulding
process, that property is equally advantageous when there is a need to incorporate fillers in the
moulding to impart for example, fire retardancy. Many systems, for example Reichhold’s Polylite
31507, a fast curing hybrid unsaturated polyester, offer low viscosity, easy pumping and good
reinforcement ‘wet-out’, even when filled to 60 or 65% by weight.

4.6.2 Fire Retardant Composite Applications

Although clearly not a composites fabrication technique, procedures for gaining acceptable levels
of fire retardancy in composites components, effectively in the matrix resin employed, is of
supreme importance.

Fire test methods vary throughout the world and specifying authorities place varying degrees of
importance on the resistance to fire and reaction to fire performance of materials which they use.
All organic polymer matrix composite materials will burn. The ease with which these matrices
ignite varies vastly from materials which are quite flammable to very fire hard resins such as the
phenolics. Their performance once alight also varies. They may be self extinguishing, they may
give off smoke and toxic gases or they may continue to burn, adding to the fire intensity and
spreading flame. In Europe, fire testing is being standardised around the classifications of prEN

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Thermoset Resins Market Report

13501-1 which involves three tests. The most important of these for thermosetting resin matrix
composites is prEN 13823, the so called ‘SBI’ test. This test measures fire growth rate by heat
release, smoke generation, spread of flame and flaming droplet formation. However, it is not
sensitive in respect of smoke and the spread of flame criterion is simply whether there is a spread
of one metre or more. As a result certain specific authorities have their own test criteria such as
those for railway rolling stock in the UK specified by BS 6853. Tests in the USA tend to be very
different and generally speaking it is very difficult to equate performance levels in different
national or even international tests.

Formerly the unsaturated polyesters that found application in, for example, building and
construction components or the mouldings required in the manufacture of railway carriages, had to
employ of necessity filled or chemically modified systems. Whilst these were able to offer a
varying degree of flame or fire retardancy, those using chemical modifications such as the
incorporation of halogens were associated often with the production of potentially toxic products of
combustion.

Such systems are still employed but are being superseded steadily by preferred matrices offering
better fire hardness and much less potential toxic evolution. Some of this has been related to the
successful development of extensive high-speed rail networks across Europe, where construction
demanded the cost-effective use of lightweight composite mouldings satisfying the improved
aerodynamic design of locomotives and aesthetic appeal of rolling stock interiors. However, the
major developments have been the result of investment in underground railway systems in large
cities where escape in the event of fire is difficult in the extreme. Demands for improvement in the
fire performance of aircraft interiors have also resulted in a move away from the traditional epoxy
materials, which have controlled this area for so long.

Along with this improvement in fire hardness, ease of processing and a high-quality surface finish,
even if painted, were both essential. Consequently the matrix resin competition has been severe.
Phenolic resins, either in traditional hot-cure prepreg form or as low temperature cure, acid-
catalysed systems have, without question, the best fire performance properties of any unmodified
or unfilled resin and can be processed by all the conventional processing techniques. However,
modified or filled polyesters, acrylic-urethanes and epoxies have been developed whose fire
performances are far superior to the simple resins on which they are based and which satisfy many
of the application fire specifications in place.

At the same time there has been competition between the form of reinforcement employed and the
fabrication technique, principally contact-moulding, spray-deposition, resin-transfer moulding and
pre-impregnated techniques to achieve the best fire performance in the finished product. These are
developments which will undoubtedly spin-off into other composite market sectors.

The Hexcel company, is just one supplier that has concentrated on supplying the pre-impregnated
fabrics demanded by this market sector, for example in their M34 system, a self-extinguishing
epoxy resin/glass/carbon prepreg for large structures, including rail application. M34 demonstrates
a comparatively long shelf-life, cures at 75 °C and can be processed by vacuum bag moulding, to
satisfy standard S3-SR2-ST2 of DIN 5510, and is classified M2 F1 according to NF 1601.

4.6.3 Matrices for Composites

4.6.3.1 Acrylics

In the true sense of the word, acrylics, polymethylmethacrylate and other polymers of acrylic or
substituted acrylic acid, are thermoplastic materials. However, they can be used in conjunction with
other polymers, to produce several thermosetting resin systems, suitable for use in composites. The
most important of these, the urethane-methacrylate prepolymer dissolved in methyl methacrylate
monomer (MMA) has already been considered in Section 3.

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Thermoset Resins Market Report

Unlike, for example, the unsaturated polyesters, urethane-methacrylates are produced by only two
manufacturers, Ashland Chemical and Ineos Acrylics. That situation suggests, correctly, that they
have a much more limited application. They are not for example, suitable for open-mould
processing but they do have a very important part to play in closed mould technology, particularly
resin transfer moulding (RTM) and pultrusion. Indeed the first systems of this type, under the trade
name Modar, with their low initial viscosity, good toughness and flexibility, were specifically
developed during the first half of the 1980s, for RTM.

Continued formulation and processing development has resulted in success in a number of


important composites applications. Their low, as supplied, viscosity enables high mineral filler
loadings to be employed, which brings the fire properties of mouldings from these resin systems
within the performance criteria demanded by several specifying authorities in the railway industry.
Exterior panels, interior mouldings and seat shells have all been made from acrylic-urethane resin
systems with suitably high mineral filler levels. In this respect, they offer some competition to the
usually preferred, naturally ‘firehard’ phenolics. Pultruded alumina-trihydrate filled Modar
cableways, were selected and extensively built-into the Channel Tunnel.

4.6.3.2 Bismaleimides

Even compared to the epoxies, the bismaleimides (BMI) comprise high-performance, continuous
high temperature resistant (200-240 °C) resins. Being also more expensive, their use as composite
matrices is currently restricted to advanced applications such as aerospace and military aircraft
composites components. Another restriction is their solid state at ambient temperature, leading to
obvious processing restrictions, although their typical viscosity at elevated temperature could, with
processing development, make them suitable for resin injection type techniques should the call-off
volume prove sufficient. Work in this direction continues and a new BMI was announced recently
based on allyl methyl phenol and diallyl bisphenol A chemistry as reactive diluents and co-
monomers. Although there is a reduction in the permissible service temperature (180 °C under dry
conditions), such a resin can be injected at around 75 °C and can exhibit a useful pot-life of 12
hours or more.

BMIs also find application in printed circuit board manufacture and as heat-resistant coatings.

4.6.3.3 Epoxy

Owing to their excellent viscoelastic characteristics, epoxy resin systems are eminently suited to
the manufacture of high-strength composite structures operating at either low or elevated
temperature. Although solvent-containing systems retain their popularity for certain applications,
hot melt resins and epoxy prepregs are available to answer environmental concerns. For example,
the latter have become increasingly indispensable for the construction of some large scale wind
energy blades and performance yachts. Optimum mechanical properties are readily achievable
without over-designed or unnecessarily heavy structures, a situation assisted by several new pre-
impregnated fabrics employing the latest epoxy chemistry with both fast and extra slow hardeners.
A typical example is Ampreg 22 from SP Systems, a well-recognised worldwide supplier.

It is worthy of note however, that like all the ‘sophisticated’ thermosets and, to a lesser degree, with
general purpose, unsaturated polyesters, the operating temperature is not the only factor delineating
the permissible in-service conditions. Many factors, such as chemical attack, must be considered
but of much greater importance is whether those conditions are ‘dry’ or ‘wet’. High levels of
humidity can often cause fairly pronounced reductions in mechanical properties.

Commensurate with the increasing development of higher performance epoxies and rubber-
modified epoxies is the application of microwave curing systems. Here the objective is to control
the temperature throughout the crosslinking reaction and during the physicochemical

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Thermoset Resins Market Report

transformation undergone by the moulded component. That control is of particular importance in


the curing of large epoxy-based composite structures, of the type of particular interest to the
aerospace, land and sea transportation industries.

4.6.3.4 Furanes

Furane resins produced by a self-condensation reaction of furfuryl alcohol with furfural, have
found application in the manufacture of composites tooling and for components subjected to
chemical attack under oxidising conditions. However, they have processing disadvantages with
somewhat difficult to control reactions using acidic catalysts. Therefore, with the
commercialisation of other thermosets better formulated for these two applications they have now
fallen out of favour.

4.6.3.5 Hybrids

Hybrid thermosets are a major development area for the industry. These two or more polymer
component systems combine, by clever chemistry, the salient advantages of those starting-point
raw materials, without any major loss of property. It is seen as likely, therefore, that most major
thermoset developments in the future will be centred around this hybrid approach. Equally, the
most successful of these often novel hybrids, must enable the composites industry to penetrate new
market areas or extend their feasibility within sectors already penetrated.

The resin system most commonly referred to as simply ‘hybrid’, is a two-part polyester-
polyurethane resin suitable for RTM and other techniques where the matrix is injected into the fibre
reinforcement. The first portion consists of an isocyanate with the second being a low molecular
weight unsaturated polyester typically dissolved in styrene monomer, but where both A and B
components also contain carefully selected additives. The final, fully crosslinked molecular
structure offers strength and stiffness from the combination of properties achieved in the chemistry.

Following from the development of polyurethane/polyester hybrids, polyurethane/vinyl ester


systems are equally possible, although work suggests that the system and the catalyst employed can
produce a greater property variation both in terms of the initial matrix and the finished component.
Finally, there are systems based on isocyanates and epoxies being developed to offer the desirable
properties of high glass transition temperatures, good long-term heat resistance, good dimensional
stability, low thermal expansion coefficient and some flame retardancy.

4.6.3.6 Melamine and Urea Formaldehyde Resins (Aminos)

These resin systems are used principally in moulding compounds, but do find application in paper
reinforced laminates for the decorative and wear surfaces of domestic worktops and the like.

4.6.3.7 Phenolic

Phenolic resins are the oldest of man-made polymers and, in some respects, all their multifarious
applications could be seen as being matrices for composites. However, this report will restrict itself
to the application of phenolic resins as matrices for structural composites where their application is
usually to take advantage of their excellent, inherent fire resistance present without the need for any
additives or modifications to the chemistry of the resin. Phenolic composites applications may be
divided into two distinct types of composite product.

Firstly there is the traditional, high pressure, high temperature (120-170 °C) cure laminate. These
are produced by the prepreg route where suitable reinforcements are impregnated with phenolic
resol resin in solution. The solvent, usually a ketone or alcohol, is driven off and the cure of the
resin advanced, thermally, to the point where the resol is solid but not crosslinked. The resulting

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Thermoset Resins Market Report

sheet material is simply impregnated reinforcement, which may be glass, carbon or aramid. This
material is used (as described in Section 4.6.1.1) for the production of aerospace and other
components where maximum achievable mechanical properties are required, combined with high
fire resistance. In recent years, phenolic materials have replaced epoxies for passenger aircraft
interior fittings to improve the fire ratings in the cabins.

The second type of laminate are those produced, as with polyesters, by the whole range of
composites production techniques described in Section 4.6.1. Phenolic resins may be cured with
acid catalysts at low temperature (50-70 °C) and systems have been developed which, by careful
selection of resin viscosity and catalyst reactivity, allow all processing techniques. Delayed action
catalysts are also available which do not react at any appreciable rate until the temperature of the
laminate is raised to, e.g., 60 °C. The excellent fire, smoke and smoke toxicity performance of
these materials have led to their selection as matrices of preference for authorities such as London
Underground. For certain processing techniques, phenolics are the only resin system available
which meet that authority’s requirement for internal components for underground rolling stock.

For pultrusion, thermal cure systems are preferred to acid catalysed since the temperature necessary
to cure thermally is available and the acid catalysts tend to corrode the pultrusion dies.

Phenolic resins suffer from one major disadvantage and that is that they cannot be reliably coloured
in a manner which is stable. All phenolic mouldings need painting or otherwise surface finishing if
a decorative effect is required. Fortunately paints are available to meet the fire requirements.

Polybenzoxazine resins are highly modified phenolics and are produced by the reaction of a
diphenolic compound, a primary amine and aqueous formaldehyde. The resins have been reported
as having very high glass transition temperatures (Tg), up to 350 °C, and could become lower cost,
competing materials for expensive aerospace matrices such as PMR-15. Work continues by
companies such as Hitachi.

4.6.3.8 Polyimides

Polyimide resins are a very different material to most of the matrices discussed here. Polyimides
are really thermoplastics, which have a very lightly crosslinked structure under normal processing
conditions. However, the small degree of crosslinking makes their processing by traditional
thermoplastic means very difficult and, processed more akin to thermoset materials, they are
becoming increasingly favoured and employed for cryogenic and aerospace applications. To obtain
high performance crosslinked products, polyimides need to be moulded at ca. 300 °C and post
cured at 400 °C. The resins produce water as a by-product during cure, which, at the curing
temperatures, is a further complication.

Polyimides have high heat resistance, up to 540 °C is quoted for short periods, good high
temperature stability, good impact and tensile performance and an inherent resistance to
combustion. However, although a number of systems are available (some in the form of
preimpregnated fabrics), and there has been some penetration beyond the advanced applications
into, for example, tubes and electronic component manufacture, both their cost and their processing
difficulty appear to limit any early increase in their consumption by the composites industry. Under
licence from NASA, work is nevertheless proceeding in a number of locations such as Culver City
Composites, Cytec Engineered Materials and the Georgia Institute of Technology, to extend both
their aerospace but, more particularly, their commercial application.

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Thermoset Resins Market Report

4.6.3.9 Modified Polyimides

There is a range of modified polyimide resins available for the advanced technology industries such
as aerospace. These include polybismaleinimide, a high temperature curing material (200-260 °C)
which can be used for filament winding. Suppliers include DuPont, Amoco and Rhone-Poulenc.

4.6.3.10 Unsaturated Polyesters

Irrespective of the competition from both well-established and recently introduced composites
matrices, the unsaturated polyesters remain and will long remain the workhorses of the composites
industry. Literally thousands of different commercial systems are available, whether based on
ortho-, or iso- phthalic chemistry, and their success has long been proven. Whatever the finished
component application, from simple enclosures, through automotive components to massive tanks
or components operating under a wide range of temperature and environmental conditions, there
will be a number of standard, off-the-shelf, first-quality resins to call upon, all competitively
priced.

At the same time they exhibit viscosities, gel times, reactivity and pot lives suited to any chosen
fabrication technique and moreover are available in both standard and accelerated condition, UV
stabilised and also offering a varying degree of fire retardancy. Most are surprisingly tolerant to the
processing and environment of the shopfloor and, finally, all may be used with a wide range of
catalyst systems to promote cure.

Manufacturers continue to work at reducing VOC emission levels during processing and curing.
Effective low styrene emission (LSE) resins with acceptable processing properties are now
available as standard and the introduction of dicyclopentadiene (DCPD) grades is another
alternative for the fabricator to consider in this context. Other than this benefit and reduced
monomer content, the latter offer additional advantages to the fabricator, such as lower shrinkage
during polymerisation, a smoother surface showing less ‘print-through’ of the underlying
reinforcement, improved curing and quicker demoulding.

4.6.3.11 Urethanes

The urethanes (PU or PUR) are a very versatile range of thermosetting resins when cured. Unlike,
polyesters or epoxies, the moulder does not buy ‘polyurethane resin’ but the starting materials for
the manufacture of that resin, isocyanates and polyols. Hence their processing is totally different
from that of any other thermoset resin.

The production of composites from polyurethanes is usually by means of a high pressure


impingement mixing machine. The two components are mixed at high pressure by impingement
and fed to a mould where the chemistry of polymerisation and crosslinking takes place and the
product is formed in one process. The reinforcement is usually in the form of short glass fibres
suspended in one or both of the components of the reaction. The process is known as RRIM
(reinforced reaction injection moulding). There are also processes known as RIM where the
urethane is moulded unreinforced, and SRIM (structural reaction injection moulding), which
produces a product closer in nature to a true composite since long reinforcement, usually glass, is
placed in the tool before injection of the reactants. This is similar in principal to RTM with more
conventional matrices. Moulding cycle times are low, often less than one minute. The finished
components, frequently employed for a large range of automotive under-the-bonnet, external body
parts and decorative components, can vary in nature from rigid, reinforced parts to flexible, foamed
components for the tops of dash boards, etc. The other very useful and functional property of
urethane systems (formulated for the purpose) is the ability to self skin. Hence a component with a
reinforced foam as the bulk of the moulding can leave the mould with a uniform solid skin.

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Thermoset Resins Market Report

Improvements in machinery and in the ability to inject longer fibres are speeding the process for
the production of structural materials from urethane moulding processes. One example is Fiberim
from Huntsman Polyurethanes Automotive of Belgium. With this system it is claimed to be
practical to directly inject glass reinforcement in lengths of up to 10 cm, as well as rovings. The
result is that the reinforcement is more accurately distributed across the entire moulding cross-
section, producing a finished component with equal mechanicals to a traditional SRIM component
but at lower weight, reduced wall thickness and producing significantly less glass scrap and a
reduced total cycle time.

4.6.3.12 Vinyl Esters

Vinyl esters are becoming increasingly attractive thermoset composite matrices because they can
be considered as combining the best resin and finished property characteristics of both the
unsaturated polyesters and the epoxies, at lower cost than the latter whilst not much higher than the
former. They are easier to process than the epoxies but their mechanical properties lie between
those of polyesters and epoxies.

However, it is their high laminate strength and excellent chemical resistance at elevated
temperature that are particularly attractive, together with their good electrical and thermal
insulation and their resistance to impact, fatigue and water absorption. It is the latter characteristic
and, hence, resistance to blistering, which makes them a popular choice in the fabrication of
swimming pools and liquid storage tanks.

Like most other thermosets considered by this study, the vinyl esters can readily be modified either
chemically or by the use of additives, such as rubber-modified epoxy, to secure benefits in
adhesion, wear resistance, toughness and elongation. Indeed some modifications can result in
effective cost savings, although at the expense of certain properties.

The synthesis of a new class of commercial vinyl esters based on aliphatic oliogomers and
methacrylate terminated aromatic oliogomers, diluted with low molecular weight reactive
monomers such as styrene, was announced recently by B. Starr and co-workers at Virginia State
University. These are expected to find increased application in civil engineering structures as they
offer improved long-term degradation resistance, enhanced corrosion resistance and intrinsic low
UV absorption.

4.6.4 Composite Applications

4.6.4.1 Aerospace

First utilised for the defence sector but, latterly, extending in a more comprehensive manner into
the commercial sector, composites are playing an ever-increasing part in the design and
construction of aircraft and other aerospace items. The performance expectations of these markets
can only really be satisfied by the epoxies, vinyl esters, BMIs and similar thermosets. As with all
high-tech applications there is major advantage to the remainder of the worldwide composites
industry and, hence, to all the standard resin systems through the amount of downward spin-off that
has resulted, in terms of materials, equipment and processing technology. With wings, control
surfaces and tail assemblies already largely of composites construction, the day of the all-
composites airliner cannot be too far off; a development that will boost the whole thermoset resin
industry.

4.6.4.2 Chemical and Corrosion

There is truism in the statement that the chemical plant and corrosion-resistance industry would be
very much the poorer without the advent of composites over 60 years ago and the development,

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Thermoset Resins Market Report

principally by Dow Chemical, of Derakane vinyl ester/bisphenol resins some 30 years ago.
Composites have had a major influence on the ability to contain successfully, process and move, by
tanks, pipes and in other ways, all manner of chemically active, corrosive liquids, solids and gases.

Nevertheless, it is a market sector that only accounts for around 7% of the total output of
composites, a figure that suggests room for a respectable growth rate, as track-record, education
and life-cycle benefits are better recognised.

4.6.4.3 Energy Generation

Unsaturated polyester and epoxy resin composites have had considerable success over recent years
in the manufacture of evermore massive wind turbine blades for wind-energy generation. Many
composites solutions to this new challenge have been tried with reinforcement ranging from glass
to carbon and laminated timber. Indeed much of the new success which is claimed for wind energy
is the direct result of the steady replacement of the earlier all-wooden blades by composites. Blades
have been fabricated by a range of techniques: contact moulding, RTM, autoclave and, most
recently, resin infusion. As the blade length continues to grow with 40 metres working and 50
metre blades being built, the latter is becoming the favoured fabrication route. Whilst initially it
was thought that the high tip speeds and aerofoil design of these blades would lend themselves to
aerospace, autoclave manufacturing techniques using prepreg, the sheer size has prevented this.
The cost of an autoclave to take such blades would be prohibitive.

Taking into account their often highly corrosive locations (sea-salt laden atmospheres), widely
varying operating temperatures (–15 °C or less to +45 °C), together with a high probability of
lightning attack, wind energy blades can be an unexpectedly severe application for composites.
Consequently, there is now little doubt that this is an application from which many design,
manufacturing and technology principles will spin-off downwards, to be of particular benefit, for
example, to the infrastructure market sector.

In the same way, there are a number of alternative energy-generation systems, such as wave and
tidal power, whose increasing success will, with time, owe much to techniques developed by
workers in the wind-energy generation field.

4.6.4.4 Infrastructure

The building and construction industry has always been a major composites market, typically
consuming, irrespective of country or geographical area, over 20% of the annual output. However,
including the whole of the civil engineering sector, infrastructure has, over the last 5-10 years,
begun to show that this sector will have a major influence on the future appearance of the
worldwide composites industry. The expected annual growth rate is estimated to be around 4-5%.
This massive growth will be reflected over the whole of the thermoset resin industry. The
infrastructure sector includes adhesives, coatings and almost every other application type
considered by this study.

Examples are included throughout this report. However, new-build pedestrian and road bridges,
transmission pylons, marine pilings, structural assemblies, pipes, tanks and enclosures are worth
emphasis as to the way in which composites for infrastructure application are moving. In situ
infrastructure repair is also important, for example, by the use of epoxy resin impregnated
multidirectional carbon fabrics, in carefully tailored pieces, for the repair of prefabricated
prestressed concrete beams. One of the first of such repairs was in November 1996 on the A10
motorway in France, between Paris and Chartes. The ‘repair patches’ were simply roller-pressed
over a pre-cleaned defective area and heat cured in situ, with the epoxy acting as not only the
matrix but equally the adhesive and the working surface coating. More recently, bridge
enhancement and repair has tended to use prefabricated, pultruded carbon/epoxy elements stuck

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Thermoset Resins Market Report

into place on the concrete with epoxy adhesives. This had the advantage of more control over both
the cure and the fibre placement of the repair ‘patch’.

A further infrastructure application, which is being accepted slowly in the market place, is the use
of composites reinforcing bars for reinforced concrete in place of the traditional mild steel. The
problems which are being seen today with reinforced concrete buildings, only 40 or 50 years old,
failing as a result of reinforcement corrosion within the concrete have turned attention to this non-
corroding alternative. The full technology has still to be developed but the potential is very large.

Once life-cycle economics and associated benefits are much better recognised, then an explosion of
interest will be generated in infrastructure applications for thermoset resins in composites.

4.6.4.5 Marine

A visit to any marina will indicate clearly the supremacy of composites for the construction, both
below and above the water-line, of all types of vessel, from small dinghy through to ocean cruisers,
fishing and work boats. Timber, steel, aluminium or other materials are now rarely seen among
leisure and smaller work boats. This worldwide success and proven long-term, maintenance-free
service has undoubtedly helped to promote the use of composites in perhaps every other market-
application sector. The situation has undoubtedly been helped by the designer’s ability to create
clean, sculptured moulded lines in composites together with the readily noticeable resistance to
mechanical and environmental attack; and the sea environment can be severe. Perhaps the ultimate
example of marine use are the fleets of mine hunters used by the UK Royal Navy and other navies
around the world. These vessels, up to 68 metres (220 feet) in length, are warships and demonstrate
the confidence which naval architects have in the material.

In non-ship, marine applications, there has been an increase recently in the use of composites in
quays, jetties and similar structures, where the lack of corrosion puts the life expectancy of a
composites structure well ahead of those in timber or steel. Furthermore, timber requires treatment
with chemicals to prevent biological attack and these can leach into the water with subsequent
environmental problems.

4.6.4.6 Transport

Examples of land, sea and air transport, which increasingly employ composites successfully, can be
found throughout this study. Collectively, over the years, they have consumed high tonnages of
most of the commercial thermoset resins available and, as the need for lightweight, high strength,
cost-effective, environmentally resistant materials for use in transportation grows, that tonnage can
only increase. The expected annual growth rate for composites in this sector is 5%. Another reason
for this success, demonstrated by the mouldings required by the railway industry, is the ability to
manufacture large one-piece assemblies. The phenolic composite front-end mouldings used in the
construction of the motive power units of the Channel Tunnel vehicle shuttle trains are a particular
and noteable example, as are the polyester examples used on the Eurostar passenger trains and
many other railway passenger surface trains throughout the world, and the phenolic cabs on many
London Underground trains.

Figure 4.1 depicts a considered estimate of the market shares for composites in transport
applications.

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Thermoset Resins Market Report

Shipping
Aerospace
10%
15%

Railways
30% Automotive
25%

Trucks and
buses
20%

Figure 4.1 Estimated market share for composites in transport applications

4.7 Encapsulation

4.7.1 Epoxies

As the range of applications grows, it is becoming increasingly difficult to differentiate between


what is a true encapsulation, or even casting, and what is only a coating. The increasing use of UV
curing epoxy systems as ‘sealants’ to cover or encapsulate microchips on, for example, credit and
‘smart’ cards, is one particular example. Whilst the consumption per card is small at less than 1 g,
the consumption is growing through the use of resins which offer enhanced card security, ‘water-
white’ colour and minimal ‘coating’ thickness at optimum viscosity, tensile strength, elongation at
tear and coefficient of thermal expansion.

The largest encapsulation use of epoxy resins is in the electronics industry where parts of or
complete circuits are encapsulated to ensure electrical insulation and make handling and
installation processes easier.

Similar epoxy systems also find increasing application as ‘sealants’ for a wide variety of electrical
items from coils and cable connectors, through strain-sensitive circuitry, to transformers. In
addition, if carefully chosen, re-entry access to encapsulated components for adjustment and/or
repair, may also be possible.

4.7.2 Hybrids

Encapsulation as a means of enhancing electrical insulation and/or creating more readily


handleable electrical assemblies is nothing new and now commonly applied to semiconductors,
transistors and microchips. However, as the severity of their operating condition increases, so does
the need for improved heat resistance, for example, without alteration to the initial processing

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Thermoset Resins Market Report

conditions. This has spawned the development of a range of suitable hybrid resins and one example
is Sumitomo Bakelite’s, silicone-modified polyimide blended with a special epoxy resin.

4.7.3 Others

Low molecular weight aromatic thermosetting polymers based on polynapthalene or polyphenylene


(such as Dow Chemical’s new SiLK resins), are being used in the manufacture of faster, smaller
and higher performance integrated circuits. Thin films of low dielectric constant after cure (at
400 °C or higher), are applied by conventional spin-coating equipment (illustrating the dilemma
between coating and encapsulation).

4.8 Flooring

4.8.1 Epoxies

Epoxy resins have long been employed successfully in the formulation of usually unreinforced
systems suitable for coating concrete, other flooring materials and substrates such as timber. These
coatings provide decoration, perhaps with pigment and/or aggregate additives, and enhance their
skid resistance as well as their durability to pedestrian and vehicle traffic or protection from harsh
environments such as oils, petrol and salt. With the advent of lightweight bridge decks and similar
structures employing composites, epoxy overlays are the preferred alternative to the former
cementitious formulations. The latter typically suffer from significant fracture and delamination
from the substrate when subjected to flexural loading. Such epoxy overlays, which markedly
reduce the overall dead load on the structure as a result of their lower density and thinner film
application, have also been used successfully on concrete-filled steel grid and steel orthotropic
decks.

For reasons of VOC reduction, these overlays are beginning to move from solvent to water-based
systems, as typified by EPOXYShield, a two-part, low odour epoxy from Rust-Oleum. Excellent
adhesive properties are claimed and the overlay, onto which vinyl acetate ‘chips’ can be sprinkled
whilst wet to provide decoration, cures, touch-dry, in twenty minutes.

4.8.2 Polyesters and Vinyl Esters

Where the environmental conditions permit, both the unsaturated iso-polyesters or, preferably, the
vinyl esters, can be successfully employed for ‘flooring’ type applications. Furthermore, ‘walling’
must be included in the term ‘flooring’, as typified by the in situ application of glass fibre
reinforced linings employing either polyesters or vinyl esters to timber, concrete, brick or stone
substrates, to provide an easily cleaned, biological, fungoid and chemically inert, but often self-
decorated, surface. Industrial kitchens, food manufacturing and processing factories and abattoirs,
are typical applications, competitive to ceramic tiles as a result of their ease and ready application.
Like true composites mouldings, all these usually employ a resin-rich top coat. Application to the
substrate may be by hand or spray techniques.

With polyesters, unlike the epoxies, adhesion, irrespective of substrate, needs to be noted as a
possible long-term in-service problem. This has been addressed by resin manufacturers and those
employed in the application of this type of lining and is now much improved.

Swimming pool linings, both domestic and commercial, also need inclusion under this ‘flooring
and walling’ heading even if they are of modular composites moulding design. It is a thermoset
resin application that, at best, is surprisingly severe. Basically, pools can be considered as chemical
tanks. The ease of obtaining patterned, different coloured decoration is one of several reasons for
the competitive attraction of thermoset resins over ceramic tiling.

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Thermoset Resins Market Report

Flat roof covering (a floor on the roof) is another polyester application that has grown in recent
years. Having suffered from a number of ‘cowboy’ contractors in its early years, the advantages of
the application of polyester/glass laminates, either by hand application using glass mat or spray
deposition, are becoming recognised once again. It is a perfect way to ensure that there are no leaks
in a flat roof. The result is a single roof sheet, sealed to the edges and incapable of leaking if the job
is done correctly and a huge advantage over felt or asphalt type finishes.

4.8.3 Phenolic and Furane

Low temperature or ‘cold’ cure phenolic systems are used for acid and chemical resistant flooring
screeds and are probably the oldest of such formulations. Such systems offer good mechanical and
thermal resistance and are therefore ideal in the repair of cracked or otherwise damaged surfaces.
Additional applications include chemical process equipment, acid resistant constructions, conduits,
gas scrubbers, chimneys, acid towers and effluent treatment equipment.

4.9 Gelcoats and Pigment Pastes

Gelcoats and pigment pastes are essential raw materials consumed by the composites industry.
Both employ every type of unsaturated polyester and vinyl ester resin and, occasionally, bisphenol-
A based epoxies in their formulation. Although gel and rear-face flow coats may be unpigmented,
pigmentation is much more typical. Pigment paste is the vehicle by which pigmentation is
introduced into either a gelcoat or the matrix, laminate resin.

Gelcoats form the exposed or working surface of a thermoset composite moulding. Usually
unreinforced, this thin (0.40-0.90 mm (0.016-0.035")), resin-rich, usually pigmented surface coat
applied by hand or spray, provides a hard decorative and protective finish, the resistance of which
to fading or ultraviolet attack is related to the base resin but may be enhanced by the addition of
stabilisers. It is not unusual for the gelcoat to be textured, taking a low profile pattern, if required,
direct from the mould-tool surface.

Specialist gelcoat grades, typically formulated with neopentyl glycol (NPG) offer superior
resistance to osmosis (surface blistering as a result of continued water immersion), chemical or
other more severe corrosive attack. In this context, ongoing development work is important, in
view of the part that the gelcoat plays in protecting the underlying laminate. One example is the
recent announcement by Scott Bader of Microban®, the world’s first and so far only ‘sanitary’
gelcoat, which provides long-term built-in antibacterial protection where hygiene, such as in the
wall-coating of industrial kitchens, is of vital importance.

Finally mention should be made of other types of gelcoat, perhaps better classed as ‘surface
improvers’ or ‘surface pastes’ that find application for the surface coating of phenolic laminates.
These materials are not normally pigmented but serve to improve the quality of the moulded object
surface to aid painting.

4.10 Paints and Lacquers

This is a vast subject with more types of resins, thermoset and thermoplastic, involved than with
almost any other application except, perhaps, adhesives. It is therefore too great a task in a study
which is, by definition, a summary, to discuss all of these and a few systems have been selected for
inclusion. Many man-made materials such as alkylphenol resins are used to modify natural
thermosetting materials in paint systems. These are not included.

Not too many years ago, industrial and domestic paints and lacquers, were based on boiled
(polymerised) linseed oil technology. Then came the alkyds, the urethanes and, in certain cases, the
epoxies, systems which have all undergone considerable chemical and formulation development as

45
Thermoset Resins Market Report

the need for solvent-less paints and lacquers has grown commensurate with the need to reduce, or
even eliminate, VOC emissions. At the same time, as far as industry is concerned, there is
considerable interest in UV radiation curable systems and equipment offering marked productivity
improvement.

The Japanese company, Dainippon Ink & Chemicals is one of many helping to ease the VOC
emission problem when painting timber, perhaps still the most common substrate for paints and
lacquers. Their entirely styrene monomer-free unsaturated polyester based paint systems also boast
equal or superior film properties and surface texture, with rapid room or even lower temperature
cure.

Protective paints and surface coatings account for some 20% of the European consumption of alkyd
resins and a significant proportion of that is employed in the painting of electricity pylons.
Consequently, this is one application which, if a viable alternative was available, offers a large
potential for reducing the quantity of liberated volatiles. Work by DSM Resins and the UK-based,
EA Technology, has shown the effectiveness of such an alternative, employing an emulsified D4-
epoxyester and an emulsified urethane alkyd for the finishing coat.

High solids content (80% or even 90%), epoxy-based paints offer the same VOC emission
reduction potential, although sometimes at the cost of application characteristics and the important
long-term stability of the system. Relatively high molecular weight epoxy plus phenolic-based
systems, are also important in the manufacture of lacquers used for the coating of metal packaging,
as in for example, food and beverage cans and larger capacity drums and canisters. As well as
protecting both contents and container from corrosion and other potential damage, such coatings
(typically only 6- P WKLFN PXVW H[KLELW JRRG DGKHVLRQ DQG HODVWLFLW\ DV ZHOO DV ZLWKVWDQGLQJ WKH
manufacturing conditions first employed to produce the container. Other industrial ‘lacquers’ based
on the same thermoset resin chemistry, have applications such as anti-corrosion protection for heat
exchangers, tanks, ducts and piping and are employed for the coating or even impregnation of
electrical equipment such as the windings of electric motors. Whilst the majority need only satisfy
ambient and mildly elevated temperature conditions, environments of perhaps 150 °C are not
unusual.

The whole land transport vehicle market, cars, buses, trucks and railway wagons is, like electricity
pylons, a massive paint and coatings user. This market sector is beginning to benefit from the
development of aqueous two-component polyurethane systems, which better satisfy the
increasingly severe environmental regulations, without any loss in coating and drying speed or
long-term in-service weather and colour resistance. The same is true for UV curable paints for the
same range of applications, which can offer a complete cure in less than 2 minutes, and
occasionally within seconds, even in ‘shadow areas’.

Finally, a whole range of other ‘paints and lacquers’ for a wide spectrum of applications from
flooring to furniture, is changing steadily to water-borne systems based, for example, on aliphatic,
fatty-acid modified polyurethane dispersions, or aliphatic self-crosslinking urethane/acrylic
copolymers.

4.11 Pastes and Putties

Like the adhesive market, the ever-growing use of a wide and diverse variety of pastes and putties
has usurped many otherwise traditional materials formerly employed as gap-fillers, for repair, for
sealing or as a ‘thick’ adhesive application. Indeed, there is good indication that with time it will
become even more difficult in some situations to differentiate between what is an adhesive and
what is a paste or putty.

As far as thermoset resins for pastes and putties are concerned, the supremacy of the orthophthalic
and isophthalic unsaturated polyesters in their manufacture, cannot be questioned or challenged.

46
Thermoset Resins Market Report

Since their introduction, as carefully blended compounds with critically selected and particle-sized
mineral fillers, circa. 1960, the consumption has grown, thousands fold. With justification, as
confirmed by the trade statistics appearing elsewhere in this study, it has become a major market
for the unsaturated polyesters. Hence the continual introduction of new, improved grades now often
also incorporating glass fibre reinforcement, can be expected. It is a growth industry, which has
also spawned new manufacturers owing to the relatively low capital investment required.

Much of this success, can be put down to the ease with which these materials can be employed and
the tolerance there is in the quantity of catalyst necessary to achieve cure under a temperature
environment from 5-30 °C and with an equally wide humidity variation. They are true DIY
materials, and indeed this is the market to which they owe much of their success. Although the
repair of car bodies undoubtedly predominates, under either commercial or home conditions, the
cost-effective availability of these polyester pastes and putties in a wide-range of container sizes,
from a wide-range of sources and offering a guaranteed long-term in-service life has opened
numerous applications. Only one other example needs high-lighting in confirmation. Not too many
years ago, many painters and decorators judged the water-based filler/plaster compounds to be
optimum surface preparation materials, even for external application. Today they have recognised
the advantages offered by using thermoset-based versions and these now predominate, at least in
the professional market.

Finally, however, it is necessary to recognise that where higher temperature and enhanced
corrosion resistance is demanded, then epoxy and even phenolic and furane-based pastes and
putties, perhaps used as bonding or grouting materials with ceramic tiles or carbon bricks, become
increasingly essential. Although not as easy to use as the polyesters, and the epoxies are more
expensive, the improved bonding properties may also be accompanied with much better abrasion
and wear resistance. Many industrial plants are exposed to highly aggressive environments and
these typically cold-curing, two-component thermoset systems containing mineral fillers such as
quartz sand and flour or pitch coke, are essential in securing a long in-service life.

Suppliers of pastes and putties include BUFA Reactive Resins, Hawkeye Industries, U-Pol, etc.

4.12 Polymer Concrete

Although water remains the most typical and widespread dispersion medium in the production of
sand and aggregate-based cementitious formulations and products, the alternative use of epoxy,
unsaturated polyester and phenolic resins, is far from unusual for specialised applications. These
include grouts, adhesive pastes, screeds and in rock fixing devices, mine-bolts and similar. All are
applications that utilise the higher strength and markedly enhanced chemical resistance of the
product.

One of the largest user of this type of product is the resin bonded roof tile and artificial slate
product. The roof tile offers higher surface attrition resistance than its Portland cement bonded
equivalent, although at a higher price, whilst the latter offers excellent appearance, almost
indistinguishable from the real thing, at a fraction of the price of a real slate.

Other applications for polymer concrete include machine bases for very accurate cutting and
turning machines (the polymer concrete has higher mechanical damping than steel or cast iron) and
decorative items such as statuary and artificial stone facings for buildings, etc.

4.13 Printing Inks and Associated Applications

Many resin systems are involved in the production of printing inks and associated materials, but
probably the most frequently found is the phenolic group. These are used to modify colophonium
resins (a wood gum) to produce systems which will meet the extremely high drying speeds required

47
Thermoset Resins Market Report

for modern magazine presses. The resins produced by this modification have the ability to lose
solvent very rapidly and, although only being perhaps 15% of the ink formulation, a considerable
amount of resin is consumed in this way.

Carbonless copy paper uses zinc or aluminium salts of aryl or alkyl-phenol-formaldehyde novolak
resins in combination with other chemicals as colour developers. The carbonless copy paper market
is in excess of 500,000 tonnes per year of which ca. 10% is chemicals. It is easy to see that an
apparently insignificant application can consume a lot of resin.

4.14 Tooling

One advantage of the low-capital/labour-intensive sector of the composites industry, is the ability
to employ both ‘open’, male or female, and ‘closed’, male and female, tooling, itself cost-
effectively fabricated as a composite moulding. It is a technique which has been able to extend into
other manufacturing sectors, simply because, as in composites moulding, a wide variety of
thermoset resins, both reinforced and unreinforced, can be employed. Initially the furanes tended to
dominate but, with time, other more suitable more readily processed and improved epoxies and
isophthalic unsaturated polyesters were developed, specifically as tooling systems.

4.15 Friction Materials

Friction materials are the group of materials that are designed to have a high coefficient of friction,
and include all types of brake pads and shoes for road and rail vehicles and machines and clutch
facings for vehicles and other applications. These materials were, for many years, manufactured
from a phenolic resin binder and asbestos fibre. Clearly, in recent times, the use of asbestos has
ceased but phenolic resins remain the almost universal binder for the glass, aramid and metal fibres
that have replaced the asbestos.

Phenolic resins are ideal for this application since they may be relied on to have excellent high
temperature properties. The energy absorbed in a braking system or when engaging a clutch is very
high indeed and it is not unusual for these materials to reach temperatures of 800 °C plus. Many
types of resin are used, simple phenol/formaldehyde, cresol/formaldehyde, rubber modified resins,
cashew nut shell liquid resins and many others depending on the operating conditions of the
material to be manufactured. Most are added to the dry mix, prior to high pressure moulding and
curing, as a powdered novolak with hexamethylenetetramine as the curing agent.

Cashew nut shell liquid polymers, crosslinked with formaldehyde and ground to dust are an
important constituent of most vehicle friction materials. This material, known in the industry as
‘friction dust’, stabilises the friction coefficient of the pad or lining as the temperature rises in use.

4.16 Foundry and Refractory Products

Moulds for the casting of ferrous metals are traditionally made from silica sand, bound together
with a phenolic resin. There are many methods of achieving this using both novolaks and resols.
The investment process involves a novolak and a curing agent in solution poured onto and
evaporated from the sand before curing on a former to produce a ‘shell’ mould. Alternatively, a
liquid resol with or without a catalyst may be coated onto sand, which is then moulded either by
packing into a suitably shaped box to produce a ‘core’ or placed in an open box, and a pattern used
to make the cavity for the metal in the sand. The resin is then cured with heat, or at room
temperature if a catalyst is used, to bind the sand. There are many variations on this using gaseous
catalysts, etc. When the metal is cast the resin burns out and the sand may be simply knocked from
the casting and is often recycled. This is a completely destructive use of a thermoset resin system
and consumes high volumes in countries which retain a foundry industry.

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Thermoset Resins Market Report

In more modern times, some of the phenolic binders have been replaced with other thermosetting
materials such as epoxies, aminos in combination with phenolics and acrylate resins but furane, an
older resin binder, retains a share of the market. The reason for this has usually been a new process
where the chemistry allows faster cycling using gaseous catalysts such as SO2.

Refractories are those parts of the metal making process that are used for the handling of the
molten metal during casting. These are made by binding suitable mineral powders, such as bauxite,
with phenolic resin and reducing the phenolic resins, in a very low oxygen atmosphere, to glassy
carbon. The products are capable of use at temperatures well in excess of 1,000 °C. An estimate of
the resin usage worldwide for this type of application was 35,000 tonnes in 1993. A final, but
important refractory use for phenolic, furane and some other resins is ‘tap hole clays’, putty like
materials used to block holes in furnaces where molten metal has been allowed to flow out.

4.17 Wood Products

The use of thermosetting resins for the manufacture of boards of various types from timber is a
very old industry. Typically urea/formaldehyde resins have been used to bind together either
particles of wood in products such as chipboard or particle boards or laminates of timber to make
plywood. Urea-formaldehyde retains its place as a major resin for this application for products for
internal use, but the tendency of the resin to degrade under the influence of moisture means that,
for external use products such as marine grade plywood, phenolic resin binders are used.
Hardboard in it most basic form is made by compressing and heating saw dust without a binder
other than the natural resins in the wood. This product is not of high quality and phenolic resins are
often added to the saw dust to improve the strength of the final board.

Structural timber, in its natural state suffers from two problems. The first is the maximum size
available and the second is the variability of the product. In recent years the use of resorcinol resins
to produce laminated timber products for structural use has seen a rapid growth. Such beams,
‘glued’ together with resorcinol/formaldehyde resin, have guaranteed mechanical properties
because the knots and other imperfections can be removed, and the product can be made much
larger than any single piece of timber that is available. More recently still, pultruded plates of glass
or carbon fibre with resorcinol/phenolic resin have been laminated into the timber between the plies
to add stiffness to the finished product.

4.18 Foams

Thermosetting foams are the dominion of polyurethanes with two main types. The first is the
flexible foam, so well known for seating, mattresses, etc., and the second the rigid, insulation foam
found in industrial installations, pipe lagging, refrigerator insulation, etc. Flexible foam is generally
produced on a continuous belt with free rise for applications such as mattresses and the furniture
industry. The automotive industry however, uses moulded seat components, often with complicated
dual density technology, and accounts for over 670,000 tonnes per annum for seating alone. The
automotive industry consumed over 1 million tonnes of polyurethanes in total in 1998.

Rigid urethane foams are manufactured by continuous, controlled thickness lamination for
industrial insulation such as the production of steel faced panels for cold stores, etc. They may also
be made in large blocks and cut into sections for, e.g., pipe insulation. Industrial uses are high at
about 1.3 million tonnes per year in Europe alone. In situ foaming, largely for refrigerator and
freezer insulation, used 740,000 tonnes in 1998. Polyisocyanurates are a chemical variant on the
urethane theme and have improved fire properties. They are, at present, a small part of the overall
rigid foam scene.

The other thermoset resin, which is starting to penetrate the industrial sector in the urethane world
of foams, is phenolics. Phenolic foam is rigid but has a lower thermal conductivity than

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Thermoset Resins Market Report

polyurethane meaning that thinner sections will give the same effective insulation. Its fire
properties are also considerably better than the urethanes and applications where this is important
are growing. World consumption of phenolic insulation foam is probably around 10,000 tonnes.

One final application of thermosetting resins in foam applications is floral and horticultural foams.
Phenolic resins, formulated with suitable wetting agents since the normal foam is highly
hydrophobic, is used for the very low density (20-22 kg.m-3) foam used for the arranging of cut
flowers. A lower density variant is also used for hydroponic growing systems for the commercial
production of, e.g., salad crops.

4.19 Mineral Wool Insulation

Phenolic resins are used as the binder in mineral wool insulation such as rock wool and glass wool.
These resins, particularly in the case of the type made from rock fibres, are often modified with
urea to reduce cost. The resin binder content ranges from as low as 3% to as high as 15% for some
moulded high density products, but the vast majority is at the low end of this range. Resin
consumption in Europe alone is probably around 400,000 tonnes. The mineral wool insulation
market in Europe is dominated by Rockwool International.

4.20 Moulding Compounds

Phenolic resins and the aminos (urea and melamine) had their first applications as moulding
compounds. These materials, consisting of a novolak resin, a hardener such as
hexamethylenetetramine (hexa) and a wide range of fillers give properties as desired within the
limitations of the basically brittle matrices. ‘Bakelite’ the traditional, usually brown, material, from
which electrical plugs and fittings were made for many years, is a phenolic moulding powder. At
the present time phenolic and urea moulding materials have about equal market share at just over
40% each with melamine at ca. 8% and unsaturated polyester moulding compound at ca. 6%.

These materials are moulded in steel tools under high pressure and at relatively high temperatures,
normally in vertical presses. There is some injection moulding, particularly of the unsaturated
polyester compounds. Both phenolic and urea compounds have substantial uses in
household/electrical appliances with phenolics more dominant in electrical engineering. Urea-
formaldehyde is used for toilet seats and comprises virtually the whole thermoset market for this
application. Phenolic remains brown in colour and hence is not used for decorative purposes. Urea
is white and can be pigmented.

4.21 Abrasives

Abrasive wheels are made by bonding cutting material such as bauxite with phenolic or modified
phenolic resins. As many as three different resins may be used to obtain the correct wetting of the
grinding medium, the correct processing properties and the final performance, (hardness,
temperature resistance) of the finished wheel. Cut-off wheels may contain reinforcement, in the
form of open weave glass cloth, to reinforce the finished product and prevent centrifugal
disintegration.

Abrasive papers have the abrasive materials bonded to the backing paper or cloth with urea resins
for commodity papers and phenolic resins or, sometimes, epoxy resins for heavier use industrial
grades and ‘wet and dry’ applications. The production of industrial grade papers usually involves
two resins, one as a base coat on the paper or cloth and the other as a coating resin.

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4.22 Rubber Compounding Resins

The use of thermoset resins in rubber compounding, particularly phenolic and modified phenolic
resins, is standard practice. The resins serve three functions:

• an alkylphenol resol may be used to actually react with the rubber and aid vulcanisation
• a novolak alkyl phenol resin behaves as a tackifyer, a purely physical effect (strictly speaking
the resin is a thermoplastic in that state)
• thirdly, a phenolic novolak plus hexa cures during the vulcanisation and reinforces the rubber.

The use of phenolics in rubber, largely tyre stock, accounts for about 14,000 tonnes a year in
western Europe alone.

4.23 High Pressure Laminates

Laminating of layers of a wide range of materials, pre-impregnated with a resin system (under high
pressure and thermal conditions suitable for the cure of the resin) is one of the oldest uses of
thermosetting resins. For that reason, for many years phenolics dominated the market and, in total
tonnage terms they still do.

A wide range of sheet materials are used. For printed circuit board laminates craft paper is the
traditional material, impregnated with a phenolic resol in solution. The solvent is driven off and the
resin taken to a state of cure where it is still able to flow but is solid at room temperature. The usual
resins are alkyl-phenols often modified with oils such as tung oil to improve the final properties of
the laminate such as cold punching. In more recent times, for more sophisticated electronic
applications, the resin may be epoxy and the paper replaced by glass cloth. Paper is also the basis
of the decorative laminates used as kitchen worktops and a whole range of other applications. The
resin for the bulk of the laminate is also phenolic but the surface usually has two or more ‘special’
layers. The first, within the laminate, is a urea-formaldehyde impregnated paper which is printed
with the pattern required on the finished product. The final, top surface is a tissue paper
impregnated with melamine-formaldehyde resin to give a hard wearing finish. This final layer is
transparent when cured allowing the printed pattern to show through.

Cotton cloth is the material impregnated, usually with phenolic resin, to manufacture industrial
laminates known by the trade name ‘Tufnol’ which has become generic. These laminates contain
one or more phenolic resins to impregnate the cloth and are often made in thick sheets; the final
products are machined from the sheets. Typical applications are gear wheels (popular in the food
processing and cloth making industries since they can be lubricated with water, keeping the
workplace clean), cams and a wide variety of mechanical parts for the aerospace and other
industries.

Glass cloth laminates, particularly with epoxy resins but also phenolic and others, are used to make
high performance mechanical laminates and have found uses for such items as insulated fish plates
for railway track.

One traditional use of the high pressure laminating application is phenolic/wood laminates. These
are made with thin veneers of wood cured under high pressure (not as for particle and plywood
discussed above). The wood veneers are impregnated with a solution resin and pressed to high
density products from which components are machined. Typical products are as diverse as high
voltage insulators, handles for cutlery and nuts and bolts.

In most of the above laminate types it is possible to use a wide range of thermosetting resins, but
only the most commonly used for the application have been mentioned here.

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Thermoset Resins Market Report

4.24 Sports Goods

The use of carbon fibre reinforced epoxy resins in what are high tech or regarded as high tech
sports goods is a growing market sector. The manufacturing method is often autoclave from
prepreg but may be vacuum bagging, resin transfer moulding or even hand lay. Products range
from tennis racquets to skis, surf boards to fishing rods and many others.

Many of the products started life as polyester/glass products and those for the casual use market so
remain. Typical of this are surf boards where the advantages of the expensive carbon/epoxy
product could only be realised by the professional user. However, the press and peer pressure,
along with the relative wealth of the first world nations, has given the expensive composites sector
an alternative market, away from aerospace with its political uncertainties.

4.25 Others

The in situ, automatic repair of certain thermoset and thermoset-based composite structures is a
unique ability that clearly has important implications for those concerned with the selection of
these modern materials. Receiving mention elsewhere in this study, it is a ‘competitive edge’
property that is not duplicated by any other group of materials. The continued and growing
development of such resin systems can therefore, be expected.

Among them is a new electromagnetic transparent and tough polymer, named Automend, recently
announced by chemists and engineers at the University of California in Los Angeles (UCLA),
which is solid at room temperature and exhibits similar mechanical properties to epoxy resin. If a
product, such as an electronic device that heats and cools frequently, employing Automend in its
construction, cracks or fractures while in use, then it automatically repairs itself next time it is
heated to 120 °C. The subsequent repair is invisible and the mechanism has an infinite life, with
some 60% of the initial strength being retained. Many applications are envisaged from large lenses
to radomes.

In confirmation of the manner and speed in which thermosets are extending their application, there
are the following two developments. National Starch & Chemical has patented a range of Sycar
high performance organosilicone resins which their wholly owned subsidiary, Ablestik
Laboratories aims to develop into a number of products. Then there is a new insulation material,
formed by the blending of a silicone-modified polyimide and a special epoxy resin, developed by
Sumitomo Bakelite. The resin exhibits high heat resistance and good processability at low
temperatures, with the encapsulation of semiconductors envisaged as an initial application.

Equally important is the development of resin systems suitable for composites application, from
natural, renewable sources. The Composite Polymers Division of Ashland Specialty Chemical Co.
is one company involved, with their soyabean and corn based, Envirez 500 system, which has been
employed in the manufacture of a sheet moulding compound (SMC) and already found application
in the transportation, agricultural, off-road and construction industries.

In Europe, a group has been formed to further the use of renewable materials in composites. Called
the Sustainable Composites Network (SusCompNet) it is based at the University of Wales, Bangor
and is involved with natural fibre reinforcement and resins and matrices from natural, usually plant,
sources.

References

1. Z.W. Wicks, F.N. Jones and S.P. Pappas, Journal of Coatings Technology, 1999, 71, 895, 67.

2. T.F. Starr (Ed.), Pultrusion for Engineers, Woodhead Publishing Ltd., 2000.

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5 Market Development

5.1 Introduction

The research necessary for the preparation of this report was carried out using recently published
information, standard texts in their latest editions, correspondence and face to face and telephone
interviews. However, when it came to the discussion of what may be on the horizon in
thermosetting materials, many companies were reluctant to talk. It was clear, however that the
principal developments in both new materials and applications were aimed at the composites
market, with particular emphasis on the more lucrative ‘advanced’ composites sector.

Overall the aim of this independent technology, industry and market report is to assess what the
industry has achieved over the last 100 years and where the whole and various parts of that now
essential and still expanding industry are going, and why. Five years from now, there will
undoubtedly be more dramatic changes.

Although the greatest interest is being paid to developing matrix systems for composites, these
sections show equally that that industry’s needs are not exclusive. There is much technology
interchange, a polyurethane advance originally intended for say, foam manufacture, could well be
also applicable to a composites or moulding need and polyester chemistry developed for
composites could find use in an adhesive.

5.2 Market Issues

Whatever sector of the thermoset industry is examined, two words currently predominate,
‘infrastructure’ and ‘environment’. A large, if not the largest percentage of adhesives, coatings,
sealants and resin systems, find application under what can be termed infrastructure in the broadest
sense. There is a diverse range of finished products that continue to satisfy, in a very successful,
cost-effective and first-quality manner, the often high-performance specification demanded.

At the same time however, although these adhesives, coatings, sealants and resins typically offer
excellent environmental resistance, whether in respect of for example chemical, corrosion or
temperature condition, some of the initial thermoset raw materials and the finished products can
themselves pose environmental problems. These problems can be paramount either before or
during manufacture, in use or, ultimately, in disposal either as production waste or redundant
components. Many of the chemicals and resins involved are toxic to a greater or lesser degree,
demanding careful handling at each of those stages where they are used. This slightly negative
factor, opposing all the great benefits in application available from thermosets, is not unique to
those materials. Much development work in progress at the time of writing is designed to address
the environmental issues of the materials.

Indeed, one of the major environmental problems which receives virtually continual comment is
the matter of VOC emissions, or the measure and control of the quantity of volatiles evolved from
the organic solvents or active diluents frequently associated with thermoset materials. Their
presence ensures a degree of ‘workability’ in the finished product, also, like the styrene monomer
added during the manufacture of unsaturated polyester resins, some of these volatile organic
chemicals play a part in the molecular crosslinking common to all thermosets. The release of
volatiles is now governed by increasingly restrictive regulations, which affect every facet of
thermoset technology from handling through production to eventual disposal. Considerable
development work is now well in hand on alternative systems. Some of these involve water
dispersions in place of the previous resin solutions for various applications but this is far from
being possible universally. There is every expectation that within five years organic solvents will
have lost their predominance in favour of water in some industries, particularly adhesives and
surface coatings. Such change must, however, ensure no loss of application or market opportunity.

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Thermoset Resins Market Report

Another major difference which the thermoset resin industry of today will face increasingly over
the next five years is the question of both the raw material and finished product cost, whether that
be in adhesives, coatings, sealants or matrix resins. Nevertheless, in view of the many
advantageous properties offered by many thermosets over former and/or current competitive
products, those cost increases are judged as highly unlikely to adversely affect the 2.5% annual
consumption increase forecast.

The bulk of the thermoset materials discussed in this document depend for their raw materials on
oil and natural gas. The political situation at the time of writing, with a probable involvement of
areas of the Middle East in some form of conflict or political upheaval could have a short term,
adverse effect on prices for these. Indeed, further small but indicative price increases have already
begun or are in the pipeline. However, it is hoped that, in the medium term, the resulting period of
relative political stability in the major oil producing areas of the world, and a possible return to
production of some nations currently under sanctions, could lead to a period of considerable price
stability.

Many of the more common resins are commodity materials and supply and demand determine
prices more than any other factor. Indeed, a wide range of prices are offered to different customers
at different times and for different volumes for the same resin. For this reason alone, absolute price
stability cannot be assured. Oil and gas dependence will continue for the foreseeable future, and
certainly for the useful life of this report, but efforts to move away from this are already being
made by a number of bodies in their quest for using plant products as raw materials for resin
production. Even if successful technically, this could become a political/sociological problem with
the crops required for the raw materials often grown most efficiently in less developed/stable areas
of the world.

A further important environmental issue equally related to the matter of market opportunity, is
recycling. Although often, but somewhat incorrectly, judged relatively easy for the thermoplastics,
the thermosets are completely different. Whilst not impossible, the recycling of thermosets is often
impractical or uneconomic in the current economic climate, with the preferred answer perhaps
being a more lateral ‘re-use’ approach. Obviously adhesives, coatings and sealants being so thinly
‘spread’ in use, can certainly be listed as impossible to recycle. The same is not true for
applications such as composite mouldings or thermoset polyurethane foam.

There are no easy, ready solutions but the ‘recycling’ of production waste and redundant mouldings
must now be faced by the worldwide composites industry as an ultimate factor in determining the
future market size. A totally effective, universal, workable and moreover economically worthwhile
procedure for each and every thermoset, whether as raw material, production scrap or finished
product, still awaits discovery and commercialisation. However, with the filling and closure of
landfill sites, the need becomes increasingly urgent, particularly in the context of redundant
composites. There currently seems insufficient urgency to suggest resolution within the next ten let
alone five years.

Similarly it is difficult to forecast the new materials, within the whole thermoset resin spectrum,
which might be developed and commercialised within an equivalent time frame. Although a small
selection of recent developments follows, there are really no ready pointers, no suitable crystal ball.
What can however be offered with surety is an expectation for the continued development and
refinement of every one of the already well established thermoset based resin systems and their
application.

One final market conclusion is however very clear. The worldwide thermoset resin industry is here
to stay, it is thriving and growing, it is satisfying in a cost-effective and high performance, first
quality manner, an ever-increasing range of applications and markets. Many industries now depend
totally on its output and continued success and the future for the thermoset resin industry has
therefore to be summarised as both bright and exciting.

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Thermoset Resins Market Report

5.3 Epoxy Based Resins

The demand for thermosetting resins offering high elongation and toughness with good thermal
properties continues to grow as exampled by a new epoxy, Derakane 800 introduced by Dow
Chemicals. In addition, Derakane 470HT is designed for difficult high temperature applications
exceeding 180 °C and DER 329 is suitable for low viscosity applications fabricated by vacuum-
assisted resin infusion.

Nanocomposites consisting of reactive epoxy resins and mono-dispersed SiO2 nanoparticles, are
beginning to demonstrate slowly increased productivity, plus improved modulus and fracture
toughness, which this new innovative technology can offer. Even with very high nanosized particle
loadings, lower viscosity and still water-clear systems are practical, compared to the use of
conventional particle reinforcement.

The growing introduction of resins, not just epoxies, offering enhanced productivity by being
photocureable by UV irradiation, is demonstrated by an additive developed by Autex, which the
company is calling a ‘photo-latent polymerisation initiator’. In addition, there are associated
improvements in corrosion and temperature resistance, as well as outgassing.

Adhesives and also insulating materials, particularly for high-voltage engineering, constituted the
initial, successful applications for epoxy resins. Over the last half-century and with the use of
alternative raw materials for resin manufacture, that has all changed. There is now a massive
variety of both resin systems and curing agents, all carefully and precisely tailored in terms of their
final processing and cured properties, to meet a growing number of high-volume aerospace and
even industrial applications.

Although the phenolics continue to demonstrate through actual case history, their fire hardness and
low toxicity supremacy as composite matrices, work continues on the commercialisation of fire
retardant additives. Epoxies are far from being overlooked in this context and the traditional non-
reactive retardants like aluminium trihydrate, magnesium hydroxide and zinc borate, which
demand relatively high levels of addition and also act in the manner of fillers, are now finding
increasing competition from reactive versions. These are particularly important where, as in
adhesives, a good retention of the enhanced mechanical properties offered by the epoxies is vital.
Tetrabromobisphenol A (TBBA) is one typical reactive retardant, often used in conjunction with
antimony trioxide, which acts as a synergist. However, the problems of the formation of toxic
brominated dioxins in a serious fire remains. Consequently there has been the development of new
halogen-free firehard protection such as that provided by the pre-reacted phosphorus organics,
which, as with TBBA, are chemically-linked to the molecular structure of the epoxy.

A new epoxy resin, manufactured by Cuyahoga Plastics, is designed to win back some of the
ground lost to the more high performance thermoplastics by thermosets in recent years. EMC 2900
is claimed to have equivalent tensile strength, higher impact and lower water absorption than the
polyetherimide Ultem 2212 from GE Plastics, for example, although it is somewhat reduced in
flexural strength and has a 50% higher SG. The latter probably counters some of its claim to be half
the price. The new material is injection mouldable at relatively low pressure and has a very long
barrel life.

5.4 Epoxy Vinyl Ester Based Resins

Like the epoxies, the number of epoxy vinyl ester systems commercially available continues to rise.
One of the major suppliers is Dow Chemicals who several years ago introduced a range of
Momentum resins. These had the same strong chemical backbone and therefore offered identical
corrosion-resistance properties, to the much earlier and still available, Derakane resins. These
Derakane Momentum resins are claimed to offer enhanced performance resulting from their
improved reaction kinetics and production process control. Shelf-life is also said to be around twice

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Thermoset Resins Market Report

as long as previous grades and a shorter gel-to-cure property results in moulding cycles which are
improved by some 20%. Momentum 640-900 is designed for the high speed manufacture, by
pultrusion, of optical fibre tension members, an application which over recent years has seen
massive expansion. Momentum 470HT has been specifically designed for difficult high
temperature applications, exceeding 180 °C.

5.5 Phenolic Resins

Syntactic phenolic foam components, as well as ordinary phenolic composites, have become well-
established in the offshore oil and gas industry, through their inherent fire stability, low toxicity
and good thermal characteristics. They do not require (in comparison with every other commercial
thermoset resin) chemical modification nor mineral filler fire retardant additives, to guarantee high
fire performance. This is a particular and important advantage. Public safety in aerospace, marine,
mass transit, and railways generally, is benefiting from that same advantageous property. Indeed,
very few, if any, extreme fire scenarios cannot now be answered by some from of phenolic
composite system, irrespective of the size of the structure or the ambient conditions, which are
often harsh. This change from the traditional uses of phenolic resins has been brought about by the
ability to control the reactivity of the resin to the acid or latent acid catalysts used and the selection
of those catalysts to meet the demands of the processing conditions. The latter may now be any of
the processes used for thermoset composite material production from hand lay to pultrusion, RTM
to filament winding.

Innovative high temperature injection moulding systems, such as high temperature moulding
(HTM) and runnerless injection compression (RIC), for improving the moulding of phenolic
moulding materials for automotive components like solenoid caps, brake calliper pistons, power-
brake booster valve bodies and power-steering pulleys are moving from development into full-scale
use. Such new and faster processes in this sector are required as manufacturing competition
becomes intense. The utilisation of these processes together with advances in the technology of
computerised production control, can reduce manufacturing costs and, in turn, help to maintain
profit levels.

5.6 Polyimide Based Resins

It is the firm belief of NASA, who have been closely concerned with the development of polyimide
resin technology, that polyimide matrix material will eventually downspin into more commercial
applications from the present advanced engine component, aerospace uses. Suggested ultimate uses
include some of the power-train, under-the-bonnet and exhaust system component requirements of
the automotive industry. This belief is based on their patented RP 46 resin now available
commercially and manufacturing licence opportunities are being offered. Because the imide ring
remains very stable under attack by heat and chemicals RP46 can, it is claimed, be used up to
350 °C for 200 hours and can even withstand 410 °C for a short period. Kilogram for kilogram,
RP46 is stronger than aluminium, steel or even titanium. Compared with other polyimide resins
developed by NASA, such as PMR-15 and AFR-700B, RP46 offers better moisture resistance,
chemical and microcracking resistance. In addition, the resin offers a lower curing temperature
(300 °C, compared to 370 °C for example for AFR-770B) and is more ‘biologically and
environmentally friendly’ than any other widely used high temperature matrix resin. It is claimed
that it can be manufactured at a significantly lower cost than other polyimides (stated to be 22
times cheaper than AFR-700B). NASA sees the eventual application spectrum for RP46 ranging
from its greater use as a high-temperature composite matrix resin, through a wider variety of
aircraft components, adhesives and mould coatings, foam and film adhesives as well as commercial
requirements much wider than just those of the automotive industry.

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Thermoset Resins Market Report

5.7 Polyurethane Based Resins

A recent announcement by Bayer involves the use of water dispersible polyisocyanate crosslinkers
for urethanes used in adhesives. These consist of hydrophilically modified aliphatic and aromatic
polyisocyanates with the preferred material based on the trimer of hexamethylene di-isocyanate
(HDI). This development is a further illustration of the move towards water dispersed materials
where the chemistry permits.

5.8 Unsaturated Polyester Resin Systems

Perhaps the most important advance in unsaturated polyester resin supply, and one that is likely to
grow in importance, is the availability of resins that offer considerably reduced VOC emissions,
principally for open-mould processes. The most important of these are based on dicyclopentadiene
(DCPD) chemistry. Owing to complex changes in their molecular structure, these resins require
less styrene to achieve the same processing condition, but most importantly, without any under-
mining of their curing performance. In addition they also exhibit better water resistance which in
turn allows a reduced molecular weight while still retaining a ‘better than orthophthalic unsaturated
polyester resin resistance to blistering’ and allowing further styrene reduction. Other methods of
reducing styrene emission which do not impair the essential interlaminate adhesion are available
but are not as favoured.

Elsewhere in this text the use of unsaturated polyesters, and other thermoset systems, for the
finishing of walls and floors, is described. One disadvantage in the use of the former is the potential
for the development of mould and fungoid growths. This has had a limiting effect on the use of
polyesters, in favour of more expensive alternatives, in applications such as food factories and
medical units. It may have also affected, to a lesser extent, use in domestic shower trays, a major
market area.

Consumer demand for improved hygiene conditions generally, has lead the Scott Bader Company
to develop a gelcoat with built-in antibacterial protection, achieved with the addition of
Microban®. Microban®, an American company, is an acknowledged world leader in antibacterial
additives for incorporation into any plastic, textile or liquid base to provide the continuous
protection required against the growth of harmful, odour and stain-causing bacteria. A claimed
advantage is that the additive continues to work even if the surface is scratched or damaged. The
development is a major first for both companies and could help to progress the use of composites in
such applications.

5.9 Conclusions

The development opportunities open to the thermoset resin chemist and in turn to both the user and
the market consumer are massive and exciting. The competition from thermoplastics will
undoubtedly continue to grow in areas where they are acceptable and as their performance
improves. This is particularly apposite in terms of composite matrices as the application of the
newer engineering materials grows. However, continuing developments in thermosetting
technology, some aimed directly to ward off the thermoplastic challenge, continue and, for higher
temperature applications in particular, thermosets can be expected to grow their markets. The
development of so-called ‘nanotechnology’ in composites has enormous implications in respect of
material development generally, a development that is extending from computers to aerospace
systems. Structures which really do ‘heal themselves’ are mentioned elsewhere in this report and
such developments could extend through every market sector for which thermoset resins are
currently employed.

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6 Consumption – Current and Future

Whatever the material, whatever the technology, the compilation of any statistical data on a
worldwide basis, is extremely difficult. Experience shows that where consumption tonnage figures
do exist, they rarely compare like-for-like even in respect of country or geographical region, and
may for example, also have been overworked in differing ways from the same incorrect initial data.
In other words, a ‘minefield’ for the researcher and compiler.

Nevertheless, private interview, correspondence and the use of, for example, per capita
consumptions related to known circumstances, country population and measures of industrial
activity, can allow selected journal, trade association and other similar published figures to be
analysed sensibly to provide ‘best estimate’ tonnages. The methodology employed here has been
proved in use over some fifteen years in the compilation of earlier studies for the composites
industry. Some of the statistics listed here rely heavily on data compiled by Trevor Starr for
Composites: A Profile of the World Reinforced Plastics Industry published by Elsevier Advanced
Technology in 1999 [1] and reproduced with permission. Unless otherwise noted, all tonnages are
in metric kilotonnes.

Generalised price data is included where essential, but definitive price structure data is impossible
to obtain. There are a number of reasons, the predominant one being the wide range of very
different materials in use, even within the subheadings of adhesives, coatings, matrices and
sealants. At the same time, as the study went to press, considerable price fluctuations were
becoming apparent as a result of a potential Middle East crisis and its relationship to the price of
crude oil, the thermoset feedstock, and the associated stockpiling of raw materials in the context of
changing world trade economic and political patterns.

A first essential is to delineate carefully, by country, the six geographical regions employed in this
study. A more detailed breakdown was considered unrealistic in the context of the raw data
available. Dependencies and offshore islands are included with the respective country of
sovereignty.

Western Europe All EU Countries plus Norway, Switzerland, Greenland, Iceland and the
Faeroe Islands.
Eastern Europe All former European Soviet Union or Bloc and other neighbouring
countries, plus all countries of the Middle East.
Asia-Pacific Russian Federation, India and neighbouring countries, Japan, North and
South Korea, Singapore, China (including Hong Kong), Taiwan,
Australia and New Zealand.
North America Canada, Mexico and USA.
Latin America Cuba, the Caribbean and West Indies, and South America.
Rest of World Countries not otherwise defined above.

Some product grouping has also been considered necessary.

6.1 Composites Matrices

This study considers the situation, in respect of the thermosets employed for composites, in
comprehensive detail. Current tonnage and forecast consumption data through to 2007, are
included with other relevant data for each world region or country.

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6.1.1 North America

6.1.1.1 Market Size

The Society of the Plastics Industry (SPI) with offices in New York, has published annual finished
product (i.e., thermoset- and thermoplastic-based) shipment figures for the American composites
industry from 1995 to 1998 (Table 6.1). These statistics enabled assessments of the respective
thermoset resin consumptions to be calculated (Table 6.2).

Table 6.1 Shipments of finished composite components, thermoset and thermoplastic,


USA, 1995-1998 (ktonnes)
Market breakdown 1995 1996 1997 1998
Aircraft/aerospace/defence 10.8 10.8 10.9 10.3
Appliance/business equipment 75.6 80.3 84.0 89.7
Construction 285.7 297.4 317.6 340.2
Consumer and recreational 83.5 88.2 95.3 102.2
Corrosion resistant equipment 179.0 173.0 179.8 192.3
Electrical/electronic 142.9 144.7 158.1 163.4
Marine 168.9 167.0 160.2 165.1
Transportation 445.7 448.7 497.1 516.6
Unclassified 48.4 48.7 50.3 53.1
Totals finished products 1440.5 1458.8 1553.3 1632.9
% Annual growth +1.3 +6.5 +5.1
Source: Data from SPI

Table 6.2 Thermoset resin consumption, USA 1995-1998 (ktonnes)


1995 1996 1997 1998
Finished products Thermoset based 1203 1217 1297 1364
Thermoplastic based 238 241 256 269
Indicated thermoset resin consumption 752 760 811 853
% Annual growth, thermoset resin consumption +1.1 +6.7 +5.2

Since then, as part of its major, developing role as the trade body for the whole region, that
statistical responsibility has been taken over by the Composites Fabricators Association (CFA).
Although publishing an annual industry assessment not unlike that provided by SPI, the CFA also
publish on its web site (www.cfa-hq.org) each quarter, a comprehensive analysis of unsaturated
polyester resin consumption for America. In beginning to answer the worldwide need for much
more comprehensive composites industry statistics, this is a major development.

A typical example of the data available for the quarter ending September 30, 2001, is given in
Table 6.3 for unsaturated polyester resin. These are solely unsaturated polyester resin tonnages,
employing data provided by nine of the major USA suppliers:
• AOC Corporation
• Ashland Specialty Chemical Co.
• Cook Composites & Polymers
• Dow Chemical
• Interplastic Corporation
• Eastman Chemical
• Millenium Polymers
• Pioneer Plastics
• Reichhold Inc.

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Table 6.3 Unsaturated polyester resin consumption, quarter ending 30.9.01


Reinforced and unreinforced, USA (ktonnes)
Sales and captive use
Total polyester (unsaturated) resin
Third quarter Year-to-date
consumption
% %
2001 2001
change change
TOTAL DOMESTIC 182.19 -8.2 555.51 -11.8
For reinforced plastics, total 127.25 -11.2 392.16 -14.4
For unreinforced plastics, total 54.94 -0.4 163.34 -4.8
DOMESTIC REINFORCED PLASTICS
Marine and marine accessories, total 25.69 -26.2 87.02 -24.3
Transportation, total 16.75 -25.3 55.53 -20.4
Construction, total 66.70 -3.9 197.38 -10.3
Electrical/electronic, total 6.28 +12.0 20.13 +5.1
Consumer goods, total 9.97 +2.6 27.15 -9.1
Other reinforced, total 1.86 +36.9 4.95 +7.0
DOMESTIC UNREINFORCED
Transportation/body putty, total 5.54 N/A 16.28 N/A
Construction, total 32.34 -2.1 95.82 -5.6
Consumer goods, total 4.87 -10.2 14.00 -15.2
Gelcoats/surface resins/coatings 10.85 -2.4 32.46 -6.4
Other unreinforced 1.34 N/A 4.78 N/A
Source: Data from CFA

In order to offer forecast consumptions through to 2007, it is necessary first to reconcile the SPI
and CFA figures for the years 1996-2001, a difficulty compounded by the fact that three of the
market classifications formerly employed by the SPI, (Table 6.1) (Aircraft/Aerospace/Defence,
Appliance & Business Equipment, and Corrosion Resistant Equipment) are omitted from these,
relatively new, CFA figures. Whilst all three can and do employ unsaturated polyesters, more
sophisticated thermosets and thermoplastic matrices are somewhat more common in these sectors.
However, before making allowances for this situation and then employing either known or forecast
growth/decline patterns to construct Table 6.4, it was necessary to proportion the CFA three-
quarter unsaturated polyester resin consumption for 2001 (555,510 tonnes from Table 6.3) to an
annual tonnage for that year, 740,700 tonnes. That is equivalent to 522,900 tonnes employed for
reinforced products, and 217,800 tonnes for unreinforced products.

Table 6.4 Total thermoset and unsaturated polyester resin consumption USA,
1996-2001 (ktonnes)
1996 1997 1998 1999 2000 2001
Thermoset resin consumption, total 760 811 853 921 896 873
Unsaturated polyester portion 741
Annual % change (on total) +6.7 +5.2 +8.0 -2.8 -2.6

Recent fluctuations in composite industry output have, particularly in the United States, been much
more cyclic than in earlier years (1980-1986). Even though much lower finished product figures
have been noted for 2000 and 2001, Table 6.4 provides a good foundation on which to forecast the
required thermoset tonnage consumptions through to 2007, as indicated in Table 6.5. This North
American summary not only includes allowances for Canada and Mexico, to satisfy the
geographical description provided earlier, but also for the thermosets supplied by manufacturers
other than the nine majors listed earlier. Finally it suggests, on conservative annual growth figures

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only, that 2003 will see a return to a steady growth albeit lower than that experienced by that
region’s composites industry during the mid 1980s.

Table 6.5 Current and forecast annual thermoset consumption, North America (ktonnes)
North America 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
USA figures Table
853 921 896 873 873
6.4
USA-other
128 138 134 131 131
suppliers
USA total 981 1059 1030 1004 1004 1014 1029 1044 1060 1081
Allowance for
70 72.5 72.5 70 70 70.7 71.8 72.9 74 75.5
Canada
Allowance for
49.5 51.5 51.5 50 50 50.5 51 51.8 52. 5 53.6
Mexico
Total 1100 1183 1154 1124 1124 1135 1152 1169 1187 1210
% Annual change +7.5 -2.5 -2.6 Nil +0.9 +3.0 +1.5 +1.5 +2.0

Using the Table 6.5 totals, it is now practical to provide the North American consumption tonnage
breakdowns, shown by Table 6.6.

Table 6.6 Current and forecast thermoset resin consumption, composite matrices,
North America (ktonnes)
North America 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Unreinforced
323 349 339 330 330 334 339 344 349 356
unsaturated polyester
Reinforced - unsaturated
587 622 615 592 592 598 606 615 625 637
polyester
Reinforced - other
190 212 200 202 202 203 207 210 213 217
thermosets
Total thermoset
1100 1183 1154 1124 1124 1135 1152 1169 1187 1210
consumption
% Growth +7.5 -2.5 -2.6 Nil +0.9 +3.0 +1.5 +1.5 +2.0

It must be emphasised, that most of the subclassifications listed under Domestic Unreinforced in
Table 6.3 and in later tabulations as, Unreinforced Polyester, are sectors which find application
under other headings elsewhere in this study. Strictly speaking therefore, these annual figures are
not composite matrices.

6.1.1.2 Comment

According to the North American, Automotive Composites Alliance, much of the continued growth
in the use of composites for automotives and trucks is related to the use of SMC for body panels. In
one recent report covering 130 domestic and imported passenger car and truck models, from 28
international manufacturers, over 500 individual mouldings were noted.

However, SMC hot-press, high-pressure moulding is beginning to face increasing competition (not
just in North America) from new injection techniques employing similar compounds, as well as
RIM and SRIM urethane moulding, for some auto and truck applications. Other long-fibre
‘injection-type’ variants and glass mat thermoplastic (GMT) moulding techniques can offer
advantages over the often heavier SMC component, as vehicle weight, for both on and off road
vehicles, gains importance in reducing fuel consumption and therefore emissions.

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6.1.2 Western Europe

6.1.2.1 Market Size

Although there is a Statistical Office of the European Community in Luxembourg, that body of the
European Community does not yet recognise the existence of composite materials, nor the part
these materials are now playing, increasingly and successfully throughout many market sectors.
Approaches for inclusion of the composites sector in their statistics gathering process by, for
example, such organisations as the UK Composites Processing Association, have yet to meet with
success. Until the next classification revision in 2007, the optimum source of trade data for the
Western Europe composites industry will probably continue to be the French journal, Composites
and the German Reinforced Plastics Association and Technical Union (AVK-TV).

Table 6.7 shows current and future thermoset resin consumption for Western Europe.

Table 6.7 Current and forecast thermoset resin consumption, composite matrices,
Western Europe (ktonnes)
Western Europe 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Unreinforced
347 352 358 365 372 379 387 398 408 420
unsaturated polyester
Reinforced -unsaturated
629a 639 648 661b 674 688 706 723 741 763
polyester
Reinforced - other
204 207 210 214 219 223 229 234 240 247
thermoset
Total thermoset
1180 1198 1216 1240 1265 1290 1322 1355 1389 1430
consumption
% Growth +1.5 +1.5 +2.0 +2.0 +2.0 +2.5 +2.5 +2.5 +3.0
Western Europe has been taken to include Greenland, Faeroe Islands, Iceland, Norway and Switzerland.
The five additional countries included here, provide for ‘a’ an over 20% lower value of 487,000 tonnes and
for ‘b’, 546,000 tonnes.

Although continued growth through to 2007 is suggested, the possibility that Western Europe will
face the same type of fall in consumption as seen by America during the late 1990s, cannot be
overlooked. Cyclic trade patterns, both local and worldwide, are the accepted norm and the western
European composites industry has been known previously to follow the American pattern some 2
or 3 years later. It is for that reason that conservative growths only marginally exceeding an
average of 2.0% per annum have been forecast; conservative values should allow for such trade
fluctuation over forthcoming years. However, there is every likelihood that overall the composites
industry will continue to grow strongly. There is certainly no sign that composites are anywhere
near the growth plateau experienced by all traditional materials, as new products continue to be
developed and grow in their mechanical, physical and economic attraction.

6.1.2.2 Comment

The strive for weight reduction on any form of vehicle receives frequent mention throughout this
study. Although the American automotive and truck industry still leads the way, an increasing
number of highly cost-effective body panels using sheet-moulding (or alternatively glass mat
thermoplastic) techniques are appearing on European manufactured vehicles. These are not just for
the more popular, lower-priced end of the market. Taken from many possible examples, Mercedes-
Benz, in equipping its flagship CL500 coupe with a SMC rear deck lid moulding, has confirmed
the advantage of composites in competition to both steel and aluminium. Indeed it was the belief of
AVK-TV that at the end of the 1990s, “the (Western European) industry (was) benefiting above all
from the economic upswing in the automotive industry … a continuation of last year’s positive

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trend. (Together with electrical applications) they are counteracting decreases in the field of
domestic goods and sanitary products”.

Remaining with the SMC, BMC/DMC moulding technique, it is claimed that, in volume terms,
these processes form, at just over 12%, the largest consumer, in Western Europe of the unsaturated
polyesters, estimated in 1998 as more than 60,000 tonnes. Furthermore, the sector is said to be
growing at an average rate of 2.2%. However, in terms of fabrication technique, hand or contact-
moulding continues to be the most practised, suffering only marginally from the imposition of
increasingly severe controls on VOC emissions, a situation assisted by the advent of low styrene
emission thermosets. For example, following pioneering development by Cray Valley and DSM,
currently some 8% of all polyesters sold in Western Europe are DCPD-based, a figure expected to
nearly double by 2003 at the expense of older orthophthalic grades.

According to DSM Composite Resins, the omnipresence of unsaturated polyesters is related to a


well-established, but still growing, ability to provide customer-driven solutions to the industry. Its
E-Star programme will provide resin matching systems and DSM has a pan-European customer
excellence programme. In other words, resin manufacturers are supplying more tailored resin
systems exhibiting improved consistency and based on combinational chemistry, where specific
resin properties are closely matched to specific customer needs.

Other researchers examining just the unsaturated polyester in the EU market, have concluded that
the current and future resin consumption breakdown can be taken as:

• 62% orthophthalic,
• 17% isophthalic,
• 4% terephthalic,
• 8% DCPD based,
• 5% vinyl ester and
• 4% others.

They further differentiate consumption across the EU market as:

• Italy 23%,
• Germany 17%,
• UK 16%,
• France 16%,
• Spain 12%,
• Nordic 7%,
• Benelux 4%,
• Rest of EU 4%.

They suggest an annual growth rate per country of between 2% and 3.5%.

Tailoring, particularly in the context of gel coats and low styrene emission systems, is of supreme
importance to the marine sector, which consumes some 18% (around 7,000 tonnes per annum) of
the total gelcoat market and around 10% of the unsaturated polyester output. Although that market,
which is considered to include all vessels up to as long as 40 metres, showed some decline between
1990 and 1996, recent trends suggests a positive growth of 3% per annum on average.

As a final comment, it is worth recording briefly other views of the Western European composites
market, made by AVK-TV. They are not just relevant to other world regions but also apply in the
wider context of thermoset resin manufacture and supply. It is AVK-TV’s belief that the
internationalisation of the industry will, beyond any other factor during this century, open up access

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to other markets. By this they do not just mean the relocation of production abroad but rather the
growing trend to establish European and/or worldwide partnerships with other countries.

6.1.3 Eastern Europe

6.1.3.1 Market Size

Until relatively recently even outline statistical data from any Eastern European country (as
designated by this study) was virtually impossible to obtain, even though it was known that a
respectably-sized composites industry, and, therefore, a thermoset resin industry, did exist in most
of them.

For example, shortly after the Second World War the production of unsaturated polyesters (and
glass fibre reinforcement) went through a phase of rapid development in the former
Czechoslovakia, for applications such as car body prototypes, motor cycle sidecars, buses, caravans
and certain architectural components. This work was continued in both the Czech Republic and
Slovakia with the former establishing, in 1993, a Centre for Composite Materials and Structures.
The objective of that organisation was to rectify a lack of composite materials engineering and
development and to overcome, in a country with a highly developed steel industry, the persistence
of a metallic approach among all Czech engineers. With applications now extending into several
infrastructure areas as well as aerospace, that effort is beginning to see some positive reward.

Much the same can be written for example, for Romania and several other Eastern European
countries, even though, for a number, there was little composites activity prior to 1990. Political
changes and therefore the rapid growth of privately-owned companies particularly in the former
Iron Curtain countries, have steadily had an advantageous effect on the total pattern of thermoset
resin consumption. The summary in Table 6.8 has been constructed from several sources.

Table 6.8 Current and forecast thermoset resin consumption, composite matrices,
Eastern Europe (ktonnes)
Eastern Europe 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Unreinforced thermoset 148 151 154 157 160 164 168 172 178 183
Reinforced - unsaturated
270 273 279 284 290 298 305 313 322 331
polyester
Reinforced - other
87 89 90 92 94 96 99 101 104 108
thermoset
Total thermoset
505 513 523 533 544 558 572 586 604 622
consumption
% Growth +1.5 +2.0 +2.0 +2.0 +2.5 +2.5 +2.5 +3.0 +3.0

6.1.3.2 Comment

The French composites industry journal, Composites, noted in December 1999 that the success of
composites throughout the Middle East can be largely attributed to the low durability of traditional
materials, steel and concrete, under the local environmental conditions, particularly high humidity.
They claimed that the current finished product production capacity is in excess of 100,000 tonnes,
of which, in the Arab Gulf region, some 70% is composites pipe production. Even Turkey can
claim a capacity of 12,000 tonnes per annum, although local demand does not yet exceed that
overall capacity. In addition, the rapid economic development experienced by the Arabian Gulf
region has, over the past thirty years, been accompanied by, and also very largely responsible for,
an extensive investment in the development of both a modern infrastructure and industrialisation
away from, but still in many respects dependent on, the oil reserves. Composites and, therefore,
thermoset resins, continue to play a major part in that infrastructure investment. Sewerage
networks, building structures and water storage systems, are major users.

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In a further analysis, Composites stated that Gulf-based composites fabricators now rank amongst
international leaders in the development of structural components for architectural applications.
Finally, the more recent establishment of unsaturated polyester, epoxy and other thermoset resin
manufacture by, for example, Reichhold and Scott Bader, with their combined capacity of 25,000
tonnes, (as well as glass fibre reinforcement by Fibertech, Saudi Arabia, capacity 12,000 tonnes per
annum) needs to be recognised as part of the area’s rapid diversification away from oil export
dependency. Largely as a result of the economy resulting from oil reserves, the Gulf region has
seized on and successfully developed an opportunity which others have yet to grasp.

6.1.4 Asia-Pacific

6.1.4.1 Market Size

Prior to 1997 and Asia’s financial crisis which originated in Thailand, the Asia-Pacific area,
particularly Thailand, Malaysia and Singapore, were showing strong composites industry growth,
arguably, although accurate statistics were difficult to obtain, stronger than any other world region.
Perhaps because it comprises largely industrially developing regions or countries, housing some
60% of the world’s population, the overall economy is noted as one of the most active in the world
and a rapid, strong recovery was confidently expected. With rapid growth in the consumption of
composites for infrastructure applications alone, the potential is clearly enormous.

This situation was clearly reflected in a finished product forecast published in October 1999 [1].
Tonnages for 1998-2005, have been recalculated for thermoset resins (Table 6.9).

Table 6.9 Earlier forecast of the growth of thermoset resin consumption,


Asia-Pacific (ktonnes)
1998 1999 2000 2001 2002 2003 2004 2005
608.8 648.1 654.4 686.3 721.9 758.8 810.0 868.8
+6.5% +1.0% +4.9% +5.2% +5.1% +6.7% +7.3%

In fact, in comparison to two thermoset resin consumption figures, 669.4 ktonnes for 1998 and
700.0 ktonnes for 1999, (calculated from two recently published thermoset and thermoplastic based
finished product outputs), the above forecast was somewhat conservative, and there was an annual
growth between 1998 and 1999 of 4.6%. The finished product figure of 1.6 million tonnes from
which the 700,000 tonnes, 1999 figure was calculated, is claimed to be equivalent to around 27%
of the global composites market. This demonstrates the significance of this region in the
composites industry.

The analysis of consumption and growth for 1998 through to 2007 is presented in Table 6.10.

Table 6.10 Current and forecast thermoset resin consumption, composite matrices,
Asia-Pacific (ktonnes)
Asia-Pacific 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Unreinforced thermoset 197 206 211 216 222 227 233 239 245 251
Reinforced - unsaturated
352 373 383 393 397 407 417 427 438 449
polyester
Reinforced - other
120 121 124 127 135 139 142 146 149 153
thermoset
Total thermoset
669 700 718 736 754 773 792 812 832 853
consumption
% Growth +4.6 +2.5 +2.5 +2.5 +2.5 +2.5 +2.5 +2.5 +2.5

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6.1.4.2 Comment

Until 1998, the growth of the Japanese composites industry was strong, with annual consumption
second only to the USA, but recent years have seen an annual decrease measured in double, rather
than single figures. The current lassitude of the whole Japanese economy suggests that, without
some major market/application innovation, their composites industry may take some years to
recover. Thermoset tonnages for the last 10-years, have purposely not been quoted, as several years
ago the Japanese Reinforced Plastics Society made a major change to the product classifications
employed, making consistent and accurate thermoset-thermoplastic division difficult. Two reported
total industry values for 1998, do however show reasonable agreement at 402,200 and 394,700
tonnes.

The mainland Chinese composites industry is said to comprise some 3,000 typically small
companies. However, the majors are beginning to move in, to take advantage, if nothing else, of the
lower wage structure and less stringent VOC emission regulations. One feature of the industry is
the multitude of small thermoset resin manufacturing concerns. For example, a typical situation is a
resin plant on an upper floor, virtually directly feeding the fabrication unit on the ground. Several
authorities have attempted to quantify the industry but in view its small, fragmented nature, there is
every likelihood that any published figure, currently taken at around 350,000 tonnes of finished
thermoset plus thermoplastic based composite product output, will be a conservative figure.
Growth is suggested as strong, probably as high as 12% per annum, particularly to satisfy the
requirements of the infrastructure sector.

India is another country with a small but rapidly growing composites industry, with local raw
material manufacture, both thermoset resins and glass fibre reinforcement, strong and based on
western technology. Indeed in the research for this study, some thirty resin manufacturing
companies covering adhesives, coatings and composite matrices, were quoted, all members of a
manufacturers’ association.

Like Japan, the South Korean composites industry experienced serious decline at the end of the
1990s but, unlike Japan, is now seeing better recovery. In 1995, in a run-up to what had been hoped
to be better years than they were, five major thermoset resin manufacturers produced a total of
some 94,500 tonnes, achieving production figures in excess of 60% capacity.

In addition to being recognised as a major unsaturated polyester resin manufacturer, exporting, for
example, 100,000 tonnes in 1999, Taiwan is also noted for the production of carbon fibre/epoxy
sports equipment. This growing industry is using locally produced pre-impregnated materials, as
well as thermoplastic-based raw materials and finished products, the latter at the expense of the
thermosets. Much of Taiwan’s composites excellence can be related to the fact that eight major
research institutes and fifteen universities are involved in teaching, training and research into
composites and their future markets and applications.

Finally, although the total finished product output of Australia appears low and relatively small by
international standards (47,000 tonnes in 1997), this has to be seen in the context of the small
population of the country. The Australian industry’s trade body, the Composites Institute of
Australia is one of the most progressive of the thirty-five or so similar bodies that support their
local composites, and therefore thermoset resin, industries.

6.1.5 Latin America

6.1.5.1 Market Size

Five major countries, Argentina, Brazil, Chile, Colombia and Venezuela, along with around a
dozen others, comprise the Latin American composites industry which currently accounts for little
more than 5% of the global finished product output. The linked political and economic problems

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account largely for that situation. Even so, the composites market can be considered buoyant and
growing steadily if slowly. Low capital, high labour intensive fabrication techniques predominate
in a largely unsaturated polyester based market.

Comparing recent figures for Brazil [2], with earlier figures [1] on a like-for-like basis, these show
respectable agreement. This enables, in the absence of other data, the following tabulation (Table
6.11) for the whole of Latin America to be presented. However, a lower growth rate than for Asia-
Pacific has been employed in view of more recent economic difficulties experienced by for
example, Argentina.

Table 6.11 Current and forecast thermoset resin consumption, composite matrices,
Latin America (ktonnes)
Latin America 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Unreinforced thermoset 27.5 28.0 28.4 28.8 29.4 30.0 30.6 31.2 31.8 32.3
Reinforced - unsaturated
50.1 50.7 51.5 52.3 53.3 54.4 55.4 56.5 57.5 58.7
polyester
Reinforced - other
16.2 16.5 16.7 17.0 17.3 17.6 18.0 18.3 18.7 19.0
thermoset
Total thermoset
93.8 95.2 96.6 98.1 100 102 104 106 108 110
consumption
% Growth +1.5 +1.5 +1.5 +2.0 +2.0 +2.0 +2.0 +2.0 +2.0

6.1.5.2 Comment

The composites industry of Brazil is in a similar situation to many industrially developing


countries. The composites industry has a bearing on thermoset resin consumption and it is worth
examining briefly. Brazil is the area’s economic engine, with inflation under control and a rising
standard of living. Hence the attraction to foreign investors is growing. The thermoset resin
manufacturers, Cray Valley, Reichhold and Dow, who have already established themselves,
provide an excellent example. These are present among over one hundred locally owned suppliers
encompassing the vast majority of the raw materials mentioned in this study.

In 1999, Brazil’s 1,686 fabricators consumed 74,000 tonnes of unsaturated polyester and vinyl ester
resins, a slight fall from 1998. Most of these companies are situated in the south or south-east of the
country and are basically family owned concerns using labour intensive manufacturing techniques.
However, there is a steady move into resin transfer moulding and two capital intensive techniques,
hot-press moulding and pultrusion, are not unknown. Many of these companies are meeting the
challenge of product quality improvement and new markets and applications are being opened up
as part of a five-year economic and social stabilisation programme recently introduced by the
Brazilian government. Housing, transportation and sanitation are seen as offering major
opportunities to the whole industry with the good possibility of a 10% increase in output over the
next three years.

In contrast to that is Colombia where a local wholesaler, L.A. Tejada, estimates that around 30% of
the current polyester resin consumption is not employed for composites but for buttons, adhesives
and polymer concrete.

6.1.6 Rest of the World

Although in comparison perhaps an insignificant tonnage, some quantification for the ‘rest of the
world’ must be included to complete the composites matrix picture (Table 6.12).

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Table 6.12 Current and Forecast Thermoset Resin Consumption, Composite Matrices, Rest of
World (ktonnes)
Rest of World 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Unreinforced thermoset 24.9 25.4 25.8 26.2 26.7 27.2 27.8 28.3 28.9 29.5
Reinforced -
45.4 46 46.7 47.3 48.3 49.3 49.7 50.3 51.7 52.7
unsaturated polyester
Reinforced - other
14.7 14.9 15.1 15.4 15.7 16.0 16.9 17.3 17.6 18.0
thermoset
Total thermoset
85.0 86.3 87.6 88.9 90.7 92.5 94.4 95.9 98.2 100.2
consumption
% Growth +1.5 +1.5 +1.5 +2.0 +2.0 +2.0 +1.5 +2.3 +2.0

6.1.7 Summary and Analysis

Table 6.13 summarises the respective tonnage consumptions, by country, of non-reinforced


unsaturated polyester, and unsaturated polyester and other thermoset used with reinforcement for
composite manufacture.

Table 6.13 Current and forecast thermoset resin consumption, composite matrices,
worldwide (ktonnes)
WORLD
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
CONSUMPTION
Unsaturated polyester, unreinforced applications
- North America 323 349 339 330 330 334 339 344 349 356
- Western Europe 347 352 358 365 372 379 387 398 408 420
- Eastern Europe 148 151 154 157 160 164 168 172 178 183
- Asia-Pacific 197 206 211 216 222 227 233 239 245 251
- Latin America 27.5 28 28.4 28.8 29.4 30 30.6 31.2 31.8 32.3
- Rest of World 24.9 25.4 25.8 26.2 26.7 27.2 27.8 28.3 28.9 29.5
Subtotal 1067 1111 1116 1123 1140 1161 1185 1213 1241 1272
Unsaturated polyester, reinforced applications
- North America 587 622 615 592 592 598 606 615 625 637
- Western Europe 629 639 648 661 674 688 706 723 741 763
- Eastern Europe 270 273 279 284 290 298 305 313 322 331
- Asia-Pacific 352 373 383 393 397 407 417 427 438 449
- Latin America 50.1 50.7 51.5 52.3 53.3 54.4 55.4 56.5 57.5 58.7
- Rest of World 45.4 46 46.7 47.3 48.3 49.3 49.7 50.3 51.7 52.7
Subtotal 1934 2004 2023 2030 2055 2095 2139 2185 2235 2291
Other thermosets, reinforced applications
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
- North America 190 212 200 202 202 203 207 210 213 217
- Western Europe 204 207 210 214 219 223 229 234 240 247
- Eastern Europe 87 89 90 92 94 96 99 101 104 108
- Asia-Pacific 120 121 124 127 135 139 142 146 149 153
- Latin America 16.2 16.5 16.7 17.0 17.3 17.6 18.0 18.3 18.7 19.0
- Rest of World 14.7 14.9 15.1 15.4 15.7 16.0 16.9 17.3 17.6 18.0
Subtotal 632 660 656 667 683 695 712 727 742 762
Grand total reinforced
2566 2664 2679 2697 2738 2790 2851 2912 2977 3053
applications
% Growth reinforced
+3.8 +0.6 +0.6 +1.5 +1.9 +2.2 +2.1 +2.2 +2.6
applications

While there is no need to consider the unsaturated polyester resin consumption any further, that
does not apply to the ‘other thermosets’, as those totals clearly encompass every other thermoset

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Thermoset Resins Market Report

resin mentioned in this study, i.e., acrylic, alkyd, bismaleimide, epoxy, furane, hybrids, aminos,
phenolic, urethane and vinyl ester resins. Little published data is available to provide individual
tonnages per year per country but a breakdown is offered in Table 6.14. It must of course be further
admitted that these percentages are likely to change significantly with time, even by 2007.

Table 6.14 Indicative analysis of current and forecast, other thermoset resin consumptions
for composite matrices, worldwide (derived from Table 6.12) (ktonnes)
Resin 1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
Acrylic + Alkyd 53.7 56.1 55.8 56.7 58.1 59.1 60.5 61.8 63.1 64.8
Bismaleimide+Epoxy 300 314 312 317 324 330 338 345 352 362
Phenolic 47.4 49.5 49.2 50.0 51.2 52.1 53.4 54.5 55.7 57.2
Polyurethane 94.8 99 98.4 100 102 104 107 109 111 114
Vinyl esters 72.7 75.9 75.4 76.7 78.5 79.9 81.9 83.6 85.3 87.6
Others 63.4 65.5 65.2 66.6 69.2 69.9 71.2 73.1 74.9 76.4
TOTALS 632 660 656 667 683 695 712 727 742 762

6.2 Unreinforced Unsaturated Polyester Resin: Applications

As demonstrated by the latter part of Table 6.3, unsaturated polyester resins are employed for a
wide variety of unreinforced applications ranging through coatings, flow coats, gelcoats and
pigment pastes, consumer goods (e.g., encapsulated items), construction items (e.g., polymer
concrete and flooring materials), putties and pastes to markets such as button manufacture.

Other than in the CFA outline of Table 6.3, none of these markets or applications are quantified in
any authoritative, published manner. Table 6.13 includes global data on overall consumption.
However, in a study of this nature some further analysis is essential. This includes analysis by
country and then by application.

6.2.1 North America

Table 6.15 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, North America (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 29.4 31.8 30.8 30.0 30.0 30.4 30.8 31.3 31.8 32.4
Construction 191 206 200 195 195 197 200 203 206 210
Gelcoats, flowcoats, etc. 64.0 69.1 67.1 65.3 65.3 66.1 67.1 68.1 69.1 70.5
Putties and pastes 32.9 35.6 34.6 33.7 33.7 34.1 34.6 35.1 35.6 36.3
Others 5.7 6.5 6.5 6.0 6.0 6.4 6.5 6.5 6.5 6.8
Totals 323 349 339 330 330 334 339 344 349 356

Table 6.15 shows current and forecast unsaturated polyester resin consumption in unreinforced
applications in North America. Typically growth over the 7 year period amounts to 10%.

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Thermoset Resins Market Report

6.2.2 Western Europe

Table 6.16 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, Western Europe (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 31.6 32.0 32.6 33.2 33.9 34.5 35.2 36.2 37.1 38.2
Construction 205 208 211 215 219 224 228 235 241 248
Gelcoats, flowcoats, etc. 68.7 69.7 70.9 72.3 73.7 75.0 76.6 78.8 80.8 83.2
Putties and pastes 35.4 35.9 36.5 37.2 37.9 38.7 39.5 40.6 41.6 42.8
Others 6.3 6.4 7.0 7.3 7.5 6.8 7.7 7.4 7.5 7.8
Totals 347 352 358 365 372 379 387 398 408 420

Table 6.16 shows current and forecast unsaturated polyester resin consumption in unreinforced
applications in Western Europe. Typical growth over the 7 year period: 21%.

6.2.3 Eastern Europe

Table 6.17 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, Eastern Europe (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 13.5 13.7 14.0 14.3 14.6 14.9 15.3 15.7 16.2 16.7
Construction 87.3 89.1 90.9 92.6 94.4 96.8 99.1 101 105 108
Gelcoats, flowcoats, etc. 29.3 29.9 30.5 31.1 31.7 32.5 33.3 34.1 35.2 36.2
Putties and pastes 15.1 15.4 15.7 16.0 16.3 16.7 17.1 17.5 18.2 18.7
Others 2.8 2.9 2.9 3.0 3.0 3.1 3.2 3.7 3.4 3.4
Totals 148 151 154 157 160 164 168 172 178 183

Table 6.17 shows current and forecast unsaturated polyester resin consumption in unreinforced
applications in Eastern Europe. Typical growth over the 7 year period: 23%.

6.2.4 Asia-Pacific

Table 6.18 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, Asia-Pacific (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 17.9 18.7 19.2 19.7 20.2 20.7 21.2 21.7 22.3 22.8
Construction 116 122 124 127 131 134 137 141 145 148
Gelcoats, flowcoats, etc. 39.0 40.8 41.8 42.8 44.0 45.0 46.1 47.3 48.5 49.0
Putties and pastes 20.1 21.0 21.5 22.0 22.6 23.2 23.8 24.4 25.0 25.6
Others 4.0 3.5 4.5 4.5 4.2 4.1 4.9 4.6 4.2 5.6
Totals 197 206 211 216 222 227 233 239 245 251

Table 6.18 shows current and forecast unsaturated polyester resin consumption in unreinforced
applications in Asia-Pacific. Typical growth over the 7 year period: 27%.

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6.2.5 Latin America

Table 6.19 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, Latin America (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 2.5 2.5 2.6 2.6 2.7 2.7 2.8 2.8 2.9 2.9
Construction 16.2 16.5 17.0 17.0 17.3 17.7 18.1 18.4 18.8 19.1
Gelcoats, flowcoats, etc. 5.4 5.5 5.6 5.7 5.8 5.9 6.1 6.2 6.3 6.4
Putties and pastes 2.8 2.9 2.9 2.9 3.0 3.1 3.1 3.2 3.2 3.3
Others 0.6 0.6 0.3 0.6 0.6 0.6 0.5 0.6 0.6 0.6
Totals 27.5 28 28.4 28.8 29.4 30 30.6 31.2 31.8 32.3

Table 6.19 shows current and forecast unsaturated polyester resin consumption in unreinforced
applications in Latin America. Typical growth over the 7 year period: 18%.

6.2.6 Rest of World

Table 6.20 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, rest of world (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 2.3 2.3 2.3 2.4 2.4 2.5 2.5 2.6 2.6 2.7
Construction 14.7 15.0 15.2 15.6 15.8 16.0 16.4 16.9 17.1 17.4
Gelcoats, flowcoats, etc. 4.9 5.0 5.1 5.2 5.3 5.3 5.5 5.6 5.7 5.8
Putties and pastes 2.5 2.6 2.6 2.7 2.7 2.8 2.8 2.9 2.9 3.0
Others 0.5 0.5 0.6 0.3 0.5 0.6 0.6 0.3 0.6 0.6
Totals 24.9 25.4 25.8 26.2 26.7 27.2 27.8 28.3 28.9 29.5

Table 6.20 shows current and forecast unsaturated polyester resin consumption in unreinforced
applications in the rest of the world. Typical growth over the 7 year period: 18%.

6.2.7 Summary

Adding the respective consumptions per market/application per geographical region, provides the
worldwide summary shown in Table 6.21, expressed also as a percentage growth per annum.

Table 6.21 Current and forecast, unsaturated polyester resin consumption, unreinforced
applications, worldwide (ktonnes)
Market/application for
1998 1999 2000 2001 2002 2003 2004 2005 2006 2007
unsaturated polyesters
Consumer goods 97.2 101.0 101.5 102.2 103.8 105.7 107.8 110.3 112.9 115.7
Construction 630.2 656.6 658.1 662.2 672.5 685.5 698.6 715.3 732.9 750.5
Gelcoats, flowcoats, etc. 211.3 220.0 221.0 222.4 225.8 229.8 234.7 240.1 245.6 251.1
Putties and pastes 108.8 113.4 113.8 114.5 116.2 118.6 120.9 123.7 126.5 129.7
Others 19.9 20.4 21.8 21.7 21.8 21.6 23.4 23.1 22.8 24.8
Totals 1067 1111 1116 1123 1140 1161 1185 1213 1241 1272
% Growth/annum +4.1 +0.5 +0.6 +1.5 +1.8 +2.1 +2.4 +2.3 +2.5

It should be obvious from earlier text that other thermoset resins than unsaturated polyester, can be
employed for certain of the applications considered by Tables 6.14-6.20 inclusive. However,
although no specific consumption figures were discovered during the research for this study, it is

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judged that those tonnages are minimal, therefore affecting the conclusions of these tabulations,
only marginally.

6.3 Value: Thermoset Resins for Composites and Associated Applications

Having provided through Tables 6.13, 6.14 and 6.21 in particular, a summary of the current and
future global consumptions of thermoset resin, whether employed reinforced as composite matrices
or unreinforced for certain associated applications, it is now essential to offer overall estimates of
the worldwide value of that resin manufacturing and supply business.

Only the two years 2002 and 2007, have been considered and, furthermore, it has obviously been
necessary to employ only an average resin cost per tonne, In addition, a 2% per annum inflation has
been included, 2002 to 2007.

Table 6.22 Value, worldwide thermoset resin business


2002 2007
Resin type Value Value
Tonnage Tonnage
(US$) (US$)
Unsaturated polyester resin for
1140 2.3 billion 1272 2.8 billion
unreinforced application
Unsaturated polyester resin for
2055 4.1 billion 2291 5.1 billion
reinforced application
Other thermoset resins for reinforced
683 2.7 billion 762 3.4 billion
application
TOTAL 9.1 billion 11.3 billion

6.4 Adhesives

The industrial application of adhesive bonding as opposed to welding, riveting or mechanical


fastening techniques, probably began in 1949 with the use of the Redux range of epoxy resins in
the construction of the British de Havilland Comet airliner. However, remaining with the aircraft
example, many of the first timber-framed types were adhesive bonded with casein glues later
superseded with phenol-formaldehyde based adhesives.

Since then, the advantages of a continuous adhesive bonded assembly, as opposed to localised
rivets and bolts causing high stress generation over often weakened hole-drilled constructions, has
been recognised by most industries irrespective of market or application. Which came first, the
development of new, higher performance, more suitable adhesives, or the need for and, therefore,
the development and commercialisation of those new adhesives could be strongly debated. There is
no doubt, however, as to the part and the importance, thermoset resin systems have played in
answering that need. However, it is equally important to recognise that many adhesives, based on
rubber or other natural gums, may also employ small quantities of thermoset resins as modifiers or
additives in their formulation.

To attempt to put a figure on the use of phenolic resins in adhesives, many based on rubbers such
as polychloroprene or nitrile, one can find data that state that in the USA and Germany between 2.5
and 7% of phenolic resins manufactured are used in adhesives and paints [3]. Allowing for the rest
of the world and making some assumptions one could assume that about 3% of phenolic resins end
up in adhesives. The phenolic resin tonnage produced today is about 4 million tonnes worldwide
and hence some 120,000 tonnes of phenolic resins alone are used in this application.

Whilst research has revealed some data applicable to the consumption of adhesives, little of that
information can be related to either a particular adhesive, or therefore, a particular thermoset resin

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or, indeed, a particular country or geographical region. Hence whilst certainly inclusive of at least
some of the relevant thermoset resins, much that follows can only be considered of a general
nature. Accurate, authoritative and definitive tabulations simply cannot be offered. For example,
one report records that prior to the turn of the century, the European adhesives market, particularly
those supplied to the household and D.I.Y market was unstable, although promising growth was
foreseen in certain countries, such as Italy. The value of this European market sector was put at
US$840 million.

Adhesives with polyurethane (isocyanates and polyols) in their formulation, provide another
example of the difficulty of defining size, simply because polyurethane is such a universal material.
Total polyurethane production was said to be 7.5 million tonnes in 1998, (growing at 5% to 6% per
annum) but it was impossible to obtain figures for the use of this type of chemistry in adhesives
alone. In general urethane terms the market is approximately equally divided between North
America, Europe and Asia but the vast proportion of urethane chemicals are used to make foams.

Whilst the use of thermoset resins in adhesive formulations is on the increase, solvent-borne
systems are steadily losing market share in favour of those demonstrating lower VOC levels,
whatever means is employed to achieve that reduction. Ten years from now, and some would claim
five years, volatile solvent-based adhesives may no longer be sold or available, whether for
industrial or domestic consumption. It is a situation currently driving the R & D engine and,
although demand is healthy, a change that is squeezing profit margins as hard as rising raw
material, oil prices and operating costs.

The growing use of thermoset resins for a wide-range of construction application has already been
highlighted, but their use in adhesive formulations is becoming increasingly important to that
market sector. For example it is claimed that construction is the second-largest industry segment
for non-pressure sensitive adhesives, representing some 17-20% of the total US volume and
moreover, growing at over 3% per annum [4]. Flooring and dry-wall type products account for a
large percentage of this consumption, with low-solvent, waterborne and polyurethane adhesives
being those most highly favoured particularly for thin flooring materials. Like the major use of
adhesives in the manufacture of plywood, this is also a market sector where there remains a steady
use and consumption of melamine, urea and phenolic resins.

It is predicted that the demand for construction adhesives as employed in both initial build and
repair and refurbishment, will grow at some 2.5% per annum, to an annual total of some 2.6 million
tonnes in 2003 [5]. If this figure is taken as 17% of the total sales of adhesives worldwide, it places
the world figure at 15.75 million tonnes in 2003, equivalent to some 17.5 million tonnes by 2007.
Even allowing for the large numbers of adhesives in which thermosets are a small proportion of the
formulation, it is, therefore, a massive market for the several thermoset systems on which those
adhesives are based.

Other workers such as IAL Consultants [6] suggest that high technology applications are driving
the Western Europe structural adhesives market, totalling in 1999 some 38,000 tonnes and growing
over the five years to 2004 at 2.2% per annum, to reach 42,000 tonnes. However, they noted wide
differences in the growth rate for specific product types and applications. Taking epoxy film and
epoxy paste structural adhesives (as used for plate-to-plate bonding and honeycomb sandwich
panel construction in the aerospace industry) as an example, growth to 2004 could be expected to
average 6.6% per annum compared to only 0.4% for phenolic-based structural adhesives in the
automotive industry. As far as the latter is concerned, epoxy paste and polyurethane structural
adhesives are favoured and even though both offer promising potential in this sector, growth until
halfway through the current decade may not amount to much over 1% per annum. Taken overall,
the polyurethanes account for nearly 65% of the total structural adhesives market in Western
Europe with the epoxies (both film and paste) at 30%. Further, whilst their current usage remains
low, polyimide-based adhesives can be expected to grow at perhaps 5% per annum over the next
few years.

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Irrespective of the sale of Shell Chemical and Ciba Specialty Chemicals, both of whose businesses
remain active, Dow Chemical continues to be referred to as the world’s top epoxy resin producer.
Reporting in late 2000 that the epoxy adhesives sector is expected to slow from a current annual
growth of 5.7% to 3.3% by 2004, they noted that general epoxy demand was continuing to growth
at between 4% and 5% and as a consequence there were plans to increase capacity. In respect of
Europe, Dow noted that the hot-melt adhesives market was expected to grow at 3.7% per annum
from its 1999 value of $US794.6 million to $US997 million by 2006.

In July 2000, the American journal, “Adhesives Age” [7] reviewed the US adhesives and sealants
industry. Although they are difficult to separate statistically, the total sales in 1999 was some
$US9.2 billion at an annual growth of 3%. Employing that value with the earlier conclusion
suggests a 2003 worldwide market value of $US54 billion, or $US60 billion by 2007, although
clearly only an uncalculatable percentage relates to thermoset resin base. Perhaps surprisingly,
packaging at 42%, remains the largest adhesive end-user.

In another study [8], the US-based Freedonia Group estimated that the local demand for
polyurethane-based adhesives, sealants and caulks, would reach 292,500 tonnes during 2002, a
growth equal to 3.5% per annum and comparing well with a value of 3.4% for all other types. They
further estimated a US market size of fractionally over 1 million tonnes valued at $US3.3 billion.

The automotive industry is increasingly employing adhesives for both original equipment and
repair applications. For example, a Western European market survey, undertaken by IAL
Consultants [4], found that in Germany structural adhesives accounted for some 25% of the total
adhesive demand, typical end-uses being for automotive followed by marine, consumer goods and
sandwich panel markets. In terms of adhesive types, those formulated on polyurethane chemistry
accounted for over 62% of the whole market.

Although welding used to be and remains, a common automotive industry bonding procedure,
today’s fuel economy standards demand a more inventive approach [9]. This in turn demands,
lighter, stronger structures offering better handling and crashworthiness, hence the steadily growing
use of adhesives, said for the US automotive industry to be growing at 1.3% per annum and
expected to reach a consumption level of over 800,000 tonnes by 2003. In part it is a demand which
results principally from the increased use of polymer-based mouldings by that industry, whether for
internal, external or under-the-bonnet application. While specially formulated and fast-cure
polyurethane-based systems find major utilisation to answer many of the adhesive demands of this
industry sector, in securing structural and decorative items and window glass; epoxy, acrylic,
cyanocrylate and PSA tapes are also common. Equally, many find application later, during vehicle
repair.

In a recent study [10], the American consultants Frost & Sullivan classified four adhesive types:
solvent-based adhesives such as starch, dextrins, casein and polyvinyl alcohol; waterborne systems
such as ethylene-vinyl acetates, acrylics and urethanes; hot-melt adhesives such as polyolefins,
EVAs, acrylics, urethanes and block copolymers with a final fourth ‘miscellaneous’ group
consisting of epoxies, radiation curing systems and cyanoacrylates. Like others, they concluded
that environmental regulations are contributing to the typically 4.5% annual growth, to a total 59%
industry demand, of waterborne varieties.

Finally, the use of UV photocuring techniques in adhesives and sealants is becomes steadily more
important and has been estimated for 1999 to involve between 300 and 500 tonnes of adhesive.

6.5 Encapsulation

Similar, but lesser, statistical difficulties apply for encapsulation as for adhesives. Although
encapsulation, coating and sealing are virtually impossible to separate, at least there is better and
clearer differentiation between the thermosets which are applicable. While the unsaturated

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Thermoset Resins Market Report

polyesters can offer good encapsulation properties, suitably dealt with under non-reinforced
applications, it is the epoxies which are of principle interest.

As demand and therefore production capacity increase, with commensurate reductions in raw
material cost, the superior epoxies find increasing utilisation. Even in Japan, where severe
economic restraints continue, the demand for epoxy resins for encapsulation, as composite matrices
or for coating is a growing markets and is now estimated at over 160,000 tonnes per annum.

6.6 Coatings, Flooring and Allied

As has already been reported, virtually every thermoset resin finds application in some form of
paint, flooring or other surface treatment or coating application. At the same time an accurate
indication of the respective annual thermoset resin consumption for each of these diverse
applications, is simply not available. However, out of a mass of data reviewed in the compilation of
this study, certain conclusions and, in some cases tonnage data, can clearly be drawn.

Table 6.23 Value ($US Billion) of the global coatings


market, 1999 and 2003
Region 1999 2003
Africa 3.5 4.3
Asia 14.8 17.8
Europe - Eastern 3.9 5.1
Europe - Western 19.5 22.0
North America 18.6 18.1
South America 3.9 4.6
Rest of World 3.0 3.8
Total 67.2 75.7

The principal change within the coating industry over the last few years, has been in connection
with the rising use (8% per annum, but now beginning to slow) of the powder coating process,
which is expected to total around 200,000 tonnes, valued at $US1.3 billion, by 2003 in the US. The
world market is estimated at well over double that value. Although epoxies remain the leading
coating material for automotive, appliance and furniture application, their high cost has been a
limitation to even better growth. Less expensive epoxy-polyester hybrids are now becoming
available in addition to the TGIC polyester and polyurethanes employed for heavy duty exterior
type applications. Some thermoplastics can equally be employed but the thermosets dominate at
over 90%. High solids system polyurethanes have been developed for polyurethane coatings as a
move to lower VOC emissions and this type of trend will continue.

In 1997, the Japan Paint Manufacturers Association published an assessment of paint production in
Japan and considering solely those that were expected to be formulated in part with thermoset
resins, their data was ‘Ship Bottom Paints’ 18,886 tonnes; ‘Road Marking Paints’ 100,000 tonnes
and ‘Powder Coatings’ 24,710 tonnes.

In another summary by the China Coating Industry Association for 1998, a total consumption of
1.68 million tonnes was quoted of which 464,700 tonnes was employed for architectural purposes.
In respect of polyurethane based coatings, whilst the 1991 output was only just over 17,000 tonnes
that figure had, by 1997, exceeded 110,000 tonnes. This represented an 8% share of the entire
coatings market, just behind those based on alkyd resins and those based on phenolic resins. Indeed
the average growth rate of polyurethane coatings is some four times greater than the average
growth of the whole China coatings industry. As far as the Chinese industry is concerned, five
distinct categories exist: wood furniture paints, flooring paints, automotive paints, anti-corrosive
paints and specialty paints. The first two account for more than 80% of the total and although

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Thermoset Resins Market Report

waterborne systems do exist, most are aromatic solvent systems with the isocyanate more
commonly TDI.

Late in 1999, the American journal, Chemical Marketing Reporter [11] published several articles
appertaining to the US coatings market. They reported the value of the current and future global
coatings market to be as shown in Table 6.23.

6.7 Polyurethanes

Clausius [12] quoted the 1998 demand for polyurethane systems as 7.5 million tonnes, up from 6.9
million in 1996. He predicts a growth rate of 5% per annum to 2003, a slight reduction on previous
years blamed mainly on the economic problems of the Far East. However, the three principal
geographic market areas, Europe, NAFTA and Asia each consume about 30% of the total.
Promising areas for future growth include South America (principally Brazil and Argentina) and
the Far East despite its current problems.

Volumes are not evenly spread among the countries making up the regions. In the NAFTA area the
USA accounts for 90% of the volume, whilst in Europe Germany and Italy each consume about
20% of that areas tonnage. Equally, growth rates are not expected to be uniform. In the Far East,
the growth rate in China is expected to be around 10% for the next few years compared to ca, 2-3%
for Japan.

The vast majority of the urethanes market is for foams, either flexible (automotive seating,
transport seating, furniture, etc.) or rigid for thermal insulation in buildings and industrial
equipment.

MDI based systems appear to be growing at the expense of TDI but this may be because it is a
relatively young product.

6.8 Other Thermosets – North America

Even though a slowdown in building construction is expected, the estimated demand for phenolic
resins throughout North America should increase at around 2.2% per annum, to reach over 2.1
million tonnes in 2004. In terms of epoxy resin the North American market was expected to reach a
total of $US1.5 billion by the close of 2000, with the strongest gains coming from waterborne,
powder, electrodeposition and radiation curable varieties.

6.9 Overall Summary, Analysis and Conclusions

In this section an attempt is made to summarise the world consumption of thermoset resins from a
number of sources. It indicates that figures quoted as authoritative are perhaps not as good as they
appear although agreement in these is probably acceptable. The one case where the tonnages
determined from different sources are very different is for urea-formaldehyde resins and comment
is made on this figure later.

In a review by the Freedonia Group, the 2004 worldwide demand for thermoset resins is given as
24 million tonnes, equivalent to growth in excess of 4% per annum. Their breakdown of demand is
shown by Table 6.24. Earlier, they had reported that the slow down in growth during the 1990s,
could be attributed principally to the need to reformulate the thermosets specifically employed for
coatings and adhesives, in accordance with VOC/environmental regulations. Since then there had
been an above average growth in the consumption of polyurethanes, epoxies and silicones, with
many thermosets being employed for household durables, transportation or in the construction
market. The respective percentage breakdown per resin type is shown to the right of each annual
total.

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Table 6.24 Worldwide thermoset resin demand (ktonnes)


% Annual
1989 1999 2004
Growth
Consum- Market Consum- Market Consum- Market
89/99 99/04
ption share ption share ption share
Alkyds 1422 9.5% 1545 7.9% 1905 7.9% 0.8 4.3
Aminos 2655 17.7% 3484 17.8% 4215 17.6% 2.8 3.9
Phenolics 2849 19.0% 3607 18.4% 4270 17.8% 2.4 3.4
Polyurethanes 4580 30.4% 6123 31.3% 7600 31.7% 2.9 4.4
Unsaturated 1963 13.1% 2438 12.4% 3025 12.6% 2.2 4.4
Polyesters
Unclassified 1550 10.3% 2389 12.2% 2980 12.4% 4.4 4.5
Total Demand 15019 19586 23995 2.7 4.1

There is seemingly, a surprising omission, epoxy resins, from this tabulation. It is considered that
this important class of thermosets would by the date of the research (1999) have presented a
sufficient consumption to have been shown separately rather than, apparently, included under
Unclassified.

Turning now to a second source of information, in their book, Gardziella, Pilato and Knop [3]
quote figures for the production of the major thermosetting resins in terms of percentage of the
thermosetting total. However, there is no mention in this data of alkyd resins which in Table 6.24
forms 7.9% of the 1999 production. They do not include polyurethanes either since, as explained
elsewhere, there is no such thing as a 'polyurethane resin', the end user buying the isocyanate and
the polyol from which to make the resin and crosslink it in one operation. They do however quote
the fact that thermosets, including urethanes and silicones, make up 18-20% of the world total
plastics production of 100-120 million tonnes. This gives a figure for thermosets of ca. 22 million
tonnes. Urethanes are responsible for about 7.5 million tonnes per annum [12]. The distribution of
thermoset production, including the epoxies omitted from the previous source but omitting the
alkyds, deduced from the reference information, is given in Table 6.25.

Table 6.25 Calculated world tonnages of various thermosetting resins


Tonnage
Resin Market share (%)
(ktonnes)
Polyurethanes 34 7,500
Urea-formaldehyde 32.3 7,105
Phenol-formaldehyde 14.5 3,190
Unsaturated polyesters 9.2 2,030
Epoxies 5.3 1,160
Melamine-formaldehyde 4 870
Furanes 0.7 145
Total 100 22,000

Before moving on, there must be some comparison and rationalisation of this data. The unsaturated
polyester figure for world consumption in 1999 in Tables 6.13, 6.24 and 6.25 are 3.115, 2.438 and
2.030 million tonnes respectively. The correct figure is unknown but since the last two were
calculated from very different sources, and are closer one to the other, a reasonable figure is
probably closer to 2.5 million tonnes. Furthermore, the figures in Table 6.13 came from deductions
from the composites industry data rather than from general overviews of the thermosets industry
which, it is hoped, are more accurate.

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The amino figures (a summation of urea and melamine-formaldehyde resins) are very different.
However there is a possible explanation for this. Very large quantities of urea-formaldehyde resin
are made in-house by the timber products industry. If the first survey either did not 'see' this
material or deliberately ignored it as not being part of 'the market', the disparity is explained. In a
similar manner, the alkyd resins, used almost exclusively in the paint and surface coatings industry,
may have been excluded from the second reference.

Using all the above calculated and tabulated data, it is necessary to provide a best possible estimate
of the total current (2002) and forecast (2007) tonnages and values of the worldwide thermoset
resin industry, as was provided in Table 6.22 for those used in composite materials. Firstly a
decision on the figures for tonnages most likely to be accurate for the latest year for which data was
commonly available has to be made (1999). Using the projected growth rates in Table 6.24 where
relevant, the tonnages for the present day and 2007 may be estimated as in Table 6.26.

Table 6.26 Estimated worldwide thermoset resin consumption, 2002 and 2007 (ktonnes)
World Thermoset Resin Consumption 2002 2007
Alkyd 1750 1950
Amino 8900 9800
Phenolic 3500 3850
Polyurethane 8500 10600
Unsaturated Polyester 3200 3600
Epoxy 1250 1400
Total Demand 27100 31200

Pricing and, therefore, placing a value on the market for thermosetting resins is not a practicable
thing to attempt if authoritative data is to result. There is a wide range of values for these resins,
symptomatic of two major factors. The first is that the resins described variously as 'phenolic' or
'unsaturated polyester' vary enormously in their chemical complexity, hence manufacturing costs
and market price. The second is that many of these resins are commodities and the price is open to
negotiation to each and every customer depending on tonnage purchased, supplier-customer
relationships, other products which may be purchased from the same supplier, etc.

Gardzielle and co-workers [3] puts the resins in the price ratio shown in Table 6.27 from which can
be calculated a range of values, in this case for 1999, as indicated.

Table 6.27 Calculated relative market values of some thermosetting resins


Resin Price ratio Relative value of market
Phenol-formaldehyde 1.0 3190
Urea-formaldehyde 0.6-0.7 4263-4973
Melamine-formaldehyde 1.5-1.8 1305-1566
Unsaturated polyester 1.5-2.4 3045-4466
Epoxy 2.2-2.6 2436-2668

Alkyds are not included in this table since relative price data for these materials was not available
from the same source and hence not comparable. Polyurethane chemicals are not 'a resin system', as
stated before, and the mix ratio for the polyols and isocyanates will vary from factory to factory
and application to application. Polyisocyanurates for example, increasingly used in the foam and
other industries, use similar starting chemicals to polyurethanes but in different ratios. Hence no
simple price can be applied.

The unusual ratio system applied, using phenolic as 1.0, not only indicates the variation in the price
range of other resin systems but in phenolic resins themselves. At 2002 market values, for example,

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Thermoset Resins Market Report

phenolic resins sell for prices ranging from as low as US$650 per tonne for a simple phenol-
formaldehyde resin sold in large quantities to as high as US$3,000 for a resorcinol resin, sold in
smaller quantities.

References

1. T. Starr, Composites: A Profile of the Worldwide Reinforced Plastics Industry, Markets and
Suppliers, Third Edition, Elsevier Advanced Technology, 1999.

2. Composites, 2000, No. 39-40, June/August, 11.

3. A. Gardziella, L.A. Pilato and A. Knop, Phenolic Resins, Springer-Verlag, 1999.

4. M. Bowtell, Adhesives Age, 2000, 43, 5, 10

5. G. Valero, Adhesives Age, 2000, 43, 7, 18.

6. J. Schwartz, Adhesives Age, 2000, 43, 2, 21.

7. Adhesives Age, 2000, 43, 7, 15.

8. Urethane Technology, 1999, 15, 6, 48.

9. B. Gascoigne, Machine Design, 2000, 72, 6, 60.

10. Adhesives Age, 2000, 43, 5, 27.

11. Chemical Marketing Reporter, 1999, 256, 15, 15.

12. R. Clausius, Kunststoffe Plast Europe, 1998, 88, 10, 42.

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Thermoset Resins Market Report

7 Major Players and Company Profiles

7.1 Acquisitions and Related Information

Over recent years the thermoset resin industry in general, particularly that sector supplying the
composites industry, has seen considerable consolidation. There has been some quietening down in
further consolidation at the present time. An interest continues, however, in the acquisition, through
joint ventures with local companies and governments, of production facilities in the less well
developed countries of the world. This is seen in two lights. Firstly as a means of reducing
overheads, improving productivity and profitability and, secondly, as being present in advance in
the countries which, because of their relatively backward position in the industrial hierarchy at
present, are, potentially the seats of greatest future growth. The acquisitions, ownership changes
and new plant growth which are identified below are meant to be illustrative rather than a
comprehensive listing and are considerably less in number than they would have been only a few
years ago. Only changes since 1998, and only the more important of those, are considered, with
those that are most recent being described first. Further company acquisition data appears in some
of the Company Profiles reproduced later (Section 7.3).

Following the sale of Ciba Specialty Chemicals’ polymer business to Morgan Grenfel Private
Equity, Vantico Inc., a recently established, privately owned venture was formed to carry on the
company’s well-established, high performance epoxy resin manufacturing interests typified by the
Araldite brand leader. Vantico owns manufacturing, marketing, sales and R&D operations,
worldwide. To further strengthen the Asian customer base spanning aerospace, electronics and
document security, it has recently completed production facilities in both India and China. The
company reported a nearly 10% rise in sales for 2000 over 1999, and continues to work to improve
margins, currently around 10% in comparison to the sector average of 16%. As a result of these
changes the 50:50 epoxy resin joint ventures Asahi Ciba and Nagase Ciba have been sold to Asahi
Chemical and Nagase respectively. Asahi has been concentrating its marketing efforts on an
increase in the consumption of their product range to the electric-electronic sector, such as sealants
for printed circuit boards, whereas Nagase’s concentration has been modified epoxies and the
development of acrylics, PUs, photocuring resins and resin mouldings.

Another major epoxy manufacturer, Shell – probably the world’s largest – was, as a result of a
private venture purchase, forced to change its name on 19 September 2000 from Resins &
Versatics to Resolution Performance Products. Composites based on Resolution’s range of epoxy
resins, modifiers and curing agents, find such applications as aerospace components, chemical-
resistant pipes, off-shore mouldings, sporting goods and the blades for wind energy generation.

Yet another epoxy manufacturer, Dow Chemical has increased its investment in China by adding
40,000 tonnes per annum of converted epoxy resin capacity and is also planning to add further
capacity to its proposed complex at Tianjin. Dow’s aim, similar to Ciba and Shell above, is to
counter the major problem of low margins, currently facing this particular sector of the thermoset
resin supply industry and brought about by a period of increased raw material costs, some over-
capacity and strong producer competition.

The Japanese company, Ajinomoto Fine-Techno, has doubled its production capacity of Amicure
to 200 tonnes per annum. This amine adduct type, one-pot latent hardener/curing accelerator is
employed in the manufacture of ‘temporary attachment’ adhesives used in electrical component
manufacturing processes, as well as in structural adhesives and fibre-reinforced prepregs. Amicure
is stated to exhibit outstanding low temperature curing characteristics and storage stability.

Owing to an increased demand for BMC materials throughout Asia-Pacific generally, Eternal
Showa Highpolymer plans to install a new 200 tonnes per month production line within its existing
100 tonnes per month plant in Bangkok. Eternal Showa is a joint venture between Showa

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Thermoset Resins Market Report

Highpolymer and the Thai unsaturated polyester resin manufacturer, Eternal Resin. It is anticipated
that over 50% of the plant’s output will be exported from Thailand.

Two major players in the Australian composites industry, Huntsman Chemical Corporation and
Synthetic Resins recently merged to form Huntsman Composites. The change is said not to
represent a new ownership, but a step towards streamlining a better business approach and in turn
causing less confusion in the market place, with an enviable range of products. Huntsman is the
world’s largest privately owned chemical company employing around 8,000 people worldwide and
the company has been manufacturing a broad range of polyester and vinyl ester resins in Australia
for 45 years, while Synthetic Resins have been distributing quality products for over 35 years.
Combining forces means bringing experienced local knowledge and global support to better deliver
new products, with quality licensors and supply partners.

In a move to strengthen their flame retardants business, during May 2002, Ciba Specialty
Chemicals announced its purchase of DSM’s, Melapur technology. Recognised as a leading range
of melamine products, and comprising four major grades together with a number of promising
development products, these Melapur flame retardant systems are targeted at the engineering
plastics sector, typically automotive and electronic applications. In the first quarter of 2001, the
sales of Ciba’s plastic additives business were down by 4% to £209m, with profits falling by £8m
to £40m.

In an example of the ‘internationalisation’ spoken of by AVK-TV, the North American resin


manufacturer AOC entered into a vinyl ester toll manufacturing agreement with Thai Epoxy and
Allied Products Co. Ltd. of Bangkok. The aim of the deal is to enhance AOC’s marketing strategies
throughout the whole of the Asia-Pacific region. Taking two examples, this will ease the setting up
of composite business in such countries as Australia, and assist China in its emerging composites
fabrication industry. Equally it is expected to assist their UK operation in enhancing AOC’s ability
to meet the universal material specification requirements of global customers. Thai Epoxy, ISO
9002 and 14001 certified, is one of several Thailand-based businesses of the Aditya Birta Group,
one of India’s largest business houses.

The European Resin Manufacturers’ Association (ERMA) recently announced the formation of an
unsaturated polyester sector group with Ashland and Resinous Chemicals, Cray Valley, Deltech,
DSM, Reichhold and Scott Bader, and their distributors as its initial members. The principle aim of
the group is to address issues affecting the manufacture and supply of unsaturated polyesters, such
as environmental and packaging matters and raw material trends. In the latter respect they aim to
review ways of ensuring much more consistent price and supply levels for the many raw materials
they purchase. The members have recently been hit badly by increasing monomer prices, the
shortage of styrene and the expected price increases in both phthalic and maleic anhydride as well
as glycol. Although vagaries in oil pricing, aggravated by political events, do play their part, the
real momentum seemingly comes from a combination of genuine prospects of economic recovery,
coinciding with marked shortages in certain sectors.

Having the aim of accelerating the development of its core business during 2000, Penn Specialty
Chemicals sold, inclusive of technology, process data, specifications and trade marks, the Furcarb
and Farez phenolic resin production lines, to Perstrop Chemitec a division of Perstrop AB. The
latter had been a key supplier of raw materials for the Furcarb process and the acquisition is
expected to strengthen Perstrop’s position as a leading phenolic resin supplier to Europe.

In the oldest of thermoset resins, phenolics, the change in producers continues. In the early 1990s
BP Chemicals sold its phenolic resins production business at Barry in South Wales, UK, to
Blagden Chemicals. After only a few years the business was sold again to Borden Chemical UK
who have since consolidated their production by closing their original UK factory near
Southampton and concentrating all production at Barry. In July 2002 Bakelite purchased the
phenolic reins business of WBB Minerals, which belonged previously to Sibelco Minerals and

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Thermoset Resins Market Report

Chemicals and prior to that to Hepworth Minerals and Chemicals. There are, at the time of going to
press, rumours of a large, traditional US phenolic producer being up for sale.

The Lonza Group, Switzerland has agreed in principle to sell its Polymer Intermediates Business
for over CHF 1 billion to the private equity arm of Prudential plc, UK, PPM Ventures (PPMV).
This includes the manufacture of oxidation catalysts, dibasic acids, anhydrides and their
derivatives, plasticisers, resins and compounds at 9 facilities located in Italy, Germany, the USA,
Singapore and China.

Reichhold has announced plans to build, by the end of 2002, a new gel coating facility in
Fredrikstad, Norway, moving current production from Sandfjord.

At the time of writing, there have been small but significant price rises in much of the thermoset
industry, resulting from a rise in raw material prices. The underlying factors are: the steadily
increasing, although fluctuating, cost of crude oil and natural gas, coupled to escalating energy
costs; the declining inventories of these materials held by both the United States and European
producers; as well as uncertain political issues in the Middle East. However, there is one additional
factor, as the overall world economy improves the demands for the wide variety of products now
produced from thermoset resins will undoubtedly increase, placing even more demand on the raw
material supply chain. It is the vicious circle faced by any valuable market commodity.

7.2 Companies’ Directory

Whilst there has been a serious attempt to ensure inclusion of the major companies involved in
thermoset resin manufacture and a wish to see most countries represented, no claim is made as to
the completeness of the following list. There are many annually updated lists of companies
involved in the thermoset industry available and there is no point in reproducing a ‘point in time’
list here. Many of those listed have manufacturing units and/or offices in other world locations than
those shown and these can all be accessed through the respective web site. At the same time, no
attempt has been made to classify those listed in respect of the thermoset resin and/or the
market/application of major interest to each. Finally, and in line with other recently published
directories, the web, or email address, replaces telephone and fax numbers where available.

ABATRON INC
5501 95th Ave, Kenoshe, WI 53144, USA

AEROPIA LIMITED
Aeropia House, Newton Road, Crawley, West Sussex, RH10 2TY, UK
E-mail: jkeating@aeropia.com

AdTECH PLASTIC SYSTEMS CORP


815 W Shepherd St, Charlotte, MI 48813, USA
www.adtechps.com

ADVANCED COMPOSITES GROUP LTD


Adams Close, Heanor Gate Industrial Estate, Heanor DE75 7SP, UK
www.advanced-composites.com

ADVANCED POLYMER SCIENCES INC


951 Jaycos Road, Avon, OH 44011, USA

AMBER COMPOSITES LTD


94 Station Road, Langley Mill, Nottingham NG16 4BP, UK
www.ambercomposites.co.uk

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Thermoset Resins Market Report

ANTOCOROSIV S A
Th Pallady 57, Bucuresti 7321, Romania

AOC
950 Highway 57 East, Collierville, TN 38017, USA
www.aoc-resins.com

AOC HAWK LTD


Factory Lane, Brantham, Mannitree CO11 1NT, UK
www.aoc-hawk.co.uk

ARISTECH CHEMICAL CORPORATION


7350 Empire Drive, Florence, KY 41042, USA

ASHLAND SPECIALTY CHEMICAL CO


Composites Polymer Division, Box 2219, Columbus, OH 43216, USA
www.ashchem.com

ASTAR SA
Sangroniz 30, Sondica, 48150 Vizcaya, Spain
www.astar.es

ATL COMPOSITES
PO Box 2349, Southport, Queensland 4215, Australia
E-mail: sales@atlcomposites.com

ATUL LIMITED
Atul 396020, Dist. Valsad, Gujarat, India
E-mail: vyg@atul.co.in
www.atul.com

AXSON FRANCE
PB 444, Cergy Cedex 9005, France
www.axson.fr

BAKELITE AG
Gennaer Straße 2-4, D-58642 Iserlohn-Letmathe, Germany (Postfach 7154, D-58609 Iserlohn)
9DU]LQHU 6WUDH  '-47138 Duisburg-Meiderich, Germany (Postfach 120552, D-47125 Duisburg)
Glockenrain 2, D-34621 Frielendorf, Germany (Postfach 61, D-34619 Frielendorf)
E-mail: info@bakelite.de
www.bakelite.de

BAKELITE IBERICA S.A


Carretera a Navarra, Epele 39, E-20120 Hernani (Guipí]FRD  6SDLQ

BAKELITE ITALIA S.P.A


Via Mazzini, 104, I-21058 Solbiate Olona (VA), Italy

BAKELITE OY
Teollisuustie 20b, FIN-82430 Ouhos, Finland

BAKELITE POLYMERS UK LTD


Syer House, Stafford Court, Stafford Park 1, Telford, Shropshire TF3 3BD, UK

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Thermoset Resins Market Report

BAYER AG
Polyurethanes Business Group, D-51368 Leverkusen, Germany
www.pu.bayer.de

BAYER CORP. POLYMERS DIVISION


100 Bayer Road, Pittsburgh, PA 15205-9741, USA
E-mail: polymers.communications.b@bayer.com

BAYER PLC
Strawberry Hill, Newbury, RG14 1JA, UK
www.bayer.co.uk

BAYRAKII (DEWILUX)
AOSB, 1003 Sok, No 2 Gigli, Izmir 35620, Turkey

BEHN MEYER KIMIA SDN BHD


No 5 Jalan TP2, Taman Perindustrian Sime Uep Subang
Selangor, Darul Ehsan 47600, Malaysia
E-mail: bmkmnsj@tm.net.my

BENTLEY CHEMICALS LTD


Hoo Farm Industrial Estate, Kidderminster, DY11 7RA, UK
www.bentleychemicals.co.uk

B F GOODRICH CHEMICAL (DEUTSCHLAND) GmbH


Gorlitzer Strasse 1, 41460 Neuss, Germany

BIP LTD
PO Box 3180, Tat Bank Road, Oldbury, Warley B69 4PG, UK

BORDEN CHEMICAL UK LTD


Sully, Vale of Glamorgan, CF64 5YU. UK
www.bordenchem.com

BOTADARA IMPEX
G-2A, Sai-Zarukha, Opp. SNDT Mahila College, Liberty Garden Road
Malad (W), Mumbai 400 064, India
E-mail: botadara@vsnl.com

BOYTEK
Yenibosna Merkez Mah, 29 Ekim Cad No. 6
34530 Bahçelievier, Istanbul, Turkey
www.boytek.com

BÜFA POLYURETHANE GmbH & Co. KG


Mittelkamp 112, D-26125 Oldenburg, Germany
E-mail: polyurethane@buefa.de
www.buefa.de

BUSING & FASCH GMBH & CO


Hohe Looge 2-8, Rastede, D-26180, Germany
www.buefa.de
www.gelcoat.de

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Thermoset Resins Market Report

CAM ELYAF SANAYII AS


E-5 Karayolu, Bayramoglu Sapagi, Cayirova-Gebeze, Kocaeli 41401, Turkey
www.camelyaf.com.tr

CARLO RICCO & FUI SpA


Viale Della Vecchia, Ferrovia 8-10, Correggio, Italy
E-mail: poliplast@ricco.it

CHEMVAL SRL
26843 Castelnuovo Bocca D’Adda (Lodi), Italy
E-mail: info@chemval.it
www.comcom.it
www.chemval.it

CHINA SCIENTIFIC & TECH IND CORP


No 11 Sanlihe Road, Beijing 100831, China

CHROMOS TVORNICA SMOLA


Zitnjak BB, Zagreb 10000, Croatia

CIBA POLYMERS MATRIX BUSINESS CENTER


281 Fields Lane, Brewster, NY 10509, USA

CIBA SPECIALTY CHEMICALS


4917 Dawn Avenue, East Lansing, MI 48823-5691, USA

CIBA SPECIALTY CHEMICALS


8 rue Lionel Terray, Rueil Malmaison, France

CIBA SPECIALTY CHEMICALS (INDIA) LTD


Building No. 40, Aarey Road, Goregoan (East), Mumbai 400 063, India

COMPOSITES ONE
723 W Algonquin Road, Arlington Heights, IL 60005, USA

COMPOSITE POLYMERS & SPECIALITY CO


4 Deen Dayal Upadhyaya Marg, New Delhi, Delhi 110002, India
E-mail: composit@bol.net.in

COMPOSITE RESINS
Poststraat 1, PO Box 43, 6130 AA Sittard, Netherlands

COMPOSITE TECHNOLOGY DEVELOPMENT INC


1505 Coal Creek Drive, Lafayette, CO 80026, USA
www.ctd-materials.com

COOK COMPOSITES & POLYMERS


816 E 14th Ave, North Kansas City, MO 64116, USA
E-mail: cook@aol.com

CRAY VALLEY
16 rue de la Republique, Puteaux Cedex, Paris la Defense, 101 92970, France
www.crayvalley.com

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Thermoset Resins Market Report

CRAY VALLEY LTD


Laporte Road, Stallingborough, Grimsby DN41 8DR, UK
www.crayvalley.com

CRAY VALLEY RESINS


Baltex Road, PO Box 32211, Mobeni, Durban, Kwazulu/Natal, South Africa

CRAY VALLEY RESINS INDIA LTD


D-43, (I) Trans ThaneCreekm, MIDC Industrial Area, Navi Mumbai 400 706
E-mail: nishit.parikh@crayvalleyindia.com

CREST COMPOSITES & PLASTICS PVT. LTD


D-6 & 7 Hare Krishna Estate, Narol-Sarkhej Bye Pass
Narol, Ahmedabad 382 405, India
E-mail: crespolad1@sancharnet.in

CULVER CITY COMPOSITES CORP


5915 Rodeo Road, Los Angeles, CA 90016, USA
E-mail: lescohen@aol.com

CYTEC ENGINEERED MATERIALS


1440 N Kraemer Blvd, Anaheim, CA 92806, USA
www.cytec.com

CYTEC ENGINEERED MATERIALS LTD


Abenbury Way, Wrexham Industrial Estate, Wrexham, Clwyd, LL13 9UZ, UK
www.cytec.com

DEGUSSA CANADA LTD


4261 Mainway Drive, Burlington, Ontario L7R 3Y8, Canada

DE YSSEL COATINGS BV
Postbus 4, AA Moordrecht 2840, Netherlands
E-mail: hermanb@worldonline.nl

DIST FIBERGLASS DE MEXICO SA DE CV


Fco Silva Romero No 989 SR, Guadalajara, Jalisco 44430, Mexico
E-mail: dfmsa@vianet.com.mx

DOW CHEMICAL (AUSTRALIA) LTD


Kororoit Creek Road, Altona, Victoria 3018, Australia
www.derakane.com

DOW CHEMICAL (CHINA) LTD


Suite 1101 Shui On Plaza, No 333 Huaihai Zhong Road, Shanghai 200021, China
www.dow.com

DOW CHEMICAL CO (NORTH AMERICA)


2040 Dow Center, Midland, MI 48674, USA
www.derakane.com

DOW CHEMICAL INTERNATIONAL LTD


Unit 1, Corporate Park, Sion Trombay Road, Chembur Mumbai 400 071, India
www.dow.com

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Thermoset Resins Market Report

DOW CHEMICAL JAPAN LTD


8/F Tennoz Central Tower, 2-24 Higashi Shinagawa, Shinagawa-ku, Tokyo 140, Japan
www.dow.com

DOW CHEMICAL PACIFIC LTD


Lot 6, CP Tower, No 11 Section 16/11 Jalen Damansara, 46350 Petaling Jaya, Selangor Darul
Ehsan, Malaysia
www.dow.com

DOW EUROPE SA
Rachtobelstrasse 3, Horgen, CH 8810, Switzerland
www.derakane.com

DOW LATIN AMERICA


Rua Alexandre Dumas 1671, PO Box 3174, 04717-903 Sao Paulo, Brazil
www.derakane.com

DSM COMPOSITE RESINS


PO Box 12 27, CH-8207 Schaffhausen, Switzerland
www.dsmcompositeresins.com

DSM COMPOSITE RESINS


DSM House, Papermill Drive, Redditch, B89 8QJ, UK

DSM COMPOSITE RESINS


Via Silvio Pellico 12, PO Box 321, 22100 Como, Italy

DSM COMPOSITE RESINS


Tour Atlantique, 9 Place de la Pyramide, La Defense 9, 92911 Paris, France

DSM COMPOSITE RESINS


U 508, Carl-Bosch-Str 38, 67056 Ludwigshafen, Germany

DSM COMPOSITE RESINS


Edificio EURO-3, 08960 Sant Just Desvern, Barcelona, Spain

DSM COMPOSITE RESINS


Varvsvagen, PO Box 619, 26126 Landskrona, Sweden

DULUX RESINS
15 Gow Street, Padstow, NSW 2211, Australia

DYNOMER (MALAYSIA) SDN BHD


Plo 491, Jln Keluli. Pasir Guadang, Johor 81700, Malaysia
E-mail: kim-hai.wong@dynoind.com

ELEKEIROZ
R.Dr.Edgardo de Azevedo Soares, 392 Várzea Paulista, São Paulo, Brazil
E-mail: resinas@elekeiroz.com.bt
www.elekeiroz.com.br

EMERSON & CUMING


46 Mannig Road, Billerica, MA 01821, USA

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Thermoset Resins Market Report

EMS-CHEMIE
Reichenaverstrasse, Domat/Ems, CH 7013, Switzerland
E-mail: welcome@emschem.com

ENTRA ILBERICA SA
Jose Ortega Y Gasser, Nr 20-8, Madrid E-28001, Spain
E-mail: entrai@teleline.es

EPOXA SA
Av Carlos Valdovinos 3081, Santiago, Chile
E-mail: spiedeah@oxiquim.cl

ETERNAL CHEMICAL CO LTD


578 Chien-Kung Road, Kaohsiung, Taiwan
E-mail: major@ksnotes1.eternal.co.ta

FERRO CORP - Specialty Plastics Group


Ctra. Valencia-Barcelona, 12550 Almazor, Castellon, Spain
www.ferro.com

FERRO INDUSTRIAL PRODUCTS LTD


8390 124th Street, Surrey, British Columbia V3W 3X9, Canada

FERRO INDUSTRIES INC


35200 Union Lake Road, Mount Clemens, MI 48045, USA

FERS RESINS SA
Arquimedes, 1-08930 Sant Adria de Besos, Spain
www.fers.es

FIBER COTE INDUSTRIES INC


172 East Aurora Street, Waterbury, CT 06708, USA

FIBER KEMI AS
Strandveien 50, Lysaker 1366, NORWAY

FICI
8550 West Flagler Street, Suite 101, Miami, FL 33144, USA
E-mail: sales@ficimiami.com

FRP SERVICES & CO


FRP Building, 15-9 Chome, Awaza Nishi-Ku, Osaka 550-0011, Japan
www.frpservices.com

FRP SERVICES & CO (AMERICA) INC


10 Bank Street, Suite 450, White Plains, NY 10606, USA
E-mail: info@frpservices.com

FRP SERVICES (ASIA) PTE LTD


396 Alexandra Road, #06061 BP Tower, Singapore 119954, Singapore
E-mail: info@frpservices.com

FRP SERVICES (AUST) PTY LTD


Level 2, Dunlop Street, Newsread, QLD 4006, Australia
E-mail: info@frpservices.com

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Thermoset Resins Market Report

FRP SERVICES & CO (CHINA)


Room 5, 10th Floor Zhengyan Bldg, 29 Nanping Kaifa Road
Chongqing 400060, People’s Republic of China
E-mail: info@frpservices.com

FRP SERVICES & CO (TAIPEI)


6F-3, 31 Sung-Chiang Road, Taipei, Taiwan, People’s Republic of China
E-mail: info@frpservices.com

FRP SERVICES EUROPE SARL


Parc de laDuranne235, Avenue Louis de Broglie, 13090 Aix-En-Provence, France
E-mail: info@frpservices.com

GENERAL FIBERGLASS SUPPLY INC


1335 E Wisconsin Ave, Pewaukee, WI 53072, USA

GLASSFIBRE & RESINS SUPPLIES LTD


Midleton, County Cork, Ireland
E-mail: grs@grsmm.aol.ie

GOLD VALLEY CHEMICAL CORP


PO Box 7928, Sharjah, United Arab Emirates
E-mail: goldvaly@emirates.net.ac

GOUGEN BROTHERS INC


100 Patterson, Bay City, MI 48706, USA

GRP MATERIALS SUPPLIES


Alchorne Place, Portsmouth, PO3 5QU, UK
www.grpms.co.uk

HARVEYS FIBREGLASS (PTY) LTD


41 Jasper Road, Robertsham, Johannesburg 2135, South Africa
www.harveysfibreglass.co.za

HAWKEYE INDUSTRIES INC


3050 Brookview Dr, Marietta, GA 30068, USA
E-mail: jreahwk@aol.com
www.duratec1.com

HB FULLER CO
3530 Lexington Ave N, St Paul, MN 55126-8076, USA
www.hbfuller.com

HELIOS
Kolicevo 65, Domzale 1230, Slovenia
E-mail: bozidar.pagers@helios.si

HENKEL TEROSON GmbH


Postbox 105620, 69046 Heidelberg, Germany
www.henkel-teroson.de

HERBERTS POLYMERS POWDERS SA


PO Box 140, Bulle, Switzerland
E-mail: hpp@herberts.ch

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Thermoset Resins Market Report

HEXCEL COMPOSITES
Duxford, Cambridge, CB2 4QD, UK
www.hexcelcomposites.com

HOS-TECHNIK GmbH
PO Box 3, A-9431 St. Stefan, Austria
E-mail: hos@hostechnik.at
www.hos-tec.com

HUNTSMAN COMPOSITES
Somerville Road, West Footscray, Victoria 3012, Australia
E-mail: geoff_houghton@huntsman.com

INEOS ACRYLICS
PO Box 34, Darwen, BB3 1QB, UK
E-mail: info@lucite.com

INTERPLASTIC CORP
1225 Willow Lake Blvd, St Paul, MN 55110, USA
www.interplastic.com

INTERSTAR LTD
Al Wahda, PO Box 23007, Sharjah, United Arab Emirates
E-mail: interstr@emirates.net.ae

ITALBEIT SrL
via A Diaz 9-11, Nerviano 20014, Italy
E-mail: italbeit@tin.it

ITW PLEXUS
30 Endicott Street, Danvers, MA 01923, USA
www.itwplexus.com

ITW PLEXUS EUROPE


Unit 1, Bushacre Court, Garrard Way, Kettering NN16 8TD, UK
E-mail: sales@itwplexus.co.uk
www.itwplexus.co.uk

JEWEL POLYMER PVT LTD


308 Adhyaru Industrial Estate, Sun Mill Compiund,
Senapati Bapat Marg, Lower Parel, Mumbai 400 013, India
E-mail: jewelpol@vsnl.com

JIAGYIN 2 SYNTHETIC CHEMICALS FACTORY


Yingbin West Road, Huangiu, Jiangsu 214445, China
www.fulichem.com

KAISER COMPOSITEK
1095 Columbria, Brea, CA 92821, USA
E-mail: psteiner@kaiercompositek.com

KIDRON PLASTICS LTD


155 Bialik Street, PO Box 8045, Kamat Gan 52180, Israel
E-mail: mail@kidron.co.il

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KÖMMERLING CHEMISCHE FABRIK GMBH & CO


PO Box 2165, 66929 Pirmasens, Germany
www.koemmerling.de

LAMINOPOL SPZ
Szczecinska 58B, Skupak 76 200, Poland
www.laminopol.com

LEDA SrL
Via Copernico 2/4, Nonantola, MO 41015, Italy
www.leda.it

LE JOINT FRANCAIS (HUTCHINSON WORLDWIDE)


BP 16, 84 – 116 rue Salvador Allente, 95870 Bezons, France
www.hutchinson-aerospace.com

LILLY INDUSTRIES INC


28335 Clay Street, Elkhart, IN 46517, USA
www.lillyindustries.com

LILLY INDUSTRIES INC


1915 Second Street West, Cornwall, Ontario K6H 5T1, Canada

LLEWELLYN RYLAND LTD


Haden Street, Birmingham, B12 9DB, UK
www.llewellyn-ryland.co.uk

LLEWELLYN RYLAND (CHINA) LTD


Unit 8 12/F, Raton Industrial Building, No. 4 Kin Wong Street, Tuen Mun,
Hong Kong

LOCTITE AEROSPACE
2850 Willow Pass Road, Bay Point, CA 94565, USA
www.loctite.com

LONZA SpA - Intermediates & Additives


Via Vittor Pisani 31, 1-20124 Milan, Italy

LORD CORPORATION
PO Box 8012, 111 Lord Drive, Cary, NC 27512-8012, USA
www.lord.com

MARTE
Via Buozzi 4, 20047 Brugherio, Milan, Italy
E-mail: martespa@libero.it

MAEDER KUNSTHARZE AG
Industrie Strausse 1, Killwangen, CH 8956, Switzerland
www.maederkunstharze.ch

MAGNOLIA PLASTICS INC


5547 Peachtree Industrial Blvd, Chamblee, GA 30341, USA
www.magnapoxy.com

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MARCHEM CORPORATION
2500 Aidie Road, St Louis, MO 63043, USA

MARTIN G SCHEUFLER KUNSTHARZPRODUKTE GMBH


Postfach 61 02 38, D-70309 Stuttgart, Germany
www.mgs-online.com

MECHEMCO INDUSTRIES
27 Kewal Industrial Estate, Senepati Bapat Mrg, Lower Parel
Mumbai, Maharashtra 400013, India
www.mechemco.com

NAPTHA RESINS & CHEMICALS LTD


510 Westminster 3rd Floor, Cunningham Road, Bangalore 560 052, India
E-mail: nrcl@bgl.vsnl.net.in

NCS RESINS
9 Pineside Road, New Germany, Kwazulu-Natal 3610, South Africa
E-mail: andrei@ncp.co.za

NESTE POLYESTER (AMERICAS)


5106 Wheeler Avenue, Fort Smith, AR 72901, USA
www.nestepolyester.com

NESTE POLYESTER (ASIA PACIFIC)


Lujia Industrial Zone, Kunshan, Jiangsu 215331, China
www.nestepolyester.com

NESTE POLYESTER (EUROPE NORTH)


PO Box 320, Porvoo, SF-06101, Finland
www.nestepolyester.com

NESTE POLYESTER (EUROPE SOUTH)


BP 01 Quartier de Bonnelles, Sauveterre, F-30150, France
www.nestepolyester.com

NESTE RESINS
5865 McLaughlin Road, Unit 3, Mississauga, Ontario L5R 1B8, Canada
E-mail: abutt@neste-resins.com

NIPPON SHOKUBAI CO LTD


Kogin Building, 4-1-1 Koraibashi, Chuo-ku, Osaka, Japan

NOBLE SYNTHETICS LTD


314 TV Ind Estate, Worli, Bombay, Maharashtra 400025, India
E-mail: nishith@bom3.vsnl.net.in

NORD COMPOSITES
Cour De La Gare, 80510 Longpre Les Corps Saints, France

NORFIELD CORPORATION
36 Kenosia Avenue, Danbury, CT 06810, USA

PERMABOND
National Starch & Chemical Co Ltd, Woodside Road, Eastleigh, Hants, SO50 4EX, UK

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PLATS CO SAHA
Behesthti Street, Babolsar, Mazandran 47441, Iran

POLIRESINAS SAN LUIS SA


Calle 76 Nro 1668, Villa Zagala, San Martin, Buenos Aires 1651, Argentina
E-mail: polial@satlink.com

POLIYA POLIESTER
Esenyert Yolu No 72, 34841 Avcilar, Istanbul, Turkey
E-mail: poliya@poliya.com
www.poliya.com

POLYGARD INC
5010 N Coolidge Avenue, Tampa, FL 33614, USA
www.polygard.com

POLYMER TECHNOLOGIES
25 Gul Avenue, 629665 Singapore
E-mail: poltech@singnet.com.sg

PROGRESS PLASTICS & COMPOUNDS CO


1100 Meyerside Drive, Mississauga, Ontario L5T 1J4, Canada

REFNOL RESINS & CHEMICALS LTD


Plot 23, Phase III, Gide Ind Estate, Naroda, Ahmedabad, Gujarat 382 330, India
E-mail: refnol@ice.net

REICHHOLD AB
Mankimichendie 10, Espoo 02780, Finland
www.reichhold.net

REICHHOLD AS
PO Box 2061, Ranvik Brygge 5/7, Sandefjord 3202, Norway
www.reichhold.net

REICHHOLD BV
Postbus 208, AE Apijkenisse 3200, Netherlands

REICHHOLD CZ AS
Veleslavinova 3, PO Box 10, 40011 Usti nad Labem, CZ-40011 Czech Republic

REICHHOLD DANMARK AS
Postbus 426, Jernet 6, Kolding 6000, Denmark

REICHHOLD FRANCE SA
105 Rue des Campanules, 77185 Lognes, France

REICHHOLD GmbH
Winsberging 25, Hamburg 22525, Germany
www.reichhold.com

REICHHOLD INC
PO Box 16911, Jebel Ali Free Zone, Dubai, United Arab Emirates
E-mail: reichhold@emirates.net.ae

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REICHHOLD INC
PO Box 13582, Research Triangle Park, NC 27709-3582, USA
www.reichhold.com

REICHHOLD SrL
Via Romagnoli 23, S Polo di Torrile, Parma 43056, Italy

REICHHOLD SVERIGE AB
PO Box 266, Klangfargsgatan I, Vastra Frolunda 42123, Sweden

REICHHOLD UK LTD
54 Willow Lane, Mitcham, Surrey, CR4 4NA, UK
www.reichhold.com

RESINOUS CHEMICALS LTD


Wellington Mills, Cross Lane, Dunston, Gateshead, Tyne & Wear NE11 9HQ, UK

REVERTEX (MALAYSIA) SDN BHD


Batu 1 ½, Jalan Batu Pahat, KB 508, Kluang Johor 86009, Malaysia

SCOTT BADER CO LTD


Wollaston, Northamptonshire, NN29 7RL, UK
www.scottbader.com

SCOTT BADER SA
65 rue Sully, 80044 Amiens Cedex I, France

SCOTT BADER SCANDINAVIA AB


Betongvagen 4, PO Box 202, Falkenberg 31123, Sweden
E-mail: composites@scottbader.se

SHOWA HIGHPOLYMER CO LTD


3-20 Kanda Nishiki Cho, Chiyoda Ku, Tokyo 101, Japan
E-mail: overseas@he.shp.co.jp

SIA ADHESIVES INC


123 West Bartges Street, Akron, OH 44311-1081, USA
www.ssc-sia.com

SINGAPORE HIGHPOLYMER CHEMICAL PRODUCTS PTE LTD


21 Tanjong Penhuru, S 609022 Singapore
www.shep-resins.com

SIKA AG
Tüffenweis 16-22, CH-8048 Zurich, Switzerland
www.sika.com

SIR INDUSTRIALE
Via Bellini 35, 20050 Macherio, Italy

SP SYSTEMS
St Cross Business Park, Newport, Isle of Wight PO30 5WU, UK
E-mail: info@spsystems.com
www.spsystems.com

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SUD-WEST-CHEMIE GmbH
Postfach 21 20, Pfaffenweg 18, Neu-Ulm 89231, Germany
E-mail: sued-west-chemie@t-online.de

SUNREZ CORPORATION
392 Coogan Way, El Cajon, CA 92020, USA
www.sunrez.com

SUQUIMICA ST
Pl Les Comes, C/Alemania 47, Igualada, Barcelona 08700, Spain

SYNTHETIC RESIN PRODUCTS LTD


A-364 Industrial Estate, Peenya 1st Stage, Bangalore 560 058, India
E-mail: synres@vsnl.net

SYNTHOPOL CHEMIE BUXTEHUDE


Postfach 15 61, Alter Postweg 35, Buxtehude 21614, Germany
www.symthopol.com

TAKEDA CHEMICAL INDUSTRIES LTD


Composite Materials - Chem Prod Co, 2-13-10 Nihonbashi Chuo-ku
Tokyo 103-0027, Japan

TRIAS CHEM SRL


Via Micheli 15, Parma, 43056 San Polo, Italy
E-mail: triaschem@triaschem.com
www.triaschem.com

VANTICO Espana SL
Balmes 117 (Apartado 744), E-08008 Barcelona, Spain

VANTICO GmbH & Co KG


Öflinger Straße 44, D-79664 Wehr/Baden, Germany

VANTICO LTD
Duxford, Cambridge, CB2 4QA, UK
www.adhesives.vantico.com

VANTICO SAS
13 rue Paul Dautier, F-78140 Velizy, Villacoublay, France

VANTICO Sri
Strada Statale 233, Km 20.5, 21040 Origgio VA, Italy

VASAVIBAIA RESINS (P) LTD


151 Eldams Road, Chennai, Tamil Nadu 600018, India
E-mail: vbr@vsnl.com

VIANOVA RESINS AG
Altmannsdorferstr 104, 1120 Wien, Austria

WESSEX RESINS & ADHESIVES LTD


Cupernham House, Cupernham Lane, Romsey SO51 1TR, UK
www.wessex-resins.com

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WEST & SENIOR LTD


Milltown St, Radcliffe, Manchester, M26 1WE
E-mail: info@westsenior.co.uk
www.westsenior.co.uk

7.3 Company Profiles

The following selection of company profiles, reproduce data published by each company.

7.3.1 AOC

950 Highway 57 East, Collierville, TN 38017, USA


Tel: +1 901 854 2800, Fax: +1 901 854 7277
E-mail: sales@aoc-resins.com, www.aoc-resins.com

It is AOC’s claim that it is the world leader in innovative resin technology and a leading producer
of unsaturated polyester, vinyl ester resins, hybrids, blends, specialty resins and gel coats for the
polymer composite and cast polymer industries. The company has six manufacturing plants
strategically located throughout North America and a local supply agreement in the United
Kingdom.

AOC is a unique global enterprise with historical roots branching in two distinct directions. The
core of what comprises AOC today was formed in 1994 through a joint venture of the resin
business of two companies – the Alpha Corporation of Collierville, Tennessee and Owens Corning
of Toledo, Ohio. Alpha was a leading producer and innovator of open mould resins while Owens
Corning’s expertise lay in closed mould resin systems. The divergent strengths of the two founding
companies were exceptionally complimentary to each other. What emerged was neither Alpha nor
Owens Corning, but a creative amalgamation of the best of two different corporate cultures and
areas of expertise. In 1998 the Alpha Corporation and an internal management group purchased
Owens Corning’s interest in the joint venture. The change streamlined the decision-making process
under a single organisation focused solely on meeting the needs of unsaturated polyester and vinyl
ester resin users.

AOC has entered into a toll manufacturing agreement with Thai Epoxy and Allied Products Co.
Ltd., of Bangkok, Thailand, for the production of vinyl ester resins. The deal aims to enhance
AOC’s marketing strategy throughout the Asia-Pacific region.

All AOC’s manufacturing facilities are certified as meeting the quality management standards of
ISO-9002. Their proprietary manufacturing process control programme sets the world standard for
producing resins of exacting consistency batch after batch.

AOC claims to create and deliver innovative resins of high-quality, consistency and value. There
are three corporate principles, customer satisfaction, employee empowerment and industry
leadership.

7.3.2 ASHLAND SPECIALTY CHEMICAL COMPANY

5200 Blazer Memorial Parkway, Dublin, OH 43017, USA


Tel: +1 614 790 3333, Fax: +1 614 790 4119
E-mail: csr@ashchem.com, www.ashchem.com

Established in 1967 and with 7,100 employees, Ashland is a leading, worldwide supplier of
specialty chemicals serving industries including adhesives, automotive, boat-building, composites,
foundry, merchant marine, paint, paper, plastics and semiconductor fabrication. Although of no

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interest in the context of this thermoset study, the company is also a leader in products and systems
for water and fuel treatment, shipboard maintenance and a programme for total energy
management.

Ashland Specialty Chemical Company is involved with adhesives as well as being one of the top
manufacturers of the thermosetting composite polymers, unsaturated polyester and vinyl ester
resins. Ashland Distribution has close involvement – through FRP (Reinforced Plastic) Supplies –
in the supply and distribution of chemicals, solvents, plastics and fibre reinforcements to
principally the composites industry throughout North America and Europe.

The Specialty Polymers and Adhesives Division is a leader in the supply of structural and pressure
sensitive adhesives, plus a full line of high-performance urethane, rubber-based, epoxy and
waterborne structural adhesives. Other products include urethane coatings, solventless butyl tapes
and electromagnetic bonding systems for plastics parts assembly.

Overall Ashland Distribution and Ashland Specialty Chemical care about protecting the
environment, the communities in which people operate and in the health, safety and well-being of
employees, customers and suppliers. The company works to provide all the information necessary
to properly use, handle and dispose of all the products that it manufactures and sells.

7.3.3 BAKELITE AG

*HQQDHU 6WUDH -4, D-58642 Iserlohn-Letmathe, Germany


(Postfach 7154, D-58609 Iserlohn)
Tel: +49 02374-925-0, Fax: +49 02374-925-506
E-mail: info@bakelite.de, www.bakelite.de

Recognised for their Rütapox® epoxy resins, their Rütaphen® phenolic and furane resins, Bakelite
AG has for many years been supplying highly successful thermosetting resin solutions across a
wide spectrum of industrial application requirements. Indeed they justifiably claim to be one of, if
not the first, manufacturer of synthetic plastic polymers, remaining today a trailblazer in the
production of epoxy resins, phenolics and moulding compounds. Their future goal is to continue to
develop and commercialise innovative high quality systems, catalysts and hardening agents,
whether for the building industry, the lacquer/paint industry, the composites industry, or, finally, to
equally satisfy the full requirements of the electrical casting industry or the manufacture of printed
circuit boards.

Bakelite’s unmodified, highly chemically resistant epoxy resins, based on bisphenol A or bisphenol
F chemistry (or combinations of the two) are available in a variety of viscosities, filled and unfilled,
with a wide choice of catalyst and hardening agents. They are used in the building industry as
decorative flooring or lining materials, in bridge, tunnel, railway or waterway construction, or in
the repair of concrete structures. Likewise, their cold-curing phenolic and furane resin based putties
and laminates, fulfil many building and industrial needs, particularly applications involving
exposure to aggressive environments, whether chemical, thermal or mechanical. Many of these
systems (including the Rütapox® epoxies) can be employed in the construction of chemical
process equipment, or in the production of technically demanding paint and varnish finishing
treatments of both high and low molecular weight, as required by the land, sea and air transport
industry. Other miscellaneous uses come under the headings of wire enamels, air-drying
oleoresinous lacquers, printing ink binders, photosensitive resists or powder coatings.

Efficient Rütapox® epoxy systems – both brominated and non-brominated depending on the
specified flame/fire resistance - have equally proved themselves in the insulation and sealing of
electrical equipment, for example in generators, bushings, transformers, switchgear components,
post insulators, ignition coils, flyback transformers and capacitors. Suitable systems are available

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for casting, coating, pressure gelation or impregnation. Many applications are equally open to the
intrinsically fire-resistant, Rütaphen phenolics.

Finally, Bakelite AG is a leading supplier of epoxy and phenolic resins used as matrices in the
manufacture of glass, carbon and aramid fibre reinforced composites, whether moulded by hand-
lay, resin transfer moulding, filament winding, pultrusion or preimpregnated techniques. These
composites find application in the aeronautics, aerospace, wind energy, transport, construction and
sports/leisure industries.

The range of applications for phenolic resins, for which Bakelite AG is one of the largest suppliers
throughout Europe, stretches from such diverse areas as the insulation industry and mining to
fabrication of mineral wool materials and floral arrangement foam. For the wood materials
industry, the company produces resins for weatherproof chipboard and fibreboard, veneer plywood
and decorative laminates for outdoor and indoor use. In addition, Bakelite AG offers the widest
product range of industrial phenolics in Europe, used in fields including the foundry and
refractories industries, and in the manufacture of textile mats and friction linings.

Bakelite AG is the world’s leading supplier in the area of thermoset moulding compounds. These
moulding compounds are mainly used in the automotive, household appliance and electrical
industries. For example, in the automotive industry they are found in the electrical systems, the
electronics, in parts of the internal and external furnishings, and increasingly in the engine
compartment as well. The electrical industry uses moulding compounds for applications including
contact bridges and switches.

The electronics industry also relies on moulding compounds. They are found in electrical
engineering subsets such as measuring, regulating and controlling systems as well as in switches,
electromechanical drive technology, power transmission and connection systems, and in lighting.
In the household appliances industry, moulding compounds are used in applications including the
production of major and small electrical appliances as well as kitchen equipment. Typical products
are oven trim, pot handles and operating controls.

In conclusion, Bakelite AG resin systems satisfy a range of important requirements with wide
applicability and premium properties.

7.3.4 BOYTEK

(Reçine Boya ve Kimya Sanayi Ticaret A.S.)


Yenibosna Merkez Mah, 29 Ekim Cad. No. 6, 34530 Bahçelievier, Istanbul, Turkey
Tel: +90 (212) 551 03 04/05 or 652 21 14/15, Fax: +90 (212) 551 28 35

Çerkezköy Organize Sanayi Sitesi 7, Sok. 59501 Çerkezköy, Tekirdag, Turkey


Tel: +90 (282) 758 20 42, Fax: +90 (282) 728 20 44
E-mail: boytek@boytek.com.tr, www.boytek.com

Established in 1978 for the manufacture of alkyd and unsaturated polyester resins, Boytek A.S has
become a leading supplier of a wide range of high quality resin systems, gelcoats, pigment pastes
and peroxides to those involved in the composites moulding of automotive, building, marine and
furniture components. Although the manufacture of alkyds was discontinued in 1982, Boytek have
retained an interest in the supply of unsaturated polyesters for the manufacture of buttons. By 1999
they had obtained full ISO 9002 Quality Management Certification and in the following year were
able to list 15 countries to whom their products were exported. Their appearance at the prestigeous
JEC Exhibition held annually in Paris, confirms that international recognition.

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7.3.5 BÜFA POLYURETHANE GmbH & Co. KG

Mittelkamp 112, D-26125 Oldenburg, Germany


E-mail: polyurethane@buefa.de, www.buefa.de

Although discovered by the German, Otto Bayer, in 1937, the full commercialisation and vast
potential open to the technology of polyurethane resins did not really become apparent until the late
1960s, early 1970s. Since then, Büfa has been actively involved in the polyurethane industry,
offering continuous improvement in the raw material formulation, in the technology and production
engineering and in a wide range of applications, which has made the material an indispensable
element in modern manufacturing technology.

Today, Büfa Polyurethane, which is part of the large German, Büsing & Fasch Group, processes
the raw material components on one of the most modern formulating lines in Europe. Here
tailormade formulations are produced to customers’ specifications and optimised for their
individual needs. These may be rigid or flexible applications, from expanded to solid, or perhaps
employed in products reinforced with glass fibre, where there is also good synergy with the 100%
subsidiary, unsaturated polyester resin division of the Büfa Group.

Overall the Group operates an Integrated Management System (IMS) where four equal-ranking
corporate principles apply – to act only in a customer-orientated fashion, to protect both humankind
and the environment and to work together to successfully manage resources.

7.3.6 CRAY VALLEY

Immemeuble le Diamant, 16 rue de la Republique, Puteaux Cedex, Paris la Defense, 101-92970,


France
Tel: +33 1 4135 6888, Fax: +33 1 4135 6118
www.crayvalley.com

It is the business of Cray Valley to develop high-technology resins and additives for the coatings
industry, industrial paints, inks, varnishes and adhesives, and unsaturated polyester resins and gel
coats for the composites industry. The company is part of the French, Atofina Group which is the
chemical branch of the Total Fina Elf Group. In the United States, the resin division is known as
Cooks Composites & Polymers, but as Cray Valley in the rest of the world. The group formed by
Cray Valley, Cook Composites & Polymers and also Sartomer, is the second largest resins
manufacturer in the world, currently employing around 3,700, with sales in 2001 of 1.7 billion
euros. Nevertheless it is basically a simple, streamlined and efficient organisation which can be
considered to be built around five main technologies: structural resins, coating resins, waterborne
polymers, powder and functional additives, and finally powder and hard resins.

Since its consolidation in 1990, Cray Valley has continued its dynamic and international growth
and the following short - and incomplete - list of acquisitions since then, and now totalling over 30,
is suitably illustrative. In 1993 the company acquired Anchor in the UK and the US company
American Colors. In 1996, the Spanish company Reposa was added, with, in the following year,
two Canadian companies, Progress and Arkem. In 1999 Cray Valley Korea was established,
followed in 2001 by the acquisition of the Malaysian company Dynomer and the resins division of
Croda from the UK.

7.3.7 DSM COMPOSITE RESINS

PO Box 12 27, CH-8207 Schaffhausen, Switzerland


www.dsmcompositeresins.com

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With new headquarters in Schaffhausen, Switzerland, but employing over 500 in other parts of
Europe, DSM Composite Resins is a leading producer of solutions for the composite resin industry.
That position has, like the manufacture of a good thermoset resin by the blending together of
ingredients of the right type and quality, been achieved over the last 30 years by acquiring the best
companies with the best technology, and using the know-how of their skilled people. Among those
acquisitions was, in 1971, the Synres company first founded near Rotterdam in 1947. Several years
later that business was then joined with Unilever’s and Scado’s unsaturated polyester and coating
resin business. Then came the acquisition of Savid from Italy and Freeman Chemicals from the UK
and in 1989 the moulding compound business of Bayer. More recently, in 1995, there was the
purchase of the Vestopal resin business of Hüls and then in 1997 came the merger of the two
leaders in Europe, DSM Resins and BASF’s resin division to create the biggest European supplier
of thermoset systems.

In 1999, DSM Resins was spilt into two complimentary companies, DSM Industrial Resins dealing
with composite resins, plasticisers, sizings and binders and DSM Coating Resins dealing with wet-
coating resins, powder coating resins and state-of-the-art UV-curable resins. Both operate local
Customer Competence Centres throughout Europe, that provide extensive commercial and
technical services. Product sale and distribution is organised through Euroresins
(www.euroresins.com) which operates in the Netherlands, the UK, Norway & Sweden, Spain and
Italy. This one-stop-shopping service enables customers to keep minimum stock levels. It also
supplies raw materials from Owens Corning Fiberglass, Vetrotex, Akzo Nobel and Resolution
Performance Products.

In one of the most recent announcements, DSM Composite Resins revealed that they had joined
forces with the German Büfa Group (Büsing & FaschGmbH & Co) to produce polyester gelcoats in
Rastede, Germany. This will be the largest plant of its kind in Europe and is a partnership that also
covers the joint development of new products, information exchange and joint technical support
services. The two partners have stated that they have confidence in fully exploiting the expertise
within the companies’ technical facilities in Germany, in the UK, Italy and the Netherlands. They
aim to achieve a stronger leadership position based on advanced product technology and
innovation. The strategic goal is to develop a fully integrated approach to the entire gelcoat
production chain.

7.3.8 DOW CHEMICAL COMPANY

2040 Dow Center, Midland, MI 48674, USA


www.derakane.com, E-mail: info@derakane.com

Just over 100 years ago Dow commenced its operations with the first commercial scale production
of bleach. Since then and largely through acquisition and joint ventures agreements, both of which
continue through to the present day, it has grown to become a leading science and technology
company that provides innovative chemical, plastic and agricultural products – and services – to
many essential consumer markets. Currently employing approximately 50,000 and with annual
sales topping $US28 billion, the company recognises customers in more than 170 countries drawn
largely but not entirely from the food, transportation, health/medical and building and construction
markets.

Dow is basically split into 7 distinct segments, with the majors being:

• Performance Plastics,
• Performance Chemicals,
• Agricultural Products,
• Plastics and Chemicals.

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It is the first, with its principal involvement in engineering plastics, epoxy products, automotive,
and polyurethanes, that is of prime concern to this study, with the vinyl ester and epoxy Derekane®
resins and their excellent chemical resistance performance, to the fore.

Dow people around the world develop solutions for society based on Dow’s inherent strength in
science and technology. For over a decade the company has embraced and advocated Responsible
Care®, a voluntary industry-wide commitment to safely handle all the chemicals manufactured,
from inception in the laboratory to ultimate disposal.

7.3.9 HENKEL TEROSON GmbH

Postbox 105620, 69046 Heidelberg, Germany


www.henkel-teroson.de

Founded by Fritz Henkel 125 years ago, the operations of Henkel Teroson are concentrated on the
following application fields – bonding and sealing, multifunctional coatings, preformed parts and
surface technology. These four core businesses are directed at industry generally, but there is a
particular involvement in both the initial supply and professional repair sectors of the automotive
industry, and also in the insulated glass industry. Typically, the whole product range is largely
aimed at energy-saving, sound deadening and what can be termed as environment, component and
equipment ‘protection’. Overall the aim is to carry on the grand vision of the founder, “to make
people’s lives simpler and easier”, and that has recently been redefined in a new corporate identity,
“Henkel – A Brand like a Friend”. Production is mainly located at the 84,000 m² Heidelberg site in
Germany, but there are also facilities in England, France, Spain, South America, the United States
and throughout the Asia-Pacific region.

Although a plastics processing enterprise rather than a pure chemical firm, Henkel Teroson remains
aware of its special responsibilities with regard to health, occupational and environmental
protection, both to its workers and to those who use, and later have to dispose of, its products.
Indeed a 6-year environmental protection programme completed by the company in 1993, involved
an expenditure of DM36 million; the annual capital expenditure is currently running at between
DM10-20 million, with annual sales – from the Heidelberg site – of some DM410 million.

7.3.10 ITW PLEXUS

30 Endicott Street, Danvers, MA 01923, USA


Fax: +1 978 777 1100, Fax: +1 978 774 0516
www.itwplexus.com

ITW Plexus is a business unit of Illinois Tool Works, a Fortune 200 company, and a worldwide
giant in fastening, joining, sealing and coating technologies. The Plexus business unit makes and
sells the patented new Plexus methacrylate adhesives for structural bonding of nearly all
thermoplastics, metals and composite materials. Epoxy-based adhesives are also available. A key
benefit of these adhesives is their ability to provide extremely durable bonds with little or no
surface preparation. Plexus adhesives have a proven record of outstanding performance in the most
demanding applications in the transportation, marine and engineering construction industries. The
following list of product developments and approvals secured over the last 6 years, offers
confirmation of that record.

• 1997 – The company announced the introduction of MA422, a very tough methacrylate
adhesive with an ‘open’ time of about 15 minutes and a fixture time of twice that, for bonding
composites, thermoplastics and metal assemblies, particularly the high volume production
boatbuilders.

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• 1998 – ITW Plexus adds a new low-odour adhesive (less than 1% VOC) to its range of
structural methacrylate-based materials for use in the automotive and marine industries.

• 1999 – Both low-shrink and fast-curing two-part adhesives were announced by the company
during the year, Plexus MA1020 and MA1025, and Plexus MA403 respectively.

• 2000 – Det Norske Veritas (DNV) approval of three Plexus adhesives (MA555, MA550 and
MA425) particularly for the structural bonding of glass fibre composite laminates, was
announced during the year.

• 2001 – During this year, the company gained the approval of the Underwriter’s Laboratories
for their Plexus MA300, MA820 and AO420 structural adhesives, as well as Lloyd’s of
London approval for Plexus grades MA425, MA550, MA556 and MA1025 in the bonding of
composite laminates (vinyl ester and polyester), stainless and carbon steel, aluminium and
combinations thereof. They also announced that Plexus MA557 had been uniquely formulated
to provide long work-times and an anti-sag property when applied to vertical surfaces.

7.3.11 KÖMMERLING CHEMISCHE FABRIK GMBH & CO

PO Box 2165, 66929 Pirmasens, Germany


Tel: +49 6331 56-0, Fax: +49 6331 56-2391
E-mail: chemie@koemmerling.de, www.koemmerling.de

The Kömmerling company was founded in 1897 for the supply of a range of ancillary items
required by the shoe industry. In 1902 Kömmerling Chemische Fabrik was established for the
manufacture of adhesives. This activity changed little until in 1949 when the company was one of
the first to introduce neoprene adhesives, a development which set the standard in bonding
technology. By 1954 this had resulted in the first major wave of expansion in the setting-up of
subsidiaries and joint-ventures in Ingwiller, France and São Paulo, Brazil. Three years later the
production of plastic profiles commenced and this lead to Kömmerling becoming one of the
pioneers in the field of PVC extrusion. The first production of a primer-free two-component sealant
was successfully introduced in 1969 and that base of manufacturing activity lead during the 80s
and 90s to a time of virtually unrestricted growth. The company established or acquired production
facilities in Italy, France, Spain, China and the USA, with sales companies in Belgium, Bulgaria,
Canada, Denmark, Great Britain, Greece, and the Netherlands and trading subsidiaries in Austria,
Poland, Rumania and Switzerland.

Today, Kömmerling is Europe’s largest independent supplier of high-performance adhesives (both


physically and chemically cured systems) and sealant products for many sectors of industry
including construction (in addition to plastic window profiles and PVC rigid foam sheets). Over
2,300 employees work in 18 companies to serve more than 3,000 customers worldwide.

7.3.12 LLEWELLYN RYLAND LTD

Haden Street, Birmingham, B12 9DB, UK


Tel: +44 (0)121 440 2284, Fax: +44 (0)121 440 0281
E-mail: sales@llewellyn-ryland.co.uk, www.llewellyn-ryland.co.uk

Founded over 200 years ago, Llewellyn Ryland is one of the oldest manufacturing companies in
England. The long experience gained in the creation of highly refined lacquers, paints and
varnishes, evolved into the production of specialist colour pastes and gelcoats for the reinforced
plastics industry. With bases in both the UK and latterly in China, the company can now offer a
worldwide service, enabling it to supply and deliver the whole product range quickly, throughout
the expanding world of reinforced plastics.

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These products, manufactured in accordance with BS EN ISO 9002:1994, include:

• Over 27,000 polyester colour pastes, in opaque, transparent and polychromatic/metallic


shades.

• Brush and spray viscosity polyester and Modar gelcoats and flowcoats in clear, white or any
required colour, with (if required) textured/slip resisting versions.

• A range of mould preparation products.

• Specialised bonding pastes for bonding GRP to GRP or to PVC, timber, metal or
polyurethane.

7.3.13 LOCTITE CORPORATION

2850 Willow Pass Road, Bay Point, CA 94565, USA


Fax: +1 925 458 8000, Fax: +1 925 458 8030
www.loctite.com

Owners of the well-known trade names Hysol®, SynSpand®, SynCore® and SynSkin®, Loctite®
formulates and manufactures a wide variety of structural bonding and structural enhancing
materials for predominantly the aerospace industry. These materials, developed and manufactured
in Bay Point, California, provide their customers with practical, economic and performance
benefits, ideally supported by a global sales and distribution network.

The Hysol® paste adhesives are both one and two-part epoxies for potting, bonding, fairing and
repair, with the related specialty resins being suitable as matrices in a wide range of composites
application. The three syntactic products are special films and typically employed to aid the
bonding of composite laminates and a range of core materials used in the creation of sandwich
structures.

7.3.14 LORD CORPORATION

PO Box 8012, 111 Lord Drive, Cary, NC 27512-8012, USA


Fax: +1 919 468 5979, Fax: +1 919 469 5777
www.lord.com

This privately-owned company, established in Erie, Pennsylvania in 1924 and now employing
around 2,300 people, designs, develops, manufactures and markets throughout 16 countries,
chemical and mechanical products for a wide range of applications. Today annual sales exceed
$US400 million. The Chemical Products Division (CPD) produces high performance adhesives,
coatings and rubber chemicals. Other divisions are largely concerned with the management of
industrial shock, vibration and noise. Among the products of the Chemical Products Division are:

• Aeroglaze® protective coatings,


• Chemglaze® polyurethane copolymers and related catalysts and primers,
• Circalok® electronic adhesives and coatings,
• Lord® cyanoacrylate adhesives,
• DBQDO® vulcanising agents and epoxy structural adhesives,
• Photoglaze® UV/EB curable coatings,
• Ty-Ply® bonding agents and
• Tyrite® urethane structural adhesive.

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The company’s four core technologies are therefore, materials science, electro-mechanical dynamic
systems, synthesis and polymerisation, and surface science.

The Lord Corporation (who pledge that their business will be conducted with integrity and to high
ethical standards) exists to generate, pursue and commercialise useful human knowledge for its
customers and, in serving those customers well, to generate benefits for their stakeholders. The
company believes in a sense of community and civic responsibility, and in the worth and dignity of
each individual, demonstrated by a need to provide an environment which promotes both individual
and team development, and in turn suitably illustrated by a continuous improvement in customer
relationships. The mission of the company is to apply their four inter-relating core technologies to
the development, manufacture and marketing of a unique range of high-quality proprietary
products fully satisfying the selected niche markets of their customers.

7.3.15 REICHHOLD

PO Box 13582, Research Triangle Park, North Carolina 27709-3582, USA


Tel: +1 919 990 7500
www.reichhold.net

The company was founded by Henry Reichhold in 1927, went public in 1955 and in 1987 was
acquired as a wholly owned subsidiary by the Japanese company, Dainippon Ink & Chemicals with
whom there had been a licensee arrangement beginning in the 1950s. Reichhold’s global operations
involving 3,500 employees and current sales of $US1.2 billion, concern 27 plants throughout North
America, 2 in Brazil and 13 in Europe with, in addition, 2 European joint venture agreements. Over
the last 20 years Reichhold has made several important acquisitions:

• Swift Adhesives in 1985.


• Koppers polyester resin manufacturers in 1987.
• The coating resin business of Spencer Kellog in 1989 and Ashland Canadian in 1995.
• During 1995, the company organised its European operations, formed a strategic alliance with
BIP Chemicals, UK in 1996 – later acquiring their polyester resin business in 1998.
• In 1997 there was the acquisition of Lyons Coating and Jotun Polymer of Norway.

As a result, Reichhold European Composites is now the largest and most experienced supplier to
the composites industry in Europe, the Middle East and Africa. The operation involves more than
630 employees with sales offices in 12 countries.

Reichhold Global Operations has four areas of business:

• coating resins,
• synthetic latex emulsions,
• unsaturated polyester resin and
• adhesive products.

Arguably the major of these operations worldwide is the unsaturated polyester resin business and
the leading brand names are Norpol® and Polylite®. Indeed adding Dainippon Ink & Chemicals –
one of Japan’s most diversified chemical companies founded in 1908 and now employing 25,700
people – the Group is the world’s leading manufacturer of printing inks and unsaturated polyester
resins. Other polymers and polymer related products, specialty plastics and compounds, and
biochemical products made by the whole Group, must however not be overlooked. Consequently
the Group supplies essential materials to a wide range of industrial users around the world and the

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aim is to further strengthen that international position while contributing to both industry and
society with innovative products and technologies.

7.3.16 SCOTT BADER

Wollaston, Wellingborough, NN29 7RL, UK


Tel: +44 (0)1933 663 100, Fax: +44 (0)1933 664 592
E-mail: sales@scottbader.com, www.scottbader.com

The Scott Bader Company holds a unique position within the worldwide polymer industry. It is
governed by its employees. With no external shareholders Scott Bader is totally independent and
cannot be acquired.

It was the intention of the Swiss founders 80-years ago, to create a ‘commonwealth’ company,
where every employee shared in a full spirit of co-operation and partnership, the responsibilties and
privileges for all the company’s actions. Although those principles have been updated throughout
the company’s history to reflect social changes, the same basic tenets – the Scott Bader way of
working; taking responsibility; working for a better society and self governance - remain firm
throughout the 7 facilities now operating worldwide.

As pioneers in glass fibre composites since the 1940s, the Crystic® brand of technically superior
unsaturated polyester resins and gelcoats, have gained a worldwide reputation for quality and
reliability. This reputation has been maintained through on-going investment in research,
innovation and new product development. One recent example of which the company is proud, and
a world first, is the development of a gelcoat containing Microban®. This anti-bacterial protective
additive has been compounded with gelcoats that are designed to be employed for surface
applications in such environments as hospitals, residential homes, in food preparation units, in
transportation and in medical laboratories. The presence of the Microban® inhibits and minimises
the growth of bacteria and harmful odours, so preventing the growth of moulds and mildew.
Composite moulded shower trays are one initial product proving the worth of this additive.

The Scott Bader Company is equally recognised by other industries as a respected and specialist
manufacturer of water based emulsion polymers, inverse emulsions, alkyds, powder coating resins
and other solid resins, many being tailored like the Crystic® polyesters to ideally meet specific
customer needs.

7.3.17 SIKA AG

Zugerstrasse 50, CH-6341 Baar, Switzerland


Tel: +41 41 768 68 00, Fax: +41 41 768 68 50
E-mail: sikagroup@ch.sika.com, www.sika.com

Two divisions comprise the business and activity of the independent Swiss-based company, Sika
AG, founded in 1910. The Construction Division with involvement in the transport, infrastructure,
health, education, leisure, water and power markets, supplies concrete and mortar admixtures,
elastic sealants and adhesives, a wide range of sealing systems, as well as paints and coatings for
concrete and steel, plus surface finishes for general industry, and the transport and sport industries.

On the other hand, the Industry Division, with involvement in the transportation, building and ship
industries, as well as those companies supplying goods and materials to the domestic appliance and
equipment market, has concern with elastic adhesives, tooling resins, flooring materials and
acoustic products. Together, those divisions offer expertise in sealing, bonding, damping,
reinforcing and protecting. For example, the first can minimise the flow of gases or liquids, or the
heat/cold reaction between cavities, with the second connecting different materials permanently

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and powerfully. Damping aims to reduce the oscillations of all wavelengths in both fixed and
moveable objects, thereby reducing the noise emitted by cavities and load-bearing structures.
Where the latter are exposed to both static and dynamic loadings, then Sika’s expertise in
reinforcement comes into play with methods of increasing the protection of load-bearing structures
and preserving the appearance and condition of renovated components and surfaces.

Sika is a global company with a strong innovative tradition, comprising a total of around 80
production and marketing companies in 60 countries. There is activity in the field of specialty
chemicals and because the two divisions, construction and industry, serve largely different
industries or different industry sectors, then the company is better protected from the effect of
economic cycles than others. Overall the aim is to speak knowledgeably from experience and with
global understanding but with recognition of the local and geographical issues faced by their
customers. The response to those customers is quick, and in an approachable and friendly manner.

7.3.18 SP SYSTEMS

St Cross Business Park, Newport, Isle of Wight PO30 5WU, UK


E-mail: info@spsystems.com, www.spsystems.com

Composite materials offer many exceptional properties which are difficult or impossible to match
with traditional materials such as steel, aluminium and wood. Today, composites are used by
almost every dynamic, high performance structure whether on land, at sea or in the air. They allow
the design and manufacture of lightweight components or assemblies which can resist corrosion,
blast, fire, impact or other severe environmental conditions. Weight reduction often has a direct
effect on performance, leading to a compelling case for using these unique materials.

However, in order to achieve optimum results, specialist knowledge and skills are required. With
this in mind, SP offers not only a large range of high performance composite materials, based on
principally epoxy-based thermoset resins and allied products, but also a comprehensive range of
technical services. From research and development to structural engineering, from prototyping to
on-site support, SP aims to form partnerships with customers in order to provide a complete
composite solution. Innovative in its approach, SP is continually developing new materials and
processes that make composites more cost-effective and easier to use, thereby attracting the more
production-orientated industries such as wind energy, automotive and marine. Its multi-award
winning SPRINT® technology is typical of the innovation seen at SP (a multilayer prepreg for
vacuum-bag production of high-fibre content components). As well as working in three key
markets, SP has also shown its expertise in the engineering of composite architectural structures
such as the Expo 98 Bridge in Lisbon, a 30 m long bridge, weighing 6.3 tonnes. It is the integration
of expertise in structural design, process engineering and materials science on which SP has based
its reputation and success.

The Swiss industrial group Gurit-Heberlein has recently acquired SP Systems for US$75 million.
SP currently employ 380 people who generate sales of $90 million. The Chief Executive of Gurit-
Heberlein, Dr. Rudolf Wehrli stated that the deal will triple the size of its composites materials
activities and make it in competition with the US-based Hexcel and Cytec, the world’s third largest
supplier of advanced composite materials. Traditionally involved in the supply of prepreg materials
to the ski industry, Gurit-Heberlein moved into the aerospace sector two years ago, following the
acquisitions of Stesalit and AIK Elitrex. The deal is important from a technological perspective,
because it adds SP’s Sprint system to Gurit-Heberlein’s established materials spectrum. Originally
developed for the production of wind turbine blades, Sprint is proving attractive in more
commercial areas such as low-volume car body construction.

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7.3.19 VANTICO LIMITED

Duxford, Cambridge, CB2 4QA, UK


Tel: +44 (0) 1223 493 000, Fax: +44 (0) 1223 493 002
www.vantico.com

Vantico was created in December 1999 through the purchase of the Performance Polymers
Division of Ciba Specialty Chemicals by Morgan Grenfell Private Equity. Vantico’s stand alone,
independent Polymers Specialties Division comprises three carefully defined and value market
sectors – Coatings, Structural Composites and Electrical Insulation Materials – with in addition two
further divisions – Adhesives and Tooling, and Optronics. All have a heavy reliance on the
chemistry and technology of the four leading thermosetting resin systems – acrylic, epoxy,
phenolic and polyurethane.

Many of the companies registered trade names, such as Aradur, Aratherm, Arathane, Kerimide,
Matrimid, Quatrex and Tactix, are familiar throughout many sectors of industry, whilst the epoxy
adhesive Araldite is well known even to the general public. Others such as Cibatool, Epibond,
Epocast, Opalva, Parts in Minutes, Probimer, Probimage, Quinbeam, Ren, Staralign and Ureol have
more specialised users and customers.

All these products and technology are resulting in an ever-increasing range of applications from
microchips to snowboards, from DVDs to power transmission. The same products that keep
bridges standing and electricity supplies operating, also have applications in the home, in cars and
in the everyday lives of people across the world.

The Coatings sector offers a broad range of epoxy resins, hardeners, crosslinkers and matting
agents all with outstanding performance in a number of formulations. These have been developed
for protective and decorative coatings and employed, for example, on steel, concrete and stone, and
by the automotive, domestic appliance, can coating, civil engineering and marine industries.

In contrast, the Structural Composites sector manufactures a range of epoxy speciality materials
and high-value thermosets for employment as matrix materials in all manner of fibre-reinforced
components ranging from wind-energy blades, exterior and interior mouldings for railway carriages
and motive-power units, to aerospace, offshore, piping and recreational applications.

The Electrical Insulation Materials sector supports the electrical industry with customised products
for safeguarding generation, transmission, distribution and control of energy. Here the insulating
thermosets are employed for encapsulating low, medium and high voltage equipment as well as for
passive electronic devices, all using systems that offer excellent electrical and mechanical
properties, reliability, durability and performance under severe conditions.

Finally, the Adhesives and Tooling sector markets high performance engineering adhesives used
throughout manufacturing industry and also sold through DIY outlets, as well as a wide range of
plastic tooling solutions.

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8 Standards and Legislation

8.1 Standards

The following selection provides a useful indication of the comprehensive nature of the
authoritative standards to which the worldwide thermoset industry now works. It does not aim to be
a definitive listing. However, there are some thermosets or derivatives and related technology,
which still need to be standardised and there are existing standards which need drastic revision.
This is particularly true in the case of adhesives, coatings and sealants. Composite matrices and
their respective products fare much better.

As industry moves to ISO and CEN standards and away from national standards, many changes
and new standards are already in the pipeline.

Examples of British standards are shown in Table 8.1.

Table 8.1 British standards relating to thermosets


Standard Year Title
BS 771 1992 Specification for phenolic moulding materials.
BS 1203 2001 Hot-setting phenolic and aminoplastic wood adhesives.
Classification and test method.
BS 1204 1993 Specification for type MR phenolic and aminoplastic synthetic
resin adhesives for wood.
BS 2554 1999 Plastics. Unsaturated polyester resin. Determination of hydroxyl
value.
BS 2572 1990 Specification for phenolic laminated sheet and epoxy cotton fabric
laminated sheet.
BS 3816 1989 Specification for epoxy resin casting systems used for electrical
insulating applications at power frequencies.
BS 3900 Group J Testing of coating powders. 13 parts.
1998 J10: Determination of deposition efficiency of coating powders.
1998 J12: Determination of compatibility of coating powders.
BS 3953 1990 Specification for synthetic resin bonded woven glass fabric
laminated sheet.
BS 5442 Classification of adhesives for construction.
1979 3: Adhesives for use with wood.
BS 5664 Solventless polymerisable resinous compounds used for electrical
applications.
1988 2.2: Methods of test. Coating Powders.
3 Specification for individual materials.
1995 3.1: Unfilled epoxy resinous compounds.
1997 3.2: Quartz filled epoxy resinous compounds.
1995 3.3: Unfilled polyurethane compounds.
1995 3.4: Filled polyurethane compounds.
1995 3.11: Epoxy resin-based coating powders.

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British/European Norm standards are listed in Table 8.2.

Table 8.2 British/European Norm standards relating to thermosets


Standard Year Title
BS EN 301 1992 Adhesives. Phenolic and aminoplastic, for load-bearing timber
structures, classification and performance requirements.
BS EN 923 1998 Adhesives - Terms and Definitions.
BS EN 1240 1998 Adhesives. Determination of hydroxyl value and/or hydroxyl content.
BS EN 1242 1998 Adhesives. Determination of isocyanate content.
BS EN1373 2000 Adhesives. Test method for adhesives for floor and wall coverings.
Shear test.
BS EN 1770 1998 Products and systems for the protection and repair of concrete
structures. Test methods.
BS EN 12003 1998 Adhesives for tiles - Determination of shear adhesion strength of
reaction resin additives.
BS EN 12192 Production and systems for the protection and repair of concrete
structures - test methods. Granulometry analysis.
1999 2: Test methods for fillers for polymer bonding agents.
BS EN 12963 2001 Adhesives. Determination of free monomer content in adhesives based
on synthetic polymers.
BS EN 14530 Plastics. Unsaturated polyester powder moulding compounds.
2000 1: Designation system and basis for specification.
2000 3: Requirements for selected moulding compounds.
BS EN 60893 Specification for industrial rigid laminated sheets based on
thermosetting resins for electrical purposes.
1995 1: Definition, design and general requirements.
3: Specification for industrial materials.
2000 2: Requirements for rigid laminated sheets based on epoxide resins.
1995 3: Requirements for rigid laminated sheets based on melamine resins.
1995 4: Requirements for rigid laminated sheets based on phenolic resins.
1995 5: Requirements for rigid laminated sheets based on polyester resins.
1995 6: Requirements for rigid laminated sheets based on silicone resins.
1995 7: Requirements for rigid laminated sheets based on polyimide resins.
BS EN 61249 Materials for interconnection structures. Sectional specification set for
unreinforced base materials, clad and unclad (intended for flexible
printed boards).
1999 3-3: Adhesive coated flexible polyester film.
1999 3-4: Adhesive coated flexible polyimide film.

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British/European/International standards are listed in Table 8.3.

Table 8.3 British/European/International standards relevant to thermosets


Standard Year Title
BS EN ISO 2535 1998 Plastics. Unsaturated polyester resin. Determination of gel time at
25 °C.
BS EN ISO 3672 Plastics. Unsaturated polyester resins.
2001 1: Designation system.
2001 2: Preparation of test specimens and determination of properties.
BS EN ISO 3673 Plastics. Epoxide resins.
2000 1: Designation.
2000 2: Preparation of test specimens. and determination of properties.
BS EN ISO 10363 1995 Hot-melt adhesives. Determination of thermal stability.
BS EN ISO 11908 1998 Binders for paints and varnishes. Amino resins. General methods of
test.
BS EN ISO 11909 1998 Binders for paints and varnishes. Polyisocyanate resins. General
methods of test.
BS EN ISO 14526 Plastics. Phenolic powder moulding compounds (PF-PMCs).
2000 1: Designation system and basis for specification.
2000 2: Preparation of test specimens and determination of properties.
2000 3: Requirements for selected moulding compounds.
BS EN ISO 14527 Plastics. Urea-formaldehyde and urea/melamine-formaldehyde
powder moulding compounds.
2000 1: Designation system and basis for specification.
2000 2: Preparation of test specimens and determination of properties.
2000 3: Requirements for selected moulding compounds.
BS EN ISO 14528 Plastics. Melamine-formaldehyde powder moulding compounds.
2000 1: Designation system and basis for specification.
2000 2: Preparation of test specimens and determination of properties.
2000 3: Requirements for selected moulding compounds.
BS EN ISO 14529 Plastics. Melamine phenolic powder moulding compounds.
2000 1: Designation system and basis for specification.
2000 2: Preparation of test specimens and determination of properties.
2000 3: Requirements for selected moulding compounds.
BS EN ISO 14530 Plastics. Unsaturated-polyester powder moulding compounds.
2000 1: Designation system and basis for specification.
2000 2: Preparation of test specimens and determination of properties.
2000 3: Requirements for selected moulding compounds.
BS EN ISO 14656 1999 Epoxy powder and sealing material for the coating of steel for the
reinforcement of concrete.
BS EN ISO 14896 2001 Plastics. Polyurethane raw materials. Determination of isocyanate
content.
BS EN ISO 15252 Plastics - Epoxy powder moulding compounds (EP-PMC’s).
2000 1: Designation system and basis for specification.
2000 2: Preparation of test specimens and determination of properties.
2000 3: Requirements for selected moulding compounds.

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Table 8.4 lists British/International standards relating to thermosets.

Table 8.4 British/International standards relating to thermosets


Standard Year Title
BS ISO 14615 1997 Adhesives. Durability of structural adhesive joints. Exposure to
humidity and temp under load.
BS ISO 14564 1999 Epoxy-coated steel for the reinforcement of concrete.
BS ISO 14656 1999 Epoxy powder and sealing material for the coating of steel, for the
reinforcement of concrete.
BS ISO 14848 1998 Plastics. Unsaturated polyester resins. Determination of reactivity at
130 °C.
BS ISO 15509 2001 Adhesives. Determination of the bond strength of engineered plastic
joints.

ASTM standards also cover thermosets (Table 8.5).

Table 8.5 ASTM standards relating to thermosets


Standard Year Title
ASTM D1763 2000 Standard specification for epoxy resin.
ASTM D1201 1999 Standard specification for thermosetting polyester moulding compounds.
ASTM D3841 2001 Standard specification for glass-fibre reinforced polyester plastic panels.
ASTM D2291 1998 Standard practice for fabrication of ring test specimens for glass-resin
composites.

International standards of relevance to thermosets are shown in Table 8.6.

Table 8.6 International standards relating to thermosets


Standard Year Title
ISO 291 1997 Plastics. Standard atmospheres for conditioning and testing.
ISO 2114 1996 Plastics. Unsaturated polyester resins. Determination of partial acid
value and total acid value.
ISO 2535 1997 Plastics. Unsaturated polyester resins. Measurement of gel time at 25
°C.
ISO 2554 1997 Plastics. Unsaturated polyester resins. Determination of hydroxyl value.

French standards covering thermosets are included in Table 8.7.

Table 8.7 French standards relating to thermosets


Standard Year Title
NF EN ISO 291 October 1997 Plastics. Standard atmosphere for conditioning and testing.
NF EN ISO 9371 September Plastics. Phenolic resins, liquid or in solution, determination
1995 of viscosity.
NF EN ISO 8988 April 1997 Plastics. Phenolic resins, determination of HTMA content by
the Kjeldahl method.
NF EN ISO 2114 March 1997 Plastic materials. Unsaturated polyester resins, determination
of acid value.
NF EN ISO 4583 July 1998 Plastics. Epoxy resins and related materials, determination of
easily saponifiable chlorine.
NF ISO 1628-6 September Plastic materials. Methylmethacrylate polymers and
1993 copolymers, determination of the viscosity number in dilute
solution.

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German standards of relevance to thermosets are listed in Table 8.8.

Table 8.8 German standards relating to thermosets


Standard Year Title
DIN EN ISO 295 October 1998 Plastics. Compression moulding of test specimens of
thermosetting materials.
DIN EN ISO 14125 June 1998 Fibre-reinforced plastic composites, determination of
flexural properties.
DIN EN ISO 899 Plastics. Determination of creep behaviour.
March 1997 1: Tensile creep.
March 1997 2: Flexural creep by three-point loading.
DIN EN ISO 846 October 1997 Plastics. Evaluation of the action of microorganisms.

Japanese standards also cover thermosets (Table 8.9).

Table 8.9 Japanese standards relating to thermosets


Standard Year Title
JIS K 7118 1995 General rules for testing fatigue of rigid plastics.
JIS K 6901 1995 Testing methods for liquid unsaturated polyester resins.
JIS K 6911 1995 Testing methods for thermosetting plastics.
JIS K 7201 1995 Testing method for flammability of polymeric materials using
the oxygen index method.

8.2 Legislative Matters

The growing need to safeguard the environment, not just nationally but internationally, has caused
all major chemical manufacturers and processors to recognise increasingly the mandatory
regulations under which they are required to operate. Indeed, many have had close concern with
compiling, if not even instigating, those regulations and the thermoset resin industry sector is
certainly no exception.

Taking a typical example, Cray Valley, like every major unsaturated polyester resin manufacturer,
has voiced its commitment to environmental protection and recycling issues in developing a range
of low-styrene emission resins and the use of heavy-metal free pigmented gel coats. In terms of
emissions from the fabricator’s shop, the company has also had close involvement in extending the
technology of the main closed-mould moulding techniques such as RTM and resin infusion
techniques. The potential of these processing techniques to offer realistic reductions in levels of
VOC emissions is equal, if not greater than that resulting from the initial use of low emission resin
systems, however they may be formulated.

In addition, as a member of the European Eurcom Programme, Cray Valley has investigated the
reuse of waste from glass fibre reinforced components, whether arising from production or from
those components that have reached the end of their service life. This work has, for example,
examined the use of fibrous powder additions to bitumen coating applications, or enzymatic
breakdown techniques enabling some measure of cost-effective raw material recovery. In fact, as
considered further in Chapter 9, the disposal of waste emanating from any thermoset resin
production or downstream activity is a problem which has the potential to impact on the
environment to a very much greater degree than any VOC emission.

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8.2.1 Chemical Emissions

The aim of ever greater reductions in organic solvent emission remains the main driving force
behind increasing legislation, a move prompted by some sectors of the general public in
conjunction with relevant health authorities. Most, if not all applicable solvents possess a strong
smell and a heavy vapour and are therefore unpleasant. Some are toxic to a greater or lesser degree
and others may be carcinogenic. To the general public solvents are a particular anathema.
Consequently, although there may be a need to continue to employ volatile solvents within
thermoset resin formulations, the increasing demand to reduce or even totally eliminate VOC
emissions has begun to result in a change to waterborne or solventless resin systems where the
chemistry will so permit. Occasionally, this can also be a change with other benefits such as cost
and improved productivity. There is frequently a need for major changes to the equipment
employed. Organic solvents disperse with relative ease at low temperature whilst water demands
greater energy input if its removal is to be achieved within an acceptable timescale. The source of
this energy will usually create extra pollution in itself since, ultimately, it will probably be
generated by burning a carbon fuel such as oil, coal or gas.

The European Council of Environmental ministers through such statuary documents as the
Integrated Pollution Prevention and Control Directive and the Dangerous Substances and
Dangerous Preparations Directive, agreed several years ago that, by 2007, VOC emissions should
be 70% lower than in 1990. It is hoped that such an idealistic figure is achievable and that the
problems of greenhouse gases will thus be much reduced. The reduction of solvent use in industries
connected with thermosetting resins will help the move towards this goal. However, whatever
means are put in place to reduce solvent emissions, e.g., water borne systems, they must be cost
effective and practical. In the words of a recent statement by the European Solvents Industries
Group, the measures ‘must not impact adversely on another industry and must also consider the
total life of the product’. Uninformed political interference with technical matters can be a
dangerous thing.

An example of this in the thermosets industry is the potential banning of the use of very low ozone
depleting HFCs as blowing agents in thermosetting foams. If some foams are made with alternative
blowing agents, their efficiency as thermal insulation materials may be seriously compromised. The
result would be an increase in the production of greenhouse gases resulting from increased fuel use
during the life of the insulated building. However, research is being undertaken to find acceptable
alternative blowing agents.

Of all the volatile organic compounds associated with thermosetting resins, perhaps the one most
often discussed is styrene. Styrene is used as a reactive diluent in the cure of polyester and vinyl
ester resins and is not simply a solvent. ‘Styrene free’ polyesters can be formulated but the system
will contain an alternative organic compound. Styrene can be metabolised to an epoxide structure,
styrene oxide, and some such structures have previously been linked to carcinogenity. However, a
45 year study of some 55,000, often high-exposure, unsaturated polyester resin workers in both the
USA and Europe, failed to show any connection between that exposure and the incidence of
cancer.

Recent years have seen industry reviews and in turn reductions in, the allowed occupational
exposure to styrene throughout the composites industry. Those permitted levels vary considerably
from country-to-country. In Germany, Scandinavia and the Benelux countries, the limit is 20 ppm,
whereas other European member countries, even those more extensively employing closed-mould
techniques, allow 50 ppm. The latter is regarded as a permitted atmospheric shopfloor level for
styrene which both the European Composites Industry Association and European Chemical
Industry Council (CEFIC) favour as being respectable, reasonable and more importantly, within
low-cost reach of all composites moulders. In Southern and Eastern Europe and in the UK, where
open-mould techniques remain favoured, the exposure limit is 100 ppm.

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Styrene is just one of many substances undergoing an EU Existing Substances Regulations review.
The UK Health and Safety Executive is also drafting a risk assessment report that considers the
risks of worker and consumer exposure to styrene. Should either show cause for concern, there
would, no doubt, be an urgent review of the EU Dangerous Substances classification and
occupational exposure limits.

The use of thermosetting resins in solution, true solution as opposed to the styrene situation of an
active diluent, is one of the oldest of technologies. Phenolic novolaks have been applied in solution
to foundry sand for decades and the solvent (usually alcohol) evaporated off. Solutions of phenolic
resols, ureas and melamine resins in ketones or alcohols are used to impregnate paper, cloth and
other continuous materials in the manufacture of prepreg for the high pressure laminating industry.
Legislation now prevents the ‘loss’ of these solvents to the atmosphere and today it is a legal
requirement to fit complicated and expensive burners and catalytic systems to exhausts to minimise
atmospheric pollution.

Many, if not all of the raw materials employed by the thermoset resin industry are toxic to a greater
or lesser degree. Acceptable and justifiable legislation is therefore in place and is under continuous
review, regarding the safe handling, storage, exposure, and use of each one.

The ultimate disposal, whether as production waste or redundant component but particularly of
waste raw materials, is becoming an increasingly important issue. Disposal has the potential to be
damaging to the environment and it is therefore a serious long-term issue. Legislation on disposal
of waste is in the news every day.

There are however, some good things to note about the polymer industry in general and the
thermoset sector in particular. Macromolecules are less likely to affect biological processes than
smaller ones. Hence, thermosets are very different from thermoplastics in that they usually start
processing as low molecular weight polymers, which may contain toxic species, but become totally
intractable fully crosslinked masses, which are most often harmless. There are plenty of FDA
approved phenolics, polyesters, melamines, ureas, etc. The isocyanate starting materials for the
production of polyurethane are, as mentioned elsewhere in this study, hazardous to health before
reaction to produce thermoset polyurethane and there are regulations governing the control and
handling of these and other hazardous substances in most countries.

8.2.2 Fire Hazards

One area of legislation, which affects the use of all materials, is that concerning fire properties of
materials used in every day life. Polyurethanes can yield highly toxic smoke in fires and give off
copious quantities of smoke. Likewise polyesters and epoxies give large amounts of smoke and, if
halogenated to improve fire performance, can also give toxic gases when involved in a fire.
Phenolic resins are probably the least harmful in this respect, giving very low levels of smoke and
toxic gases. The laws governing such applications vary from country to country but are usually
covered by building regulations, or codes for buildings, and regulations or laws for transport
vehicles. Aircraft materials are controlled by the US Federal Aviation Administration (FAA), the
UK Civil Aviation Authority (CAA) and similar bodies.

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9 Environment and Recycling

9.1 Introduction

To ensure the health and safety of every worker involved, in whatsoever capacity, in the thermoset
resin industry, their manufacture, storage, use and disposal has to be and is governed by a number
of mandatory rules and regulations. Some starting materials for thermosetting resin systems are
toxic (e.g., isocyanates, phenol) and the greatest care must be taken at all stages when the toxic
species is still present. Much legislation also applies to the vast range of different products,
adhesives, sealants, coatings, paints, resins, etc., which are manufactured from these thermoset
materials and, hence, also to their respective uses and applications. Equally, different levels of
legislation may also be exercised by different countries, different governments and different
authoritative bodies. Care must be taken at all times to ensure compliance both with local and
international regulation and with the manufacturer’s instructions for these materials and to apply
common sense and responsibility in their disposal.

Throughout this study there has been emphasis on the outstanding long-life properties and
resistance to temperature, chemical, corrosion and other conditions, offered by the range of product
manufactured from thermoset resins. Thermosets are by nature, irreversible, infusible, non-
degradable materials. In terms of environmental protection, therefore, it is axiomatic that the
ultimate disposal of these products, present either as production waste or as redundant components,
poses a different, but equally large problem, to that which occurs at any earlier manufacturing or
application stage. For example, the resins and starting chemicals may be toxic. However, many of
these materials and small molecules do degrade with time or may be reacted away to safe materials.
The fully cured thermoset resins and products are usually fairly inert chemically and do not
degrade. The fact that they are macromolecules renders them generally safe from the toxicity
standpoint but many may yield undesirable chemicals if burnt. Hence the question, “What do we do
with end of life thermoset materials?” A measure of the magnitude of that problem is the 27 million
tonnes of thermoset resins currently consumed annually.

Irrespective of the legislation now governing both material and product disposal in, for example,
landfill sites, an ability to recycle both production waste and redundant components in an economic
and useful manner, must offer the opportunity to resolve a large proportion of the problem.
Because a thermoset resin, as a finished product is chemically different from the staring materials
from which it was made, it cannot be ‘returned to source’.

Adhesives, sealants, paints, lacquers and other coatings, for example, offer no possibility of reuse
whatsoever. There are in fact only a few categories of thermoset products which do allow
collection and hence some hope of environmentally friendly disposal. These include thermoset
composite mouldings, electrical laminates and other industrial laminates, friction materials and
tyres. The latter, although containing small percentages of thermoset materials such as phenolic
resins and, as a result of the size of the industry, a large tonnage thereof, are not really the subject
of this study. The rubber industry, although thermoset by nature, is not included here. There are
only two sectors which have received careful study in terms of recycling: composite mouldings and
polyurethanes.

9.2 Composites Recycling

Over the last 10 years the worldwide composites industry has increasingly recognised the need to
dispose of both its production waste and redundant components by other methods than landfill. At
the same time, although that waste poses no direct toxicity problem to the natural environment, the
landfill method of disposal is beginning to come under severe constraints simply because of the
cost and the increasing volume involved. Obviously as the market for composites increases further,
as it undoubtedly will, so will the volume of production waste and with time, the number of

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redundant components. At the same time, for the industry to be seen as concerned about the
disposal of its waste and products will have clear advantage in the future acceptance of composites
generally. Furthermore, the landfill life of composite waste is measured in centuries rather than
decades.

Three quantifications are sufficiently indicative of the measure of the problem. In the early 1990s
the Norwegian government estimated that, at some future date, some 700,000 fibre reinforced
composite pleasure boats located around its coastline would need to be recycled or effectively
disposed of. That examination took no account of probably a smaller number of larger work and
fishing boats. Although little appears to have been published since, the Norwegian arm of
Reichhold were collaborating with the Swedish composites moulding equipment manufacturer
Aplicator AB, in developing recycling solutions [1].

In 1998, the Japanese Reinforced Plastics Society attempted a similar quantification, deciding that
at that time there was a need to dispose of some 282,000 tonnes annually. Several years earlier the
annual quantity of production waste of the American composites industry was estimated at some
22,300 tonnes or around 450 tonnes per annum per state [2].

The urgent need for alternative means of waste disposal, now increasingly recognised as being
potentially more damaging to the long-term future of the worldwide composites industry than the
styrene emission problem, has prompted the development of several recycling techniques. None to
date can be said to provide a truly commercial cost-effective answer commensurate with the
tonnages concerned. For example, producing thousands of tonnes of fine filler is no answer. As a
consequence the worldwide composites industry still needs to develop the ultimate solution.

9.2.1 The Japanese Approach

In 1991 the Japanese Government passed a new recycling law. Such was its potential severity, that
the FRP Waste Committee, first established in 1974 by the government recognised trade body of
their composites industry, joined forces immediately with a similar recycling committee of the
Japan Thermosetting Industry Association (JTPIA). There were two objectives, to investigate
viable solutions and then promote the construction of optimum plants for dealing with the problem.
Seven years later, the former body formally established a promotion centre for FRP Recycling. At
about the same time the Japanese Ministry of International Trade and Industry began investigating
the large-scale recycling of thermosetting resins by a liquid-phase decomposition process initially
developed by the country’s National Institute for Resource and Environment. Other authorities and
companies such as Clean Japan Centre and Takeda, Kubota and Mitsubishi Heavy Industries, have
also had their input.

Overlooking the related problems of first classifying, breaking up and sorting the waste to be
recycled, five different procedures were investigated in depth. All have to a larger or lesser degree
proved successful, but as yet no one universal or optimum technique stands out. Each presents
particular advantages and disadvantages, as well as different economics and, as a consequence, the
development work continues.

In a similar manner to the Ercom and Valcor approach to be discussed later, the Japanese judged a
granulation and pulverisation process producing a fine recyclate powder for use as a filler for
moulding compounds or cement roof tiles, to have favourable possibilities. However, preferred and
consistent results are seemingly dependent on an initial careful selection of the waste.

Much less dependent on the quality and type of waste employed, is the thermal decomposition or
incineration technique, where the heat generated is employed in some form of localised district
heating system. Two basic problems exist. Dependent on the waste, there can be a problem keeping
the incinerator burning efficiently, but the major problem is the eventual need to dispose of the
resulting large quantity of a low bulk density waste ‘ash’.

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In a technique which completely overcomes the latter problem, a ‘cement process’ has been studied
by several sectors [3]. Here the idea is to process the waste in cement kilns, such that the
thermosetting resin acts as the fuel, with the glass fibre and filler which is left contributing to the
mineral additive of the cement. It is believed that the process does hold real promise, to be adopted
eventually as the major and preferred recycling technique.

The Japanese have also shown that the thermal decomposition, or controlled pyrolysis, of
composites waste has the ability, when certain unspecified metal ‘catalysts’ are employed, to
produce viable quantities of a reuseable ‘oil’ and a separate clean glass fibre residue. This ‘oil’ can
apparently be introduced into the crude oil chain and the glass fibre re-employed in certain
composite mouldings. Similar development work has been undertaken in both Canada and the
United Kingdom, but that in Canada, which was supported by the glass reinforcement producer
Owens Corning, was discontinued some years ago.

Finally, there is the ‘hot water decomposition process’ where the waste material is heated in steam
at 300-500 °C to produce, through partial hydrolysis, phthalic acid, styrene, oil and a glass fibre
containing char, which is, presumably, unusable. However, it has also been reported that the
alternative use of supercritical water from a thermal power plant, results in a clean and effective
hydrolysis and decomposition, without any char remaining on the fibre [4]. The full economics of
the latter have yet to be established.

In a concluding comment, applicable to virtually any composites or other material recycling


technique, there is likely to be a need to sort the waste carefully into composite ‘categories’, e.g.,
polyester, epoxy or phenolic based, for suitable processes to provide optimum solutions. This is
seen as a serious disadvantage.

9.2.2 The French/German Approach

The work of the Ercom group in Germany and the Valcor Association (in partnership with Mecelec
Composites et Recyclage) in France [5] has been well publicised. Much more restricted in
approach, it concerns itself solely with the recycling of well-identified composites waste, i.e.,
principally end-of-life hot-press moulded automotive components (SMC, BMC/DMC). The project
grew out of the need for the car industry in particular to answer new legislation regarding the
disposal of its waste. The chosen route was to granulate and pulverise the waste into powdered
filler that could be re-used, at a low-weight percentage, as an additive to virgin hot-press moulding
compounds.

The process has the merits of being a commercial, if somewhat restricted, success. It is also a novel
technique in that it includes the difficult task of sorting the waste prior to collection and treatment.
Current plant capacity is limited and, unfortunately, no other use has been found for the product.
Indeed the major criticism voiced for the process is that it seems to be a costly way of producing
granular filler, even if that filler contains some viable, if very short, reinforcement. Mineral fillers
are widely available and cheap.

Indeed, that is seemingly the view of the French vehicle manufacturer, Renault, a company noted
for showing its responsibility towards environmental issues and thus in the recycling of end-of-life
vehicles. Over recent years the company has been steadily reducing the proportion of thermosetting
hot-press moulded components employed, in favour of thermoplastic-based composites mouldings
[6]. Whilst recycling the latter is certainly not without major problems, at the present moment those
are seen as much less difficult to deal with.

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9.2.3 The Canadian Approach

As well as the Owens Corning attempt with a pyrolysis-based technique, several years ago, an
Ontario-based company investigated and, to a limited extent, commercialised an apparently much
more lateral and better approach to the recycling or reuse of waste composites. The technique
involved the granulation, to a coarse particle size, of all and every type of composites waste and,
after blending with an unspecified binder, the low-pressure moulding of a range of new
components. These ranged from garden seats and park benches to decorative artefacts and facing
panels for building applications. With the development of a much wider product range, perhaps for
infrastructure application, the process appeared to have the opportunity of consuming high
tonnages of waste from moulders and fabricators (free of charge) as well as end-of-life products.

9.3 Recycling of Polyurethane

As already implied, any recycling process is only economic, and therefore successful, if there is a
sufficient quantity of material to be recycled but, of greater importance, that material must also be
of consistent quality. Thermosetting polyurethane, because of the large tonnage consumed and
ultimately available for disposal, albeit in a number of distinct finished product forms, falls into
this category. Consequently, arguably more commercial polyurethane recycling processes have
been developed than for any other thermoset material. All have been based on a chemical or
glycolysis technique. Typically the recyclate has sufficient functionality so that after mixing with
highly functional polyols, it is practical to produce new, stable foam structures exhibiting
acceptable mechanical and physical properties. In America polyurethane recycling developments
are being co-ordinated by the PU Recycling and Recovery Council, the American Plastics Council
and others.

Bayer also has a process involving high pressure and temperature (180 °C) for recycling granulated
crosslinked polyurethanes from production and mouldings waste as well as damaged or redundant
car body parts. Although the original tensile strength is reduced by some 50% and the elongation to
around 15%, the end-product is understood to be suitable for use in wheel arch linings, battery
covers and panelling for chassis members.

Other companies noted as being involved are BASF in America and Regra Recycling GmbH in
Germany. BASF uses an ambient pressure, moderate temperature process suitable for both rigid
and semi-rigid applications, and second-generation glycolysis chemistry producing recyclate with a
residual amine content of less than 0.1%. Regra, on the other hand, separates the waste into
different types to produce high-quality recyclate polyols which are sold to approved recycling
customers or reformulated for their own internal use. For companies with at least 100 tonnes of
waste per year, Regra can also offer complete recycling units, known as RCA 1000 plants, along
with all the operating technology required.

References

1. Composites, 1999, 35, Sept/Oct, 57.

2. T.F. Starr, Recycling: A Lateral View, 48th Annual Conference, Composites Institute, SPI,
February 1993.

3. K. Nomaguchi, S. Hayashi and Y. Abe, A Solution for Composites Recycling Cement Process,
Proceedings of CFA ‘Composites 2001’, Tampa, FL, USA.

4. Composites, 1999, 35, Sept/Oct, 58.

5. A. Marion, Composites, 1999, 35, 49.

6. A. Disoine, Composites, 1999, 35, 40.

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Glossary of Terms
B-Stage An intermediate stage in the production of a thermosetting resin where
the polymerisation has proceeded to where the resin is solid but total
cure has not been achieved.

Crosslinking The reaction by which two dimensional polymer chains join to become
a completely linked, three-dimensional structure. This reaction is also
referred to as cure.

Flowcoats (or flocoats) A thinner coating than a gelcoat, typically of pure unreinforced, but
sometimes pigmented, thermoset resin, used to provide a protective
rather than a decorative finish.

Gelcoats A layer of resin, usually pigmented but not reinforced, applied to the
exposed face of a composite moulding by application to the moulding
tool prior to the composites lay-up. This resin rich layer, usually 0.4 to
0.9 mm thick, provides the ultimate surface of the moulding and may
be high gloss, textured or copy the tool surface to which it is applied.

Laminate A term applied, irrespective of thickness, to the construction of a


reinforced thermoset resin where the reinforcement is in sheet or
‘lamina’ form. This may be a glass reinforced polyester moulding, a
carbon/epoxy moulding, a high pressure pressed sheet of
paper/phenolic for use as a printed circuit board or one of thousands of
other possible combinations of resin and reinforcement.

Moulding compound A fully formulated mixture of resin, reinforcement, filler and catalyst if
necessary, usually pigmented and in the form of a powder, pellets,
sheet or dough. The reinforcement is usually short although it can be
long (up to 5 cm) in sheet moulding compound. Resins used in this way
include phenolics, aminos and polyester. Cure is usually at elevated
temperature, under pressure between metal tools. Sometimes called a
pre-mix.

Novalak A resin formulated with a reduced amount of one monomer so that it is


not of a chemical structure to allow crosslinking without the addition of
further reactant. For example, a phenolic resin with a formaldehyde to
phenol molar ratio of less than one is a novolak resin and can be cured
only by the addition of further formaldehyde from a formaldehyde
donor such as hexamethylenetetramine. The term novolak is normally
applied only to phenolics, aminos and epoxies.

Potlife The workable life of a thermosetting resin or adhesive after the addition
of the catalyst or other chemical agent used to promote polymerisation.

Prepreg A fabric or other sheet material pre-impregnated with resin and taken to
a B-stage. The sheet material can be paper, woven glass, carbon,
aramid or cotton cloth or a large number of other forms. The most
common resins for prepregs are phenolic and epoxy.

Reactive diluent A chemical in which a resin is dissolved, partly to make it workable


and partly to supply essential chemical activity to enable crosslinking.
The most common example is styrene used to form the crosslinks when
curing unsaturated polyesters.

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Resin infusion A family of processes for the production of composites in which the
resin system is infused through the reinforcement which has previously
been placed in a tool or mould. The motive force for the resin moving
through the reinforcement is a pressure differential between the mould
cavity and the resin. The modern use of the term usually applies to a
process where the mould is under vacuum and consists of one rigid tool
and a flexible counter-tool.

Resin transfer moulding An early, and still very popular, resin infusion process where the resin
is forced under pressure into a pair of matching closed, rigid moulds in
which the reinforcement has already been placed.

Resol A thermosetting resin in which all the molecular structure is present to


achieve cure. For example, a phenolic resin in which the molar ratio of
formaldehyde to phenol exceeds one is a resol resin which can be cured
by the application of heat alone. The term is usually applied to phenolic
and epoxy resins.

Solvent A non-active diluent used to allow a resin which is either highly


viscous or solid to be applied. Many solid phenolic and epoxy resins
are supplied in solution to enable the manufacture of prepregs, etc.

Thermoset A resin, or the basic formulation within a coating or for example an


adhesive, which on polymerisation, changes to an irreversible,
infusible, environmentally-resistant state.

Two-component system A thermoset resin supplied as two components which react on mixing
in the correct ratios. As a simple example, half the resin may be
supplied with an initiator added and the other half with an accelerator.
When mixed in the correct ratio, the accelerator will react with the
initiator and start the crosslinking reaction.

VOC Volatile organic compound, a term applied to any organic material


which has a sufficient vapour pressure under normal ambient
conditions to evaporate into the atmosphere, or which is treated in a
manner which will cause it to evaporate. The term has become
synonymous with concerns about global warming and other
environmental issues since many such organic compounds are
greenhouse gases.

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Abbreviations and Acronyms


ASTM American Society for Testing and Materials
AVK-TV German Reinforced Plastics Association and Technical Union
BMC bulk moulding compound
BMI bismaleimide
BS British Standards
CAA Civil Aviation Authority (UK)
CBT cyclic butylene terephthalate
CEFIC European Chemical Industry Council
CFA Composites Fabricators Association
ClCN cyanogen chloride
DCPD dicyclopentadiene
DGE-BA diglycidyl ethers of bisphenol A
DGE-BF diglycidyl ethers of bisphenol F
DIN Deutsche Institut fur Normung
DIY do-it-yourself
EEW epoxy equivalent weight
EMB electromagnetic brush
EMM epoxy molar mass
EN European Norm
EPN epoxy novolak
ERMA European Resin Manufacturers’ Association
FAA Federal Aviation Administration (US)
FDA Food and Drug Administration (US)
GMA glycidyl methacrylate
GMT glass mat thermoplastic
HDI hexamethylene di-isocyanate
HDT heat deflection temperature
hexa hexamethylenetetramine
HTM high temperature moulding
IMS Integrated Management System
ISO International Standards Organization
JTPIA Japan Thermosetting Industry Association
LPMC low pressure moulding compounds
LSE low styrene emission
MBR Mine Bolt & Resin System
MDF medium density fibreboard
MDI Diphenylmethane di-isocyanate
MMA methyl methacrylate
NF French Norm
NPG neopentyl glycol
PES polyethersulphone
PMC powder moulding compound
ppm parts per million
PPO polyphenylene oxide
PSF polysulphone
PU polyurethane
PUR polyurethane rubber
RIC runnerless injection compression
RIFT Resin Infusion under Flexible Tooling
RRIM reinforced reaction injection moulding
RTM resin transfer moulding
SCRIMPTM Seeman Composites Resin Infusion Moulding Process
SG specific gravity

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SMC sheet moulding compound


SPI Society of the Plastics Industry
SRIM structural reaction injection moulding
TBBA tetrabromobisphenol A
TDI toluene di-isocyanate
Tg glass transition temperature
TGIC triglycidyl isocyanurate
UP unsaturated polyester
UV ultraviolet
VOC volatile organic compound
WPE weight per epoxy

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Rapra Technology Limited


Rapra Technology is the leading independent international
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Rapra publishes books, technical journals, reports,


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Shawbury, Shrewsbury, Shropshire SY4 4NR, United Kingdom


Telephone: +44 (0)1939 250383 Fax: +44 (0)1939 251118
http://www.rapra.net e-mail: info@rapra.net