Understanding Coatings Raw Materials E-Book

Vijay Mannari

• Herausgeber: Vincentz Network
• Kategorie: Wissenschaft und neue Technologien
• Serie: European Coatings LIBRARY
• Sprache: Englisch

Seitenzahl: 360

Veröffentlichungsjahr: 2015

Beschreibung

What are paints and coatings composed of? This efficient reference book offers an optimum overview of the different constituents of the different types of coatings, explaining the chemistry, system and impacts of coating raw materials. That way, newcomers to the field of coatings gain a quick basic knowledge whereas chemists and laboratory assistants will find valuable insights on future trends and developments in the field of raw materials.

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Vijay Mannari | Chintankumar J. Patel

Understanding Coatings Raw Materials

Cover: Sebastian Duda/Fotolia

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Vijay Mannari, Chintankumar J. Patel

Understanding Coatings Raw Materials

Hanover: Vincentz Network, 2015

European Coatings LIBRARY

ISBN 3-86630-603-2

ISBN 978-3-86630-603-5

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EUROPEAN COATINGS LIBRARY

Vijay Mannari | Chintankumar J. Patel

Understanding Coatings Raw Materials

Foreword

The coating industry is highly raw material intensive and uses a wide range of these raw materials, from relatively inexpensive minerals to high performance polymers and pigments to highly engineered specialty additives. Understanding Coatings Raw Materials intends to provide a comprehensive overview of the raw materials used in contemporary paints and coatings.

Significant advances have been made in the field of polymeric materials and coatings during the past few decades. Ever since the negative impacts of solventbased coatings on the environment and human health were recognized, the coating industry has been striving not only to address these impacts but also to offer better performing products to meet the ever growing demands to decorate, protect, and provide new functionalities to surfaces. This has led to the emergence and commercialization of such advanced technologies as waterborne coatings, high-solid coatings, powder coatings, radiation curable coatings, and bio-based as well as nanomaterial based coatings, to name a few. The raw materials used in today’s advanced coatings are incredibly diverse and innovative compared to those used a few decades before. Understanding this growing palette of coating raw materials and their specific roles and interactions with each other is increasingly challenging, both for new entrants as well as those already working in the coating industry.

This book is divided into five chapters. The first chapter introduces readers to the historical development and fundamentals of coatings and their compositions, thus putting the topics that follow into perspective. The following chapters cover individual families of raw materials – resins, pigments and extenders, solvents and additives – with adequate detail and practical examples in keeping with the scope of this book.

This book in hand is intended for people involved in sectors of the industry related to research and product development, production, quality assurance and testing, the supply chain, coating system specifications, technical service and marketing. Due to the extensive coverage of these topics, this book will also be very useful for undergraduate and graduate students seeking to learn the fundamentals of coating raw materials. It will also serve as a reference book for any reader interested in paints and coatings.

Vijay Mannari, Ph.D.

Chintankumar J. Patel, Ph.D.

Ypsilanti, MI/USA, January 2015

Contents

1 Introduction to paints and coatings

1.1 Why paints and coatings?

1.2 Historical perspective

1.3 Anatomy of paints and coatings

1.3.1 Resins or binders

1.3.2 Pigments

1.3.3 Additives

1.3.4 Solvents

2 Binders

2.1 Introduction

2.1.1 Introduction to polymers

2.1.2 Thermoplastic and thermosetting polymers

2.1.3 Requirements of resins and binders

2.2 Natural binders

2.2.1 Rosin (colophony)

2.2.2 Bituminous binders

2.2.3 Natural oils for surface coatings

2.2.3.1 Composition of natural oils

2.2.3.2 Classification of oils in the coating industry

2.2.3.3 Modified oils

2.3 Alkyd resins

2.3.1 Chemistry of alkyd resins

2.3.1.1 Alcoholysis process

2.3.1.2 Acidolysis process

2.3.1.3 Fatty acid process

2.3.2 Raw materials for alkyd resins

2.3.2.1 Fatty acids and oils

2.3.2.2 Polyhydric alcohols

2.3.2.3 Polybasic acids

2.3.2.4 Monobasic acids

2.3.3 Processing of alkyd resins

2.3.4 Classification of alkyd resins

2.3.5 Effect of oil modification on properties

2.3.6 Modifications of alkyd resin

2.3.7 High-solid alkyd resins

2.3.8 Waterbased alkyds

2.3.8.1 Water-reducible alkyds

2.3.8.2 Alkyd emulsions

2.3.9 Hyperbranched alkyd resins

2.4 Saturated polyesters

2.4.1 Chemistry of polyester resins

2.4.2 Formulation and raw material selection

2.4.3 High-solid resins

2.4.4 Water-reducible polyesters

2.4.5 Polyesters for powder coatings

2.4.6 Curing of saturated polyester resins

2.4.6.1 Amino resin cross-linkers

2.4.6.2 Polyisocyanate cross-linkers

2.4.6.3 Epoxy resins

2.4.7 Applications in coatings

2.5 Unsaturated polyester resins

2.5.1 Chemistry of unsaturated polyester resins

2.5.2 Curing aspects

2.5.3 Applications of unsaturated polyester resins

2.6 Phenolic resins

2.6.1 Raw materials for phenolic resins

2.6.2 Reaction chemistry

2.6.2.1 Resoles

2.6.2.2 Novolacs

2.6.3 Modified phenolic resins

2.7 Amino resins

2.7.1 Chemistry of amino resins

2.7.2 Types of amino resins

2.7.3 Use of aminoplasts in coatings

2.8 Acrylic resins

2.8.1 Polymer composition and properties

2.8.2 Acrylic resin types

2.8.2.1 Solution acrylic resins

2.8.2.2 Waterborne acrylic resin dispersions

2.8.2.3 Acrylic resins for high-solid coatings

2.8.2.4 Acrylic resins for powder coatings

2.8.2.5 Acrylic resins for radiation curable coatings

2.9 Epoxy resins

2.9.1 Types of epoxy resins

2.9.1.1 Bisphenol A epoxy resins

2.9.1.2 Bisphenol F epoxy resins

2.9.1.3 Epoxy novolac resins andhigh functionality epoxy resins

2.9.1.4 Brominated BPA epoxy resins

2.9.1.5 Cardanol-based epoxy resins

2.9.1.6 Light fast epoxy resins

2.9.1.7 Other epoxy resins and reactive diluents

2.9.1.8 Resins with internal epoxy groups

2.9.2 Modified epoxy resins

2.9.2.1 Epoxy esters

2.9.2.2 Epoxy acrylates

2.9.3 Curing agents for epoxy resins

2.9.3.1 Amine curing agents

2.9.3.2 Polymercaptans (polythiols)

2.9.3.3 Polyisocyanates

2.9.3.4 Carboxylic acids and anhydrides

2.9.3.5 Phenolic and amino resins

2.9.3.6 Self-cross-linking (epoxy homopolymerization)

2.9.4 Waterborne epoxy systems

2.9.4.1 Emulsified system (type I)

2.9.4.2 Emulsified systems (type II)

2.9.4.3 Water-reducible systems

2.10 Polyamides

2.10.1 Reactive polyamides

2.10.2 Non-reactive polyamide resins

2.10.3 Polyimides and polyamide-imides

2.11 Polyurethanes

2.11.1 Isocyanate compounds

2.11.2 Polyols

2.11.3 Polyurethane resins and coating systems

2.11.3.1 Two-component polyurethane resin systems

2.11.3.2 One-component polyurethane resin systems

2.11.3.3 Waterborne polyurethanes

2.12 Silicone resins

2.12.1 Chemistry of silicone resins

2.12.2 Pure silicone resins

2.12.2.1 Types of pure silicone resin

2.12.2.2 Curing

2.12.3 Blends of silicone resins

2.12.4 Modified silicone resins

2.12.5 Silicone modified resins

2.12.6 Waterbased silicone resins

2.12.7 Ethyl silicate

2.13 Cellulosic binders

2.13.1 Nitrocellulose

2.13.2 Esters of cellulose

2.13.2.1 Ethyl cellulose

2.14 Hydrocarbon resins (petroleum resins)

2.14.1 Coumarone indene resins

2.14.2 Petroleum oil derived hydrocarbon resins

3 Pigments

3.1 Introduction

3.1.1 Functions of pigments

3.1.1.1 Aesthetic functions

3.1.1.2 Protective functions

3.1.1.3 Other functions

3.1.2 Nomenclature – the Colour Index system

3.1.3 Classification of pigments

3.1.3.1 Classification based on color

3.1.3.2 Classification based on chemical nature

3.2 Important properties of pigments

3.2.1 Optical properties

3.2.1.1 Color

3.2.1.2 Opacity

3.2.1.3 Tinting strength and lightening power

3.2.2 Physical properties

3.2.2.1 Solubility

3.2.2.2 Density

3.2.2.3 Particle size

3.2.2.4 Particle shape

3.2.2.5 Texture of pigments (dispersibility)

3.2.2.6 Oil absorption value

3.2.3 Chemical and performance properties

3.2.3.1 Chemical purity

3.2.3.2 Resistance to chemicals

3.2.3.3 Reactivity of pigments

3.2.3.4 Resistance to oxidative degradation

3.2.3.5 Light fastness

3.2.3.6 Weather fastness

3.2.4 Environmental and toxicological perspectives

3.3 Inorganic pigments

3.3.1 White pigments

3.3.1.1 Titanium dioxide

3.3.1.2 Zinc oxide

3.3.1.3 Zinc sulfide and lithopone

3.3.1.4 Antimony oxide

3.3.1.5 White lead pigments

3.3.2 Black pigments

3.3.2.1 Carbon black

3.3.3 Colored inorganic pigments

3.3.3.1 Iron oxides

3.3.3.2 Chromium oxide pigments

3.3.3.3 Iron blue

3.3.3.4 Ultramarine blue

3.3.3.5 Chromate pigments

3.3.3.6 Cadmium pigments

3.3.4 High performance inorganic pigments

3.3.4.1 Bismuth vanadate pigments

3.3.4.2 Cerium pigments

3.3.4.3 Complex inorganic color pigments

3.3.5 Metallic pigments

3.3.5.1 Aluminum pigments

3.3.5.2 Zinc pigments

3.3.5.3 Bronze pigments

3.3.6 Anticorrosive pigments

3.3.6.1 Lead pigments

3.3.6.2 Chromate pigments

3.3.6.3 Phosphate pigments

3.3.6.4 Phosphite pigments

3.3.6.5 Borates

3.3.6.6 Molybdate pigments

3.3.7 Extenders

3.3.7.1 Carbonates

3.3.7.2 Silica (SiO2)

3.3.7.3 Sulfates

3.3.7.4 Silicates

3.3.8 Special effect pigments

3.4 Organic pigments

3.4.1 Azo pigments

3.4.1.1 Monoazo pigments

3.4.1.2 Diazo pigments

3.4.1.3 Salt-type azo pigments

3.4.1.4 Azo complex pigments

3.4.1.5 Azo condensation pigments

3.4.1.6 Isoindolinone and isoindoline pigments

3.4.2 Polycyclic pigments (non-azo pigments)

3.4.2.1 Phthalocyanine pigments

3.4.2.2 Quinacridone pigments

3.4.2.3 Anthraquinone pigments

3.4.2.4 Perylene and perinone pigments

3.4.2.5 Thioindigo pigments

3.4.2.6 Dioxazine pigments

3.4.2.7 Diketopyrrolopyrrole pigments

4 Solvents

4.1 Introduction

4.2 Theory of solvency

4.2.1 Solubility parameters

4.3 Important characteristics of solvents

4.3.1 Solvency

4.3.2 Evaporation rate

4.3.3 Other performance properties

4.3.3.1 Moisture content

4.3.3.2 Aromatic content

4.3.4 Physical properties

4.3.4.1 Surface tension

4.3.4.2 Boiling point and distillation range

4.3.4.3 Flash point

4.3.4.4 Density and specific gravity

4.3.4.5 Color

4.3.4.6 Refractive index

4.3.4.7 Electrical resistivity

4.3.4.8 Purity and composition

4.4 Classification of solventsused in the coating industry

4.4.1 Hydrocarbon solvents

4.4.1.1 Aliphatic hydrocarbons

4.4.1.2 Cycloaliphatic hydrocarbons

4.4.1.3 Terpene hydrocarbons

4.4.1.4 Aromatic hydrocarbons

4.4.2 Oxygenated solvents

4.4.2.1 Alcohols

4.4.2.2 Ketones

4.4.2.3 Esters

4.4.2.4 Glycol ethers

4.4.2.5 Other oxygenated solvents

4.4.3 Other solvents

4.4.3.1 Chlorinated hydrocarbons

4.4.3.2 N-methyl-2-pyrrolidone

4.5 Toxicity and occupational health

4.6 Environmental aspects

5 Additives

5.1 Introduction

5.2 Wetting and dispersing agents

5.2.1 Pigment dispersion process

5.2.1.1 Wetting

5.2.1.2 Grinding

5.2.1.3 Dispersion

5.2.2 Chemical composition ofwetting and dispersing agents

5.2.3 Flooding and floating

5.2.4 Polymeric dispersing agents

5.2.5 Deflocculating agents andcontrolled flocculating agents

5.3 Rheology additives

5.3.1 Rheology and its role in coatings

5.3.2 Thickeners for solventbased coatings

5.3.2.1 Organoclays

5.3.2.2 Fumed silica

5.3.2.3 Metal soaps

5.3.2.4 Overbased sulfonates

5.3.2.5 Organic thickeners

5.3.3 Thickeners for waterbased coatings

5.3.3.1 Acrylic thickeners

5.3.3.2 Cellulosic thickeners

5.3.3.3 Associative cellulosic thickeners

5.3.3.4 Associative acrylic thickeners

5.3.3.5 Hydrophobically modified ethoxylated urethanes

5.4 Flow and leveling agents

5.4.1 Solvents

5.4.2 Polymeric leveling agents

5.4.2.1 Polyacrylates

5.4.2.2 Cellulose acetobutyrate

5.4.2.3 Other polymers

5.4.3 Silicones

5.4.4 Fluorosurfactants

5.5 Defoaming and anti-foaming additives

5.5.1 Foam formation and film stabilization

5.5.1.1 Electrostatic repulsion effect

5.5.1.2 Marangoni effect (Gibbs elasticity)

5.5.2 Defoamers and anti-foam

5.5.2.1 Requirements for defoamers

5.5.2.2 Composition of defoamers

5.6 Additives for surface modification

5.6.1 Slip and mar additives

5.6.2 Matting agents

5.7 Adhesion promoters

5.8 Additives for film formation

5.8.1 Driers

5.8.2 Curing catalysts

5.8.2.1 Catalysts for polyurethane coatings

5.8.2.2 Catalysts for epoxy system

5.8.2.3 Acid catalysts for baking systems

5.8.3 Photoinitiators

5.8.4 Coalescing agents

5.9 Anti-skinning agents

5.9.1 Types of anti-skinning agents

5.9.1.1 Phenols

5.9.1.2 Oximes

5.10 Light stabilizers

5.10.1 UV absorbers

5.10.2 Radical scavengers

5.11 Biocides

5.11.1 In-can preservatives

5.11.2 Dry-film preservatives

5.12 Corrosion inhibitors

5.12.1 Flash-rust inhibitors

5.11.2 Inhibitors for long-term protection

5.13 Freeze-thaw stabilizers

5.14 Moisture scavengers

5.15 Additives to modify conductivity

Authors

Index

1 Introduction to paints and coatings

1.1 Why paints and coatings?

Looking around, we find paints and coatings virtually everywhere. We see paint on the walls of our homes or offices, and on furniture, refrigerators, washing machines, and toasters with nice colorful finishes. Outdoors, we see cars with an increasing variety of coatings. Building exteriors, equipment, bridges, pipelines, superstructures, and monuments are all painted with a variety of paints and coatings. If we examine them carefully, we can also find coatings on CDs and DVDs, fruits and vegetables, medical equipment such as catheters and surgical materials, reading glasses, electronic gadgets such as iPod tablets and cell phones… coatings are everywhere! There are virtually limitless products that use some kind of paint or coating on their surface.

Paints and coatings are not useful products by themselves, but they make other products better, more durable, more attractive, safer, and more saleable. Paints and coatings are therefore considered enabling materials that add value to manufactured products. Think of a car without paint on it, or your nice teakwood furniture without a finish. Thin coats of paint, coating, or varnish bring life to these products and make them acceptable and durable.

In general, paints and coatings are used for three primary reasons:

• providing aesthetic appeal or decorative value to surfaces and products,

• providing protection from damage by the external environment, and

• providing specific attributes to the product.

Many coatings satisfy more than one of the above reasons.

Satisfying an aesthetic need is a human instinct and there is much evidence indicating the use of some paints and coatings during the prehistoric era. In present times, many products must have aesthetic appeal for their acceptance and sale. Therefore, decorative value is one of the primary requirements of many paints and coatings. Since industrialization, we have been using a large quantity of metals and alloys, besides materials such as wood and masonry. After World War II, many polymeric materials, such as plastics, alloys, and composites, have been increasingly used. All of these materials, when exposed to the environment – heat, moisture, sunlight, wind, rain – are prone to degradation due to corrosion, erosion, or other forms of physical abuse reducing their service life. As a result, there has been a considerable need to protect these surfaces from environmental attack. Coatings are used as a barrier between the surfaces of such products and the environment to provide them with long-term protection.

Since there is a variety of material surfaces, such as wood, ceramic, masonry, metals, alloys, plastics, and glass, that have a wide range of physical and chemical characteristics, it is not surprising that we need a diverse range of coatings to protect them from the external environment. In addition to functioning in decoration and protection, many coatings are formulated to provide specific attributes to the product. For example, anti-microbial coatings on interior walls of hospitals control bacterial infections in addition to making buildings aesthetically appealing. The anti-fouling coatings on ship hulls keep barnacles under control, thus keeping ship surfaces clean. Without such a coating, growth of a thick layer of attached barnacles would keep increasing ship weight, leading to reduced fuel economy. A coating intended for a gym floor has, apart from giving it an attractive look and having general protective value, a specific property – anti-skidding – that is essential for such applications. Thus, paints and coatings are used for many different reasons and are expected to meet the specific requirements of particular products.

While the terms paint and coating are frequently used interchangeably, in general, the term paint is used to describe materials that have the major role of improving product aesthetics or decoration, such as interior wall paints. The term coating generally refers to materials that have a more protective role and provide long-term durability to products. In this book, the term coatings will be used most frequently to refer to both paints and coatings.

1.2 Historical perspective

The earliest known use of paints dates back to the prehistoric era. Humans, by nature, have a sense of aesthetics and there is considerable evidence of human beings using some type of paint for decoration of their dwellings or their bodies. The Greek and Roman civilizations (from ~ 4000 BC) used paints to decorate buildings, statues and other objects. These paints were composed of a variety of natural gums, hide glue, starches, beeswax, charcoal and various clays and minerals. Jumping forward in time, it was around 1000 AD when Rodgerus von Helmershausen, also known as Theophilus, first described coatings and gave detailed recommendations for formulas in his book Schedula Diversarium Artium. These coatings were primarily based on linseed oil and natural resins (amber), without use of any volatiles due to their unavailability. The art of extracting turpentine oil from plants became known around the 10th century, and it is believed that turpentine was first used as a solvent for reducing the viscosity of coating compositions in the early 15th century. This is an important landmark in the history of coatings because on one hand, use of a volatile solvent expanded coating applications rapidly, while on the other hand, it can be considered the beginning of the era of environmental problems due to solvent emissions that the industry is struggling hard to address even today. The development of coatings by what was known as the paint boiling process (as it required heating natural resin and linseed oil for a long time) continued, and by the 17th century, the art of making different types of coatings using different combinations of natural resins, linseed oil and volatiles was available.

The Industrial Revolution in the 18th century brought about a dramatic change in coating demand. An increasing number of coatings were now required for protection of iron, which was used in buildings and other products. This was the time when coating materials started slowly moving from their role of decoration to protection. Even in the 19th century, with the exception of a few pigments, the raw materials for coatings were all of natural origin. After heavily exploiting petroleum-based synthetic raw materials for more than a century, it is interesting that one of the major initiatives of the coating industry today in the early 21st century, for sustainability reasons, is to go back to natural-based raw materials.

Introduction of the continuous production line by Henry Ford in the early 20th century represented the industrial-scale painting technology, which required quicker drying and more durable coatings and faster coating processes. This led to the development of quick-drying cellulose-based paints and replacement of brush-application processes by spray processes. After the launch of the first entirely synthetic resin – phenol-formaldehyde – in 1907, rapid development of other synthetic polymers such as vinyl resins, urea resins, alkyds, acrylic resins, polyurethanes, melamine resins and epoxy resins, especially during and after World War II, made available a wide range of binder for coatings. It was in 1919 when titanium dioxide, the key raw material for coatings even today, was commercially available for the first time. Many synthetic pigments, both organic and inorganic types, were also commercialized during this time.

With continued industrialization and demand for coatings for a myriad of applications, the industry witnessed a steady increase in demand. It should, however, be noted that up until mid-20th century, all coating materials were almost entirely of the solventbased type. Prior to 1960, there were hardly any regulations that restricted the use of toxic substances or volatile organic compounds (VOCs) in coatings. The increased usage of such coating materials, with high VOC content, resulted in high emissions, and consequently, their harmful effects on safety, health and the environment were recognized. These concerns generated a need for regulation of paints and coatings.

Rising concerns for safety, health and the environment and establishment of agencies and regulations across developed nations heralded a new era for the paint and coating industry. Toxic materials such as lead and chrome were restricted and limits on use of VOCs for paints and coatings were established during the 1960s and later. These limits became increasingly stringent over the years and required coating formulators to think of new ways to offer coatings that satisfied customers’ needs while meeting the needs of regulatory requirements and cost. To address the issues of VOC reduction, three important approaches emerged:

• high-solid coatings, which are essentially solvent-based systems but formulated using a reduced amount of solvent (made possible by using low-viscosity binders),

• waterborne coatings, by replacing the majority of the solvents (VOCs) with water, and

• powder coatings, by eliminating volatiles and offering coatings in fine powder form.

These approaches required entirely new types of coating raw materials to meet their formulation, application, cure and performance requirements. They also required new crosslinking technologies that provided faster curing. For instance, ultraviolet (UV) radiation curable technology was developed that offered very short curing times to formulations that are ~100 % solid. All the above-mentioned approaches developed into the full-fledged coating technologies of today. Due to highly diverse product offerings based on these technologies, combined with increasingly demanding requirements both by customers and regulators, has resulted in an ever-widening palette of coating raw materials.

Today’s coating raw materials are comprised of a range of organic, inorganic and special-effect pigments, offered both in dry form as well as dispersions in water. Resins and binders are offered as traditional solutions in organic solvents, or as advanced aqueous dispersions with a variety of particle sizes and morphologies. The above development has also resulted in the availability of a wide range of additives specific for waterbased, powder, or UV-cure coatings for optimum performance.

As with many other fields of material technology, use of nanomaterials in formulations of advanced paints and coatings has been very promising. Nanoparticle size pigments and fillers, nanopolymer dispersions, and nanoadditives are now commercially available and many more such products are in the development stage. Another important challenge for the coating raw material industry in recent years has been to offer “green” raw materials that reduce the environmental footprint of coatings. With increasing awareness and consumer interest for using bio-based and greener raw materials, researchers and industries are trying to provide such raw materials at affordable costs without compromising their performance. The outlook for future coating raw materials seems to be highly advanced, multifunctional, and with a significantly lower carbon footprint, and hence more sustainable.

1.3 Anatomy of paints and coatings

We now know the primary functions of paints and coatings and their importance in enhancing and protecting many industrial and consumer products. Now let’s look at what paints and coatings are composed of. In general, paints and coatings are liquid mixtures that are applied onto the surfaces of products using a brush, roller or spray. These mixtures are supplied in a variety of forms, such as waterborne or solventborne, low viscosity or paste-like consistency, sprayable or brushable, to meet the end use application requirements. Simply put, coatings are liquid mixtures that are spread onto a surface as a thin uniform wet layer that dries to a hard and adherent film. After application, the wet liquid film is then converted to a dry and adherent coating through a physical drying or chemical curing process. The nature of the films formed depends upon the composition of the paint, and varies, for example from transparent to opaque, glossy to matte, and hard to soft.

Looking at the diversity of coating types, it is not surprising that different types of coatings would have different constituents. As one would expect, all coatings must have an ingredient that forms a film. These film forming ingredients, which are essentially polymeric materials, are called resins or binders. Resins and binders have the capability of forming transparent and adherent films, but they cannot hide or destroy the surface on which they are applied. Pigments, which are finely divided insoluble particles, colored or white, have the capability of provided color and opacity when dispersed into a medium. In general, a paint or a coating consists of pigment dispersed in a resinous binder, reduced to an acceptable application viscosity with a solvent, sometimes water. The role of the solvent is essentially to provide a suitable consistency to the pigment/resin mixture such that it can be applied uniformly as a thin layer using application equipment, such as a spray gun. In order to control some properties of coatings such as viscosity, drying time, opacity, storage stability and ease of application, some specialty chemical compounds are added to the resin/pigment/volatile mixture, in small amounts, and are known as additives. A typical coating may have several such additives added to improve or modify specific properties. In general, all the ingredients of coatings are classified into the following four major raw material categories:

• Resins or binders

• Pigments

• Additives

• Solvents.

1.3.1 Resins or binders

Resins (film formers or binders) are the most important components of coatings since many important properties of dry films, such as hardness, adhesion, chemical and solvent resistance and durability, are primarily dependent on the nature of the resins used. After application of coatings, resins form useful films by a variety of physical and/or chemical mechanisms that convert liquid films into a dry coating. The term binder is frequently used to refer to a resin since one of its roles is to “bind” pigment particles in the dry film. Resins used for paints and coatings are polymeric materials with film forming capabilities. Resins control most of the physical, chemical and mechanical properties of the coatings. It is important to note that while there are hundreds of types of polymers commercially available, only a few are useful as binders for coatings because of the specific requirements for the successful use of binders in coatings. More details on these requirements and different types of binders are covered in Chapter 2.

1.3.2 Pigments

Pigments are finely divided colored (or white) insoluble particles having a high refractive index, typically >1.70. Pigments, when uniformly dispersed in the resin (medium), impart color and opacity to the cured film. Thus, color and opacity are the primary functions of pigments. In addition, some pigments (for example, chrome pigments, zinc phosphate pigments) exhibit functional properties such as corrosion resistance, resistance to UV light, and anti-fouling properties. Pigments are also used to control rheology, exterior durability and mechanical properties of the films. Pigments with high light reflectivity and specific particle size and shape are used in special effect coatings. Pigments are classified based on their origin, whether natural or synthetic, and on their functions as organic, inorganic, metallic, and special effect pigments.

1.3.3 Additives

In order to facilitate manufacturing, storage and satisfactory application and to improve durability and performance, it is essential to incorporate special additives to coatings. Additives are compounds added in small quantities (up to ~5 % by weight) that substantially improve or modify properties of coatings. These compounds include wetting and dispersing agents, which help disperse the pigment particles in the medium, driers that help faster drying of coating films, plasticizers, UV stabilizers, rheology modifiers, preservatives, and others. Their types and amounts must be carefully selected, as they may have unintended results when used inappropriately. For their successful performance, the coating formulator must have good knowledge about the role of additives and their interactions with other components of coatings.

1.3.4 Solvents

Solvents are primarily used to control viscosity of the coatings for acceptable application. These are essentially volatile compounds that must evaporate from the film after application. Solvents also affect such properties as flow and leveling, drying time, gloss etc. A wide range of organic solvent types are used in coatings. Many of these solvents are VOCs, which have harmful effects on human health and the environment. Over the past several decades, there have been significant efforts in developed nations to reduce VOC emissions, and there are increasingly stringent regulatory requirements for use of such solvents in coatings. Waterborne coatings, which use water as the primary carrier replacing organic solvents, have therefore significantly grown over solventbased coatings as the preferred coating types for a number of end-use applications.

2 Binders

2.1 Introduction

2.1.1 Introduction to polymers

In the previous chapter, binders or film formers were described as one of the most important components of paints and coatings. Binders are essentially polymeric materials and thus presenting some concepts and definitions related to polymers will be useful in understanding the different types of binders used in paints and coatings.

Simply put, polymers are giant molecules. Unlike small molecules such as H2O, benzoic acid, and glucose that we are more familiar with, polymers are large molecules with a chain-like structure. This long chain-like polymer structure is formed by bonding between small molecular units called monomers. The chemical process by which monomers bond with each other and form long chain-like structures is a reaction called polymerization (Figure 2.1).

Figure 2.1: Simplified schematic representation of polymerization reaction

It should be noted that in a polymerization reaction, many polymer chains are formed, and these chains are not all of the same size, but rather a distribution of chains having a different chain length.

The average number of monomeric units in a sample of a polymer is known as the average degree of polymerization, expressed as DP bar. Similarly, the molecular weight (MW) of a polymer sample is also calculated by averaging the MW of individual chains, which is expressed as the average MW, or Mn bar. A number average MW can be calculated by multiplying the number average DP bar value with the MW of the repeat unit structure.

Equation 2.1:

Depending on the type of monomers and the polymerization process, the average MW of polymers can be from a few thousands to hundreds of thousands of grams per mole. Polymers with very low average MW, on the order of a few hundreds grams per mole, are frequently referred to as oligomers. Many polymers are available in nature or synthesized by living organisms and are called natural polymers, whereas those prepared from monomers by polymerization reactions are called man-made or synthetic polymers. Both natural and synthetic polymers are used in paints and coatings. In the paint and coating industry, the term resin is frequently used for polymeric materials. In this book, the terms polymers, resins, and binders are used interchangeably.

There are two basic types of polymerization reactions, as briefly described below.

Chain-growth polymerization (addition polymerization)

In this process, high MW polymers are formed by chemical bonding between monomers through a very fast polymerization reaction. This polymerization process requires an initiator compound that produces active species, such as free radicals or ions, which initiate the polymerization reaction. Once initiated, monomers combine to form a growing chain with a large number of monomer units, called a propagation step. Propagating chains then terminate by a number of different routes. Figure 2.2 shows polymerization of methyl methacrylate monomer to poly(methyl methacrylate) by chain-growth polymerization. The most common polymers used in paints and coatings that are prepared by this process are acrylics and vinyl polymers.

Figure 2.2: Chain growth polymerization of methyl methacrylate

Step-growth polymerization (condensation polymerization)

In this type of polymerization, monomers with at least two functional groups are used, and the linkages between monomeric units are formed by reaction between the functional groups of monomers that generally produce a low MW by-product, such as water. The polymer MW grows in a step-wise manner at a much slower rate compared to that for chain-growth polymerization. This type of polymerization does not produce a very high MW polymer. Figure 2.3 shows a polyesterification reaction, an example of step-growth polymerization.

Figure 2.3: Example of step-growth polymerization

2.1.2 Thermoplastic and thermosetting polymers

As mentioned in the previous chapter, resins are polymeric materials capable of forming useful films after application of coatings. For good film formation, a high MW resin is necessary. In general, in the paint and coating industry, two types of resins are used:

(1) those with very high MW that are capable of forming useful films on their own after application of coatings, without any need for a chemical reaction, and

(2) those with low MW that require, after application of coatings, a chemical reaction to increase their MW and become capable of film formation.

These two fundamental film formation mechanisms form the basis of their classification. In general, all resins, and hence all coatings, can be classified into two distinct types, thermoplastic resins and thermosetting resins.

Thermoplastic resins are high MW polymers that are capable of forming useful films without requiring any chemical reactions during or after film formation. Thermoplastic resins are essentially linear or branched polymers. The film formation of coatings based on such polymers primarily involves only the evaporation of solvent. The dry films of such resins are essentially stacks of entangled long chain amorphous polymers physically interacting with each other through Van der Waals forces. Due to their long chains, the degree of entanglement and physical interactions are strong enough to provide some useful properties, but in general, they lack some desired mechanical properties and resistance to attack by solvents. As the viscosity of a polymer solution is dependent on its MW, the high MWs of thermoplastic resins give them high solution viscosities. This requires use of higher amounts of solvents in their coatings to bring their viscosities down to acceptable levels. However, thermoplastic resin latexes (dispersions of thermoplastic resins in water) can afford coatings without necessarily using solvents. Such systems are very popular and form a major category of today’s waterborne coatings.

Thermosetting resins, the another important resin type, are polymeric materials that must undergo some chemical reaction after coatings are applied to form useful films. These chemical reactions, called cross-linking reactions or curing reactions, essentially connect relatively smaller polymer chains, leading to an increase in MW and formation of a cross-linked or network polymer structure. Thus, the structure of the polymer in the cured films of thermo-setting systems, unlike thermoplastic ones, is formed by strong chemical linkages connecting polymer chains, making these films strong and resistant to chemical and solvent attack. In general, the binders for thermosetting coatings are comprised of relatively low MW resins with reactive functional groups and an added cross-linking agent (cross-linker). After the coating is applied, under suitable reaction conditions, cross-linkers react with functional groups of resins, forming a dry film with a cross-linked network structure. Some thermosetting resins have functional groups that are capable of cross-linking by reacting with themselves (self-cross-linking) or with the components of the atmosphere, such as moisture or oxygen, without the need for an added cross-linking agent. Thus, it follows that the structure of the film formed and the properties of the coatings based on thermosetting and thermoplastic resins are fundamentally different and find application in different end uses. Table 2.1 shows typical examples and applications of resin types.

Table 2.1: Typical examples and applications of resin types

2.1.3 Requirements of resins and binders

The primary role of paints and coatings is to enhance appearance and protect the surface from environmental damage during their service life. Paints and coatings are used for a myriad of applications, and hence their service environment and the degree of protection expected vary to a large extent. Since binders and resins are the actual film formers, their proper selection in formulation is very important. Depending upon the requirements of the final dry film properties, very careful selection of resins is required. In general, resins and binders used for coatings should have the following desirable properties.

• A high MW or capability of cross-linking (curing) after application of coatings

• Solubility in solvents or dispersible in water for efficient formulation, processing and application

• Capability of forming a continuous, adherent and uniform film after application of coatings

• Physical, thermo-mechanical and optical properties as required by coating applications

• Broad range of compatibility with different resins, cross-linkers, additives, solvents and water

• Good shelf-life under normal storage conditions

• Requirement for low or no VOCs for their processing or use in coatings

• Ability to offer paint and coatings products that are compliant to regulatory requirements

• Preferably made from sustainable resources

• Be cost competitive.

2.2 Natural binders

In IS0 4618/3, natural resins are defined as resins obtained from a vegetable or animal origin. Natural resins have been used in coatings for a long time. In recent times, although technologically advanced synthetic resins have replaced these materials, certain natural resins have maintained their place for particular uses as modifiers. They are classified, based on their source, as recent resins, fossil resins and recent-fossil resins. Recent resins are typically obtained by collecting exudations from plants, while fossil resins are those that have been buried underground over geological time. In general, natural resins are low MW compared to many synthetic resins used in coatings, and chemically, they are mixture of various polycyclic and aromatic compounds. As their applications in coatings have been limited in recent years, we will briefly discuss some important natural resins in the subsequent sections.

2.2.1 Rosin (colophony)

Rosin, also known as colophony, and its derivatives are among the most important and widely used natural resins. Rosin is obtained from pine trees either by collecting exudations from the tree (known as gum rosin) or by solvent extraction of aged pine stumps (known as wood rosin). It can also be obtained as a by-product of the paper industry, where soluble salts of rosin and fatty acid along with lignin are formed as a by-product, which is further distilled to obtain fatty acid and rosin as a residue (known as tall oil rosin). Chemically, rosin is mixture of monocarboxylic acids (~90 %), with the main component being abietic acid and the remainder (~10 %) being neutral materials such as hydrocarbons, oxidized terpenes and saponifiable esters (see Figure 2.4). When heated at ~150 °C, abietic acid isomerizes to levopimaric acid. The unsaturated abietic acid can be readily oxidized, but levopimaric acid is more resistant to oxidation. Rosin is a light yellow to brown brittle solid material (softening point ~70 to 80 °C) having good solubility in aliphatic solvents and good compatibility with drying oils. But due to its high acid content, it is sensitive to water and alkali. Therefore, rosin is frequently chemically modified to increase its softening point and lower its acidity. The important chemical modifications of rosin involve either neutralization of acid groups with calcium oxide (lime) or zinc oxide to form calcium or zinc soaps, respectively, or its esterification with polyols such as glycerol or pentaerythritol for necessary molecular enlargement to the product commonly known as ester gum. The carboxylic acid group of rosin acid is sterically hindered and hence requires a higher temperature (~250 °C) for esterification, but on the other hand, its esters have better resistance to hydrolysis.

Maleic modified rosin is a commercial product and widely used as a binder in the printing ink industry. Levopimaric acid with its conjugated double bonds can undergo a Diels-Alder reaction with maleic anhydride, maleic acid or fumaric acid to produce maleic modified rosin adduct, which is a tricarboxylic acid derivative. The adduct is then reacted with a polyol such as glycerol or pen-taerythritol to produce maleic resins, which are characterized by their light color, higher melting point, improved light fastness, better hardness and oxidation resistance than rosin. A wide range of such products are commercially available, mainly varying in softening point and excess hydroxyl content.

Rosin modified phenolic resin, another important rosin derivative used in the coating industry, is derived by reacting rosin with a resole type phenolic resin. The extent of modification, the type of phenolic resin used (in terms of the phenolic compound used), and the formaldehyde to phenol (f:p) ratio are the main variations offering different grades of these products. Please see Section 2.6.3 for further discussion of this topic.

Figure 2.4: Schematic representation of some modifications of rosin

The main applications of rosin and its derivatives are in printing inks, oleoresinous varnishes, and modified alkyds to improve hardness and physical drying.

2.2.2 Bituminous binders

Bituminous binders are a crude type of hydrocarbon resin, generally produced as a by-product during distillation of crude oil or coal. Bituminous resins, based on their chemical composition, are categorized as asphalt-based and coal-tar pitch-based products. We will briefly discuss some important bituminous binders used in coatings and related industries.

Bituminous vehicles are chemically complex mixtures of hydrocarbon resins with varying content of paraffins, cycloparaffins, naphthenes and olefinic materials, depending upon their source. The asphalts are rich in aliphatic components while coal tars are mainly composed of aromatic components. Asphalts are soluble in aliphatic hydrocarbon solvents while coal tars are soluble in aromatic hydrocarbon solvents. They are very black in color due to the presence of colloidal carbon. Important properties for their use in coatings are their chemical inertness, excellent water repellency, electrical resistivity, barrier properties and most importantly, lower cost. On the limiting side, they have poor UV resistance and a tendency to bleed in solventbased topcoats, and therefore their usage is restricted to underground structures, coatings for immersed conditions and areas not exposed to UV light.

Petroleum asphalts, obtained as a residue in distillation of asphaltic crude, are used in protective coatings for buried structures and pipelines, coatings for pavements and parking lots, roof coatings and water proofing applications.

Coal tars, obtained from destructive distillation of bituminous coal, are widely used in thick, thermoplastic, hot-applied barrier coatings and linings for the interior as well as exterior of pipelines. Another important use is with other synthetic binders including epoxy-coal tar hybrids and occasionally polyurethane coal-tar hybrids for protecting steel structures in contact with water, soil and back-fills.

Bituminous emulsions are produced by emulsifying an asphalt or coal tar in water using suitable combinations of surfactants along with colloidal clays. After application as coatings, with subsequent evaporation of water, the emulsified bituminous particles coalesce to form a continuous film. Being waterbased, such systems have the potential to comply with VOC regulations.

While bituminous vehicles have been extensively used in barrier coatings over the years, their use is decreasing in recent years due to toxicity issues, especially with coal tars.

2.2.3 Natural oils for surface coatings

There is much historical evidence that plant oils and animal fats were among the first binders to be used for paints and coatings. Their easy availability and ability to form a coherent film when applied to a surface and exposed to air, which oxidizes them, have made them very attractive as a coating raw material from historical and earlier times. With the availability of synthetic resins of a wide variety and higher performance during and after The Second World War, usage of oils as the sole binders has diminished, but they are still used considerably as raw material for various synthetic binders such as alkyd resins, epoxy esters and uralkyds. In recent years, with increasing awareness of environmental issues and the need for sustainable coatings, natural oilbased resins have made a significant comeback as green materials.

2.2.3.1 Composition of natural oils

Natural oils, used as components of binders for surface coatings, are generally derived from oilseeds, though occasionally they are of animal origin, such as fish oil. Compositionally they are triglycerides of fatty acids. They are sometimes described as fixed oils to distinguish them from essential oils, which are volatile aromatic oils found in some plants. The physical and chemical properties of triglyceride oils are governed by the composition of fatty acids in them. The generic structure of a triglyceride oil is shown in Figure 2.5.

Figure 2.5: General structure of triglyceride oil

R, R’ and R” are fatty acid chains, which may or may not be of one type in a given triglyceride molecule. The fatty acid distribution is broad and characteristic in specific plant oils. Some of the important natural fatty acids commonly found in vegetable oils are shown in Figure 2.6.

Three important attributes of the structure of these fatty acids are: The length of the fatty chain, the degree of unsaturation (number of double bonds) of the chain and the position of the double bonds in polyunsaturated chains.

The chain length of fatty acids can vary from C8 to C22, but C18 is the most common fatty acid in the case of vegetable oils. Fish oil is the only animal oil that has an even broader range of fatty chain length, from C12 to C30 with variation in unsaturation. The saponification value of triglyceride oils is an indirect measurement of their chain length.

The double bonds in the chain are the reactive centers responsible for thermal and oxidative polymerization properties of the oils. A quantitative measure of the average degree of unsaturation present in a given oil is expressed by its iodine value (IV), which increases with an increasing number of double bonds. Therefore, highly unsaturated oils having the ability to form a solid or semisolid polymeric structure by means of oxidative or thermal polymerization are invaluable for coatings.