PAINTS

Definition
Paint is a formulation in which one or more pigments with other
ingredients are suspended in a carrier solvent, i.e., oil, water etc.

It is a solution or suspension (emulsion) of pigment, binder, and mineral

solvent (or water) that on drying forms an adhering film on the surface. it
is applied for protection and/or decoration.

The principal role of pigments is to impart desired color and to protect

substrates such as wood and metal surface.
 Constituents of Paints

1. Pigments: The pigments are mainly inorganic metal oxides. For example:
white lead, 2PbCO₃·Pb(OH)₂; titanium oxide, TiO2; zinc oxide, ZnO; iron
oxide, chromium oxide, carbon black, lamp black

Basic requirements of a pigment-

✓Opacity
✓Good mixing ability with solvent
✓Chemical inertness
✓No/low toxicity
✓High strength
✓Low cost
 Types of pigments
Natural:
✓ Talc- Talc is a clay mineral, composed of hydrated magnesium silicate with the chemical formula
Mg3Si4O10(OH)2
✓ Mica-
✓ Chalk- CaCO3

✓ Clay - Kaolinite (Al2O3(SiO2)2(H2O)2), a hydrous aluminosilicate.

Synthetic: white lead, zinc oxide, titanium oxide, iron oxide

Tonners: Insoluble organic dyes

 2. Extenders or fillers: Talc, silica, china clay, etc.
They are used in paint in order to decrease the cost of paint and to
supplement the pigment and increasing the covering power of film. They
improve consistency, levelling and setting of paints.

3. Film forming materials: Serve as dispersion medium and carrier solvent

Example: Linseed oil, soyabean oil, castor oil, Tung oil, fish oil etc.
*Mostly drying oil

4. Driers: Driers which are oxygen carriers to accelerate the drying through
oxidation and polymerization of film forming materials. Driers act as a catalyst
to promote oxidation polymerization. PbO, Co, Mn, Pb, Zn etc.

*Wrinkling caused by too fast drying is a defect of paint film.

 5. Thinners or diluents: It is used in paint to dissolve film forming materials
and to make low viscous for easy handling.
Example: turpentine, acetone, toluene, naphtha. (mainly aromatic
compounds)

*Lacquer: To control desired volatility by using some aliphatic chemicals.

It means a range of clear or colored wood finishes that dry by solvent evaporation
or a curing process that produces a hard, durable finish.
Example: ethers, esters, ketones, alcohols

6. Anti-skinning agents: to prevent gelling and skinning of finished products.

Example: Polyhydroxy phenols
7. Plasticizers: These are used to provide elasticity and to prevent cracking
in paints. Triphenylphosphate, dibutyl phthalate

8. Resins: They are used for water-based surface coating formulation.

No need for oil based paint. acrylic, butadiene and styrene polymer resin.

9. Binders: to fix the paint on coating surface and provide tough, tenacious
and glossy films. Alkyd resins, silicon resins

10. Extender - larger pigment particles added to improve adhesion,

strengthen the film and save binder. Protect from cracking.
clay, talc, barytes etc.
11. Some other compounds: dispersing agent (casein), antifoaming agents
 Classification of paints

Exterior house paints: pigments+ vehicle+ thinners

Interior wall paints: mixture of pigments+ vehicle+ resins

Fire resistant paints: Borax, zinc borate, ammonium phosphate,

synthetic resins as anti fire chemicals.

Chemical resistant paints: bituminous varnishes, chlorinated

rubber composition, baked oleo resinous varnishes.
 Luminous paints: Phosphorescent compositions-sulfides of Ca, Cd and Zn,
and sensitizers for activation of UV light.

Marine/ antifouling paints: Antifouling paints are formulated with cuprous oxide
(or other copper compounds) and/or other biocides—special chemicals
which impede growth of barnacles, algae, and marine organisms.

Emulsion paints: The vehicle oils ( alkyds, phenols) disperse in

pigments containing water. Highly durable, impermeable to dirt,
resistant to washing, rapidly drying, low cost water as thinner
and easy to clean.
 Latex paints: Proteins in aqueous ammonium solution + pigments in water+
Extenders ( clay, talc)+ preservative ( chlorophenol) + antifouling agent as pine oil
+ plasticizers (trybutyle phosphate) + latex ( copolymer of butadiene and styrene)

Cement paints: Mixed with cement, dry powder, water proof capacity,
stable and decorative.
Before mixing sodium silicate and zinc sulfate are added

Metal paints:
Barrier type: common paint ingredients- pigments for color
alkyd resins to resist weathering of metals and to resist from chemicals
chlorinated rubber to resist soap, detergent and strong chemicals
silicon as heat and water resistant
 Galvanic type: galvanization of zinc on metal

Distempers: paints in water

Advantages: easy applicability, good covering power, smooth and
pleasant looking, durable.
Disadvantages: These paints are not moisture proof.
 Setting of paint: Read the role of each ingredients
Paint failure: Progressive chalking or powdering of paint film due to
Destructive oxidation of the oil after drying of the paint on the surface.
Erosion: fast chalking
Flaking or peeling: poor attachment of paint film on the surface due to
the presence of dirt or grease on the surface or entering of water.
Alligatoring: center is attached but surrounding is peeled off.

cracking or checking: lack of plasticizers

Blistering: appearance of blisters

Blooming: appearance of dull patched

How to protect paint failure?
✓ Mixing of proper ingredients
✓ Proper processing of surface to be coated
✓ Using a primer coat before the application of paints
Mode of Painting:
✓ Hand painting or brushing: A surface is painted by taking the paint on
a brush and applying straight way on the surface.
✓ Spraying: electro spraying: Paint is sprayed on the surface by using
a spray gun.
Advantages of spraying mode are: uniform coating and less time.
Disadvantages : i) Jet injection makes excessive spread of paint
ii) Environmental (air) pollution-to over come this problem,
spraying can be done in a closed chamber with exhaust fan.
Electro-spraying: substrate to be painted is used as anode
✓ Dipping: Articles are painted in a tank:
Problems: tears & beads;

✓ Roller coating: This technique consists in applying

the paint on a sheet metal or flat sheet during its
slow motion through a pair of rubber coated
rollers.
✓ Tumbling: for small articles of wooded in barrel
Baking of paints: It is carried out in a steam or gas fired oven at 150-400°F
• To improve adhesion and hardness
• Resistance to corrosion and destructive agents of paint films
• Infrared lamp is also used for baking of paint
 Varnish
✓ Varnish is known as unpigmented colloidal dispersion or solution of natural
or synthetic or both resins in oils in absence or presence of thinners.
✓ They also used as protective and decorative coating for various surfaces.
✓ Drying is accomplished by evaporation, oxidation and polymerization of its
constituents.
✓ Varnishes differ from paints in that they have no pigments and in varnishes
oil is partially or completely replaced by resins. Drying of oil results in the
formation of a highly polymerized product which is quite similar to resins.
Therefore, oil is replaced by resins.
✓ Due to absence of pigment , varnishes are less resistant to light than are
paints, enamels and pigmented lacquers.
 Varnish

✓ Varnishes allow the original surface to show but add a lustrous and glossy
finish to it.
✓ Varnish is a transparent, hard and protective finish or film primarily used
for wood finishing but also for other materials. Varnish is traditionally
combination of resin, drying oil, thinners or solvent.
 Classification
Spirit varnishes: These are the solution of natural resins, such as shellac, rosin,
copal, kauri etc. in methylated spirit or other completely volatile non film
forming solvent. They dry very fast but undergo paint failure due to cracking
and peeling off in absence of plasticizer.
Example of spirit varnish: solution of natural resin, shellac, in alcohol.
Oleoresinous varnishes: These are the solution of one or more natural or
synthetic resins in drying oil and a volatile solvent. Plasticizers are also added
to the oil. Urea formaldehyde resin, phenol formaldehyde resin, vinyl resin , as
synthetic resins, are used.

Solvents: Turpentine or naphtha

Oils: linseed oil, soyabean oil, tung oil etc.
 Raw materials
i) Film forming materials: to form protective film, (in paint binders for
pigments)
✓ drying oil: linseed, tung, castor soya oil, coconut oil
✓ Resins: natural- copal, damar, rosin, shellac, manila etc
Synthetic- phenol formaldehyde, cellulose nitrate, cellulose
acetate
ii) Solvents and thinners: to dissolve resins and control flow (viscosity)
turpentine oil, kerosene, petroleum spirits, naphtha
iii) Driers: carbonate, borate of Co, Pb, Mn and lineoleates, naphthenates
of Zn Pb, Mn, and Co for oleoresinous varnishes to fasten drying.
iv) Antiskinning agents: guaiacol tertiary amyl phenol
v) Plasticizers: trycresyl phosphate, dibutylphthalate.
 Enamels or gloss finisher
Pigmented ( not more than 40%) varnishes are know as enamels. Enamels
provide glossy and lustrous (shining) finish to surface
 Lacquers
Lacquers may be regarded as a modified form of spirit varnish that gives a
transparent film. It is a dispersion of cellulose derivatives with resins and
plasticizers.

The function of cellulose derivatives is to provide durability, hardness and

water proofness. Natural or synthetic resin is to improve adhesion, water
resistance capacity and the quality of retention of original gloss.
Uses: Lacquers are generally used in the preparation of artificial leather and
for giving finish to automobile parts to be protected form abrasion, cracking
and chalking. They are also used in interior decoration such as painting of
wood work and furniture.
 Solvent vs thinner
Solvent is used to dissolve substances and thinner is used to make solution
less expensive and to reduce the viscosity.
 Resins

Definition: Resins are natural or synthetic compounds that begins in a

highly viscous state and hardness with treatment. Typically, it is soluble
in alcohol but not in water. It is transparent sticky substances
produced by plant and tress. The class of flammable, amorphous
secretion of conifers and legumes are also considered as tress resins.
 Constituents

Plant resins:- Viscous liquid composed of volatiles fluid terpenes and

non volatiles dissolved solids which make sticky and thick. The
terpenes are bicyclic like α-pinenes, β—pinenes, δ-3-carene,
monocyclic limonene and terpilonene and small amount of tricyclic
sesquiterpenes.
Exception: Jeffrey pine and gray pine resins are pure n-heptane with
little or no terpenes.
Balsams: Benzoic acid or cinnamic acid
 Classification
The resins are broadly classified under three major categories:
I) Taxonomical classification: The resins are grouped together according
to their botanical origin exclusively such as
coniferous resins : colophony, sandarac
Berberidaceae resins: podophyllum
Zygophyllaceae: Guaiacum
II) Chemical classification: Based on predominanat chemical constituents
Acid resins: colophony- abietic acid, sandarac-sandracolic acid
Ester resins: benzoin (benzyl benzoate), storax ( cinnamyl cinnamate)
Alcoholic resins: balsam (gurjuresinol)
Glyco resins: Jalap resins from jalap
 Classification
III) Based on the portion of the main constituent of the resin or resin
combination: e.g. resins, oleo resins, balsams
Natural resin: Gum
Synthetic resin: phenol formaldehyde resin
Based on thermal behavior:
Thermoplastic: Thermoplastic resins become moldable above a specific
temperature and solidify upon cooling.
e.g., acrylic resin, polystyrene (PS), polyvinyl chloride (PVC),
polypropylene (PP)
Thermosetting: Thermosetting resins always remain in a permanent solid state.
They are not moldable ( to give a new shape).
melamine, phenol formaldehyde resin (bakelite, novalac ), polyester
epoxy resin, polyurethane.
 Applications/uses

✓ Paint
✓ Anti-oxidant
✓ Plasticizers
✓ Varnishes, additives
✓ Therapeutic agent
✓ Binders
✓ Incense
✓ Rust & wood protection coatings
✓ Floor tiles
✓ Lubricants
✓ Anti-fogging
 Alkyd resins

A complex oil modified polyester that serves as film forming agent in

paints and clear coatings.
Alkyd- “alcid”…… al- alcohol and cid- acid (carboxylic acid) generally
dicarboxylic acid or its anhydrides.
An alkyd is a polyester modified by the addition of fatty acids and other
components. They are derived from polyols and a dicarboxylic acid or carboxylic
acid anhydride. Alkyds are used in paints and in molds for casting. They are the
dominant resin or "binder" in most commercial "oil-based" coatings.

Phthalic anhydride + glycerol = (polymerization) polyester

Phthalic anhydride + ethylene glycol= polyester

 Classification
Short oil alkyd resins: oil content <40-45%
Medium oil alkyd resins: oil content 45-60%
Long oil alkyd resins: oil content > 60%

Oil content refers to the proportion of mass of triglyceride or

fatty acid relative to the solvent free resin.
Drying resins:
Non-drying resins:
 Raw materials
1. Dibasic acid
2. Polyhydric alcohol
3. Oil/fatty ester
Synthesis
 1. Fatty acid process
Fatty acid process:
Higher quality, higher performance alkyds are produced in the fatty acid
process where the composition of the resulting resin can be more precisely
controlled.
In this process an acid anhydride, a polyol, and an unsaturated fatty acid are
combined and cooked together until the product has achieved a
predetermined level of viscosity. Penta alkyds are made this way.
1. Fatty acid process
1. Fatty acid process
 1. Alcoholic or glyceride process
1. More economical alkyd resins are produced but product quality control is
not as important.
2. It produces a more randomly oriented structure
3. In this process raw vegetable oil, high in unsaturated component, is
combined with additional polyol and heated to cause transesterification of
the triglycerides into a mixture of mono- and diglyceride oils.
4. To this resulting mixture acid anhydride is added to build the molecular
weight of the resin into roughly the same product as in the fatty acid
process.
 Note:
To remove the water produced as a by-product and to increase the reaction
rate, surplus phthalic anhydride was added. Water was thus removed with the
unreacted acid by heating the bulk to a temperature needed to do this. It
meant that the reaction was not as controllable as would be desired. A new
process was introduced, in which Xylene was added to produce
an azeotrope with the water. This gave greater control at a lower temperature,
this also produced resins at a lower viscosity, useful in making high solids
paints; this process was known as the AZO process/solvent process.
 Transesterification
Transesterification is the process of exchanging the organic group R″ of an
ester with the organic group R′ of an alcohol. These reactions are often
catalyzed by the addition of an acid or base catalyst.
1. Alcoholic or glyceride
process
1. Alcoholic or glyceride process
1. Alcoholic or glyceride process
 Phenol formaldehyde resin
Phenol formaldehyde resins (PF) or phenolic resins are synthetic polymers
obtained by the reaction of phenol or substituted phenol with formaldehyde.
Used as the basis for Bakelite, PFs were the first commercial synthetic resins
(plastics). They have been widely used for the production of molded products
including billiard balls, laboratory countertops, and as coatings and adhesives.
They were at one time the primary material used for the production of circuit
boards but have been largely replaced with epoxy resins and fiberglass cloth,
as with fire-resistant FR-4 circuit board materials.
 Phenol formaldehyde resin
Phenol reacts with formaldehyde at the ortho and para sites (sites 2, 4 and 6)
allowing up to 3 units of formaldehyde to attach to the ring. The initial reaction
in all cases involves the formation of a hydroxymethyl phenol:
HOC6H5 + CH2O → HOC6H4CH2OH

The hydroxymethyl group is capable of reacting with either one hydroxymethyl

group or another free ortho or para site. The first reaction gives a methylene
bridge, and the second forms an ether bridge:

HOC6H4CH2OH + HOC6H5 → (HOC6H4)2CH2 + H2O

2 HOC6H4CH2OH → (HOC6H4CH2)2O + H2O

General Synthesis
 Phenol formaldehyde resin:
Novolac
Novolacs are phenol-formaldehyde resins with a formaldehyde to phenol
molar ratio of less than one. The polymerization is brought to completion
using acid-catalysis such as oxalic acid, hydrochloric acid or sulfonate acids. The
phenol units are mainly linked by methylene and/or ether groups. Novolacs are
commonly used as photoresists. The molecular weights are in the low ( below
thousands), corresponding to about 10–20 phenol units.

Hexamethylenetetramine or "hexamine" is a hardener added to crosslink

novolac. At a temperature >90 °C, it forms methylene and dimethylene amino
bridges.
Novolac
Crosslinked resin: Bakelite
 Phenol formaldehyde resin: Resols
Base-catalysed phenol-formaldehyde resins are made with a formaldehyde to
phenol ratio of greater than one (usually around 1.5). These resins are called
resoles. Phenol, formaldehyde, water and catalyst are mixed in the desired
amount, depending on the resin to be formed, and are then heated. The first
part of the reaction, at around 70 °C, forms a thick reddish-brown tacky
material, which is rich in hydroxymethyl and benzylic ether groups.

When the molar ratio of formaldehyde: phenol reaches one, in theory every
phenol is linked together via methylene bridges, generating one single
molecule, and the system is entirely crosslinked. This is why novolacs (F:P <1)
do not harden without the addition of a crosslinking agents, and why resols
with the formula F:P >1 will.
Phenol formaldehyde resin: resole
Novolac vs Resols
Epoxy resin
Applications
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