[ChE EL 22: PAINTS AND COATINGS]

VEHICLES AND BINDERS

DEFINITION
The vehicle is composed of the binder, or, if it is necessary to thin the binder with a diluent like solvent or
water, it is the combination of binder + diluent (solvent). The binder (resin) and solvent together are
sometimes known as vehicle. The binder may be dissolved as a solution or carried as a dispersion of
microscopically small particles in a liquid.
In this case, once the paint has dried or cured very nearly all of the diluent has evaporated and only the
binder is left on the coated surface. Thus, an important quantity in coatings formulation is the “vehicle
solids”, sometimes called the “resin solids” of the formula. This is the proportion of the wet coating weight
that is binder, ie. The polymer backbone of the film that will remain after drying or curing is complete.

Binders are macromolecular mass products with a molecular ass between 500 to around 30,000. Two types
are as follows:
a. Higher molecular mass products
- Include cellulose nitrate and polyacrylate and vinyl chloride copolymers
- Suitable for physical film formation
b. Low molecular mass products
- Include alkyd resins, phenolic resins, polyisocyanates and epoxy resins

CHARACTERISTICS

To produce acceptable films, binders must be chemically hardened after application to the substrate to
produce high molecular mass cross- linked macromolecules.

Increasing relative molecular mass of the binder in the polymer film improves properties such as elasticity,
hardness, and impact deformation, but also leads to higher solution viscosity of the binder. While the
usefulness of a coating is enhanced by good mechanical film properties, low viscosity combined with low
solvent content are also desirable for ease of application and for environmental reasons.

Therefore, a compromise is necessary. The low molecular mass binders have low solution viscosity and
allow low- emission paints with high solids contents or even solvent-free paints to be produced. Here, the
binder consists of a mixture of several reactive component, and film formation takes place by chemical
drying after application of the paint. If chemical hardening occurs even at room temperature, the binder
components must be mixed together shortly before or even during application (two or multicomponent
systems).

Today, most binders are

a. Synthetic resins
- Such as alkyd or epoxy resins
- Based on cyclohexanone, acetophenone, or aldehydes
- Are softer and more flexible than hard resins
- Impart good elasticity, impact resistance, and improved adhesion, even to critical undercoats
- Offer adequate resistance to weathering and chemicals

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- Produced with a property profile tailored to suit particular application methods

- Comply with a range of technical requirements, including environmental protection, low
toxicity, and suitability for recycling and disposal
b. Natural resins
- Most commonly used is rosin, which is often tailored by chemical modification to suit specific
applications
c. Hard resin binders
- Increase the solids content
- Accelerate drying
- Improve surface hardness, luster, and adhesion

FUNDAMENTAL FUNCTIONS OF VEHICLES AND BINDERS

** For vehicles:
1. The main purpose of the vehicle is to adjust the viscosity of the paint. It is volatile and does not
become part of the paint film. It can also control flow and application properties. Its main function
is as the carrier for the non- volatile components. Water is the main vehicle for water-based paints.
2. Vehicles are only liquids in which the body and pigment are soluble
3. Vehicles facilitate the paint to be conveniently spread over the surface or substrate.

*** For binders:

1. The binder or resin forms the matrix of the coating, the continuous polymeric phase in which all
other components can be incorporated.
2. The resin is the film-forming agent of the paint.
3. Its density and composition are primarily responsible for determining the permeability, chemical
resistance, and ultraviolet (UV) resistance of the coating

SOURCES AND TYPES

** For binders:
The three most important binders (resins) in modern paints are:
- Acrylic polymers (resins)
- Alkyd polymers (resins)
- Epoxy polymers (resins)

1. Acrylic polymers (resins)

The binder in many emulsion paints is based on homopolymers or co-polymers of ethenyl ethanoate
(vinyl acetate) and propenoate (acrylic) ester.
Other acrylic esters used as co-monomers with ethenyl ethanoate are ethyl propenoate, butyl
propenoates, or a co-polymer of butyl propenoate and methyl-2-methylpropenoate.
The polymers used in these paints are carried in water (water-borne emulsion paints) which as
described above is much better for the environment than paints in which the binders are in organic
solvents.
2. Alkyd polymers (resins)

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Decorative gloss paints typically contain alkyd polymers (resins). A typical resin is that produced from a
polyol such as propanr-1,2,3- triol (glycerol) with a dibasic acid such as benzene- 1,2- dicarboxylic
(phthalic) anhydride and a drying oil (linseed or soybean oil). On being heated together, ester linkages
are formed, and water is a by-product. The name alkyd is derived from alcohol and anhydride.
3. Epoxy polymers (resins)
Epoxy resins are often used as the binder in industrial coatings (primers). They give the paint excellent
adhesion together with high resistance to chemicals (corrosion), and physical resistance necessary, for
example, on ships and chemical storage tanks.

The epoxy resins are made from 1-chloro-2,3- epoxypropane (produced from 3-chloropropene) and
substituted phenols.

Epoxy resins can be carried in solvents such as aromatic hydrocarbons, alcohols, ketones and esters
(solvent-borne paints) or as dispersions in water (water-borne paints) as true emulsions. They are not
normally used in topcoats for outdoors because they are susceptible to UV degradation, but they make
excellent interior coatings and exterior primers.

Epoxy resins are also used as adhesives (eg. Araldite) and electrical insulators.

** For Vehicles:
Solvent based, sometimes called oil-based, paints can have various combinations of solvents as the
vehicle, including aliphatics, aromatics, alcohols, and ketones. These include organic solvents such as
petroleum distillate, alcohols, ketones, esters, glycol ethers, and the like. Sometimes volatile low-
molecular weight synthetic resins also serve as diluents, Linseed oil, Soya bean oil, fish oil, dehydrated
castor oil.

MANUFACTURING AND INDUSTRIAL STANDARDS

** For binders in paints and varnishes

ISO 11908:1996 Amino resins- General methods of test
ISO 10283:2007 Determination of monomeric diisocyanates in isocyanate resins
ISO 11668: 1997 Chlorinated polymerization resins- General methods of test
ISO 11909:2007 Polyisocyanates resins- General methods of test
ISO 13632: 2012 Rosin- Sampling and sample preparations for color measurement
ISO 13885-1: 2008 Gel permeation chromatography (GPC) - Part 1: Tetrahydrofuran (THF) as eluent
ISO 14446: 1999 Determination of the viscosity of industrial cellulose nitrate solutions and
classification of such solutions
ISO 15715: 2003 Determination of turbidity
ISO 16805: 2003 Determination of glass transition temperature

PAINTS BASED ON BINDERS/ SOLVENTS

Enamel-based paints (Alkyd) - An enamel paint is a paint that dries to an especially hard, usually glossy,
finish. Enamel paints contain either glass powder or tiny metal flake fragments instead of the color

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pigments found in standard oil-based paints. Enamel paint is also mixed with varnish to increase shine as
well as assist its hardening process.
QDE - Quick Drying Enamel is an alkyd type paint that provides great durability while being noted as a fast
drying paint. It is formulated to give a tough, durable, beautiful and high build film on wood and metal.
Flat Wall Enamel #800 is a flat alkyd type paint that provides great durability while being noted as a fast
drying paint. Levels evenly, showing no lap and brush marks when applied skillfully.
Tinting color is a liquid solution mixed with enamel paint to produce color (TRU-TONE)
Acrylic Water-based Paint (LATEX) - Latex paint is a water-based dispersion of sub-micrometre polymer
particles. Latex paints cure by a process called coalescence where the water, solvent and binder are fused
together into irreversibly bound networked structures.
LATEX is a water emulsion of a synthetic rubber or plastic obtained by polymerization and used esp. in
coatings (as paint) and adhesives
**Water is used as a thinning agent to latex paints.
ACRI-COLOR is a liquid solution mixed with masonry paint to produce color
Acrylic Solvent-based Paint - Boysen® Acrytex™ is an acrylic solvent-based coating that forms a seamless,
non-porous, watertight film that repels water and prevents seepage. It is noted for its excellent adhesion
and long-term durability. Creates a very tight film, serving as a moisture sealant for concrete and a stain
inhibitor for wood.
Epoxy-based Paint - Epoxy Primer a high quality, two-component, epoxy-polyamide system that has
exceptional adhesion to practically any surface including steel tanks, coastal installations, galvanized iron,
pipelines, aluminum, structural steel, etc. Has excellent corrosion resistance and sealing properties. Highly
alkali-resistant so there is no need for neutralization of new concrete.
Lacquer-based Paint
Lacquer Primer Surfacer is a nitrocellulose lacquer type sealer with excellent holdout properties that
provide good foundation for the desired lacquer topcoat. (primer for indoor surfaces)
Automotive Lacquer is a nitrocellulose, solvent-based, high gloss, lacquer type paint that is easy to apply
and dries rapidly to a long-wearing attractive finish. (indoors surfaces)

BINDERS
- This is the fluid material in the paint which must harden after application
- The binder, or resin, is the actual film forming component of paint. It is the only component
that must be present; other components of paint are included optionally, depending on the
desired properties on the cured film.
- Binders can be specified according to drying, or curing mechanism.
NOTE:
Drying and curing are two different processes.
• Drying generally refers to evaporation of vehicle , whereas
• Curing refers to polymerization of the binder.
Thus, there are paints that dry only, those that dry then cure and those that do not depend on drying for
curing.
• The hardening process may be due to one of the following
a) Polymerization by chemical reaction with air in the atmosphere.
Such paints tend to form a film. They include ordinary oil paints
b) Coalescence of an emulsion.

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Emulsions are pre-polymerized into very small particles which are prevented from coalescing by an
emulsifying agent. They set by water loss leading to ‘breaking’ of the emulsion
c) Evaporation of a solvent.
Solvents need to be volatile, hence they are often flammable

• Paints based on (a) and (b) are described as convertible coatings because once set, they cannot be
easily re-softened. Once weathered , application of new coatings to these paints therefore rely on
the previous paint being roughened to provide a key.
• Paints based on type (c) are described as non-convertible since they can be re- softened by
application of a suitable solvent.
– Subsequent coats also tend to fuse into previous coats and they do not form films

DRYING AND FILM FORMATION

• As the paint dries on the substrate, a firmly bonded film is formed. The properties of this film are
determined both by the substrate and its pretreatment (cleaning, degreasing) and by the
composition of the coating and the application method used.
• In practice, drying of coatings and paints does not take place by one method alone. With solvent-
containing and waterborne heat-curing coatings, physical drying by solvent evaporation always
precedes chemical drying.
• Depending on the composition of the binder system, physical and chemical drying can take place
simultaneously, and the various mechanisms of chemical drying can proceed concurrently or
consecutively, depending on the nature of the binder.
• A knowledge of binder composition is important in order to assess the drying of a coating and able
to accelerate it by heat, radiation, and addition of catalyst.
• Drying of the paint on the substrate takes place physically (1-3) or chemically (4):
1) Evaporation of the organic solvents from solvent-containing paints
2) Evaporation of water from waterborne paints
3) Cooling of the polymer melts (powder coatings)
4) Reaction of low molecular mass products with other low or medium molecular mass binder
components (polymerization or cross-linking) to form macromolecules

Physical Drying

• Physical drying takes place mainly for paints with high molecular mass polymer binders such as
cellulose nitrate, cellulose esters, chlorinated rubber, vinyl resins, polyacrylates, styrene
copolymers, thermoplastic polyesters and polyamide and polyolefin copolymers. These materials
give good flexibility and stability because of their high molecular mass.
• Film formation can be accelerated by drying at elevated temperatures (forced drying). Physically
drying solvent-containing paints have a low solids content because the molecular mass of the
binder is relatively high. Films formed from physically drying paints, especially those formed from
solutions, are sensitive to solvents (dissolution or swelling).
Chemical Drying
• Chemically drying paints contain binder components that react together on drying to form cross
linked macromolecules. These binder components have a relatively low molecular mass, so that

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their solutions can have a high solids content and a low viscosity. In some cases, solvent-free liquid
paints are possible. Chemical drying can occur by polymerization, polyaddition, or
polycondensation.
a) Polymerization
When polymerization is used as the hardening principle, reactive components combine to form the
binder. Here, one component often behaves as a reactive solvent for the other, and low-emission
coating systems are the result. Cross-linking can be carried out at room temperature (cold curing)
or by radiation curing.
b) Polyaddition
- In drying by polyaddition, low molecular mass reactive polymers such as alkyd resins react with
polyisocyanates or epoxyresins to form cross-linked macromolecules. Because this reaction can
take place at room temperature, the binder components must be mixed shortly before
application.
- The period of time during which a coating of this type remains usable after mixing of the
components is known as the pot life.
- Chemically blocking one of the polyaddition binder components (e.g., the polyisocyanate) gives
a coating system stable at room temperature. Heat is required to deblock the component and
enable cross-linking to occur. Stoving paints of this type are used in industry and in powder
coatings.
c) Polycondensation
- Polycondensation drying requires the addition of catalysts or the use of higher temperatures.
Acid catalyzed coatings are well-known cold-curing paint systems used in the furniture industry,
while heat-curing and stoving paints are used as industrial and automotive coatings.
- The binding agents used are functional alkyd resins, saturated polyesters, or polyacrylates in
combination with urea resins, melamine resins, or phenolic resins. On cross-linking, water, low
molecular mass alcohols, aldehydes, acetals, and other volatile compounds are released.
Curing
• For a coating to be effective, it must be properly cured. Unless this is allowed to take place, the
coating will not provide the protection required nor have the expected lifetime.
• Most organic resins are liquid, which cure or dry to form solid films. They are classified as
thermoplastic or thermosetting. Thermoplastic resins dry by solvent evaporation and will soften
when heated and harden when cooled.
• Thermosetting resins will not soften when heated after they are cured. Most organic resins are
affected by solvents.
• Coatings are also classified by their various film-forming mechanisms, such as solvent evaporation,
coalescing, phase change, and conversion.
• Additionally they are classified as room-temperature curing (sometimes called air drying) or heat
curing (generally referred to as baking or force drying), which uses elevated temperatures to
accelerate air-drying. Thermoplastic and thermosetting coatings can be both air-drying and baking.
Air Drying
• Air-drying coatings cure at room or ambient temperatures, forming films. The films are formed by
one of three mechanisms:
• Solvent evaporation. Shellac and lacquers such as nitrocellulose, acrylic, styrene-butadiene, and
cellulose acetate thermoplastic resins form films by solvent evaporation.

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• Conversion. As solvents evaporate, films are formed that are cured by oxidation, catalysis, or cross-
linking. Thermosetting coatings crosslink to form film at room temperature by catalysis or oxidation.
The addition of catalysts will accelerate the oxidative curing of drying oils and oil-modified resins.
• Coalescing. Emulsion or latex coatings, such as styrene-butadiene, acrylic ester, and vinyl acetate
acrylic, form films by coalescing and dry by solvent evaporation.
Baking
• Coatings requiring baking will form films at room temperature but require elevated temperatures of
300 to 372°F (150 to 200°C) to cure. Curing is either by conversion or phase change.
Force Drying
• The cure rate of many thermoplastic and thermosetting coatings can be accelerated by exposure to
elevated temperatures that are below those considered as baking temperatures.
Reflowing
• Certain thermoplastic coating films will soften and flow, becoming smooth and glossy at elevated
temperatures. The automotive industry uses this technique on acrylic lacquers to eliminate buffing.
Radiation Curing
• Bombardment with ultraviolet and electron-beam radiation with little increase in temperature will
form and cure films. However, infrared radiation increases the surface temperature and is therefore
considered a baking process.
Vapor Curing
• This method is used for two-component coatings. The substrate is coated with one component of
the coating in the conventional manner. It is then placed in an enclosure filled with the other
component — a curing agent in vapor form-where the catalysis or cross-linking conversion takes
place.

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