Basics of

Decorative
Paint
Formulation
Content
 Definition of Paint
 Constituent of Paint and their function in brief
 Processing of water based paint in HSD and mode of addition
 Basics of various ingredients used in paint formulation and their role
Definition of Paint
Paint can be defined as a surface coating which when applied on to a substrate in the form of thin layer, will form a solid ,
adherent & coherent film.
 Paint applied on to a substrate to decorates and protects the surface.
 It is a uniform physical mixture of pigment, binder, solvent and additives.
 Some paints may not contain solvent. It is available in liquid or powder form.

Some example of paints in powder form are Dry Distemper, Powder Coating ant Cement paints etc. These are converted
to fluid (1) by addition of suitable thinner prior to application, (2) by application of heat or can be directly applied to the
substrate using special application techniques.
 Paint film may be opaque, translucent or transparent
 Paint film may be of glossy, matt, eggshell, satin or semi-glossy finish.

 Substrate condition
 Surface preparation The success or failure of any paint is largely depends
 Application Technique on the following factor
 Environmental condition
 Quality of paint
Constituent of Paint and Function – In General

Pigment
Binder
 Biocide/ Fungicide/
Extender - Film former. Co-Solvent Additive Algicide
 In can stabilizer/
- Provides like medicine or, preservative
- Colour - Reduce cost of - Binds pigments
- paint formulation
workable vitamins  Defoamer
& extenders consistency.
Opacity - Modify flow together. - Improve  Rheological Additive
- Hardness - Influence flow & properties  Neutralising agent
(Viscosity)
- leveling and - Improve process
- Sedimentation drying.
 Anionic Surfactant
Durability ability
Tendency
- Enhances (Pigment & Extender
- Provides gloss. - Impart new wetting)
- Film Strength performances.
- - Adherence. properties
 Non ionic Surfactant
Functional - Elasticity.
performances (Dispersion Stabiliser)
- Functional  Coalescing Agent
performances
Processing of Water Based Paint
The water based paint formulation can be processed in
To
To obtain
obtain optimal
optimal
High Speed Dispermat Pug Mill
dispersion
dispersion the the geometry
geometry
of
of the
the dispersion
dispersion vessel
vessel
has
has to be matched with
to be matched with Stiff Paint can be
the
the peripheral speed and
peripheral speed and
the distance of the
processed in Pug Mill
the distance of the
impeller
impeller disc
disc to
to the
the
bottom
bottom of of the
the vessel,
vessel, asas
well
well as
as with
with the
the viscosity
viscosity  All the ingredients
The mill base
The mill base should behavior
should be
behavior of
be of ofof the
high millbase.
viscosity
millbase.to
theviscosity
high to need to be added
guarantee
guarantee that that the
the different
different speed
speed of of one by one at same
impeller
impeller disc/mill
disc/mill base
base causes
causes the the dispersion
dispersion speed by adjusting
of
of the pigment agglomerates. When the
the pigment agglomerates. When the water to get a
dissolver is applied properly, the
dissolver is applied properly, the millbase millbase
desired viscosity
exhibits
exhibits laminar
laminar flow
flow without
without turbulence.
turbulence.

Liquid Paint can be processed with High Speed Dispermat.  Typically Emulsion
use to be added at
It’s a 3 stage process: the end of the
 Premix – Low speed, Rheology build up with thickener dispersion
 Grinding – Very high Speed, dispersion of pigments and extender to get an
uniform finish  Typically distemper, putty are processed in Pug Mill
 Let Down – Stabilization of dispersion and addition of Polymeric Binder
 Most economical dispersion machine
(Emulsion) to achieve ultimate finish product
Processing of Water Based Paint
in HSD  Rheological Additive (Non associative)
 Non Ionic Surfactant
 Defoamer
 Coalescing agent
 Emulsion
 Rheological Additive (Associative)
Stabilization  Polymeric Opacifire

Low - Medium Speed  < 1000 rpm

 Pigment
 Extender Typ
Grinding ica
High Speed  > 1500 rpm lS
eq
ue
nc
eo
Premix  Biocide/ Fungicide/ Algicide fA
dd
 In can stabilizer/ preservative itio
Low Speed  < 500 rpm n
 Defoamer
 Rheological Additive (Associative/Non associative)
 Neutralising agent
 Anionic Surfactant (Pigment & Extender wetting)
 Non ionic Surfactant (Dispersion Stabiliser)
Basics of Formulation
A typical water based formulation comprises of following ingredients:
Ingredients Stage of Paint Purpose to use
Preparation
1. Water Premix Dispersion media
2. Biocide/ Dry paint films are vulnerable to a variety of microorganisms that provide a basis for algal, fungal, moss, or lichen growth and
Fungicide/ cause severe problems, such as discoloration and physical degradation.
Algicide Physical deterioration leads to an increase in porosity of the surface coating, loss of adhesion to the substrate, and moisture
penetration, which results in the decay of the underlying substrate.
Algae are one of the two main organisms encountered on exterior coatings that actually disfigure the dry paint film.
Unfortunately, they are sometimes confused with fungi, especially if they are brown or orange instead of green, which is more
common.
Dry film preservatives are typically blends of an algaecide and one or more fungicides, designed to ensure resistance to a broad
range of algae and fungi. The blends are added to the architectural paint, which is then applied to a variety of exterior surfaces.

3. In can In-can preservative used to avoid deterioration and degradation of aqueous systems caused by bacteria, fungi and yeast. Is
stabilizer/ useful for the in-can protection of various water borne end-use products
preservative

4. Defoamer A defoamer or an anti-foaming agent is a chemical additive that reduces and hinders the formation of foam in liquids. The
terms anti-foam agent and defoamer are often used interchangeably. Commonly used agents are insoluble oils,
polydimethylsiloxanes and other silicones, certain alcohols, stearates and glycols. The additive is used to prevent formation of
foam or is added to break a foam already formed.
Generally a defoamer is insoluble in the foaming medium and has surface active properties. An essential feature of a defoamer
product is a low viscosity and a facility to spread rapidly on foamy surfaces. It has affinity to the air-liquid surface where it
destabilizes the foam lamellas. This causes rupture of the air bubbles and breakdown of surface foam. Entrained air bubbles are
agglomerated, and the larger bubbles rise to the surface of the bulk liquid more quickly.
Basics of Formulation
Ingredients Stage of Purpose to use
Paint
Preparation
5. Cosolvents Premix Usually glycols are used. It attribute freeze-thaw stability, due to low evaporation rate improves flow and levelling in the wall i.e.
enhances the open time of the film leads to improve ease of application, smooth finish, low patchiness etc. However, excess
level of inclusion can lead to hamper mechanical properties like wash ability, scrub resistance, optical performance and surface
leaching tendency.
6. Rheological Rheological additive could be associative or non associative. Associative thickeners (HEUR – Hydrophobically modified ethylene
Additive oxide urethane thickener or NISAT - Non ionic synthetic acrylic thickener attribute association with polymer leads to increase in
viscosity of the paint. In premix high shear associative thickening agent can be used to maintain a good viscosity to achieve
stable dispersion. Non associative thickening agent like HEC (Hydroxyl Ethyl Cellulosics) or CMC (Carboxy Methyl Cellulose)
attributes thickening effect through association with water phase.
Non associative thickeners are more water sensitive w.r.to associative thickener.
Flow and levelling property are found to be better in case of associative thickener.
However, non associative thickeners are more cost competitive than associative thickener. This draws the attention of paint
formulator while designing high PVC economical paint. In case of low PVC premium paint, the usage of associative thickener is
almost inevitable.
7. Neutralising Usually amines or amine deivatives, NaOH are added in the mill base recipe to maintain alkalinity of the medium. The
agent (Base) adjustment of pH in waterborne coatings is important in order to maintain a stable pigment dispersion, minimize corrosion,
reduce biological growth and generally optimize the performance of the coating during storage and application.
8. Anionic Anionic surfactants are used in the formulation to disperse the pigments and extender having carboxylic, phosphate etc
Surfactant functional group. Surfactants are usually comprised of hydrophobic and hydrophilic groups. Depending on the hydrophilic
(Pigment & groups, surfactants are classified as anionic, cationic, non-ionic or amphoteric. Anionic surfactants dissociate in water into a
Extender negatively charged ion and a positively charged ion and the hydrophilic head is negatively charged (anion). Anionic surfactants
wetting) are the most common and inexpensive surfactant. Based on the efficiency of anionic surfactants, pigment wettability of the
system increases which attribute better optical performance.
Basics of Formulation
Ingredients Stage of Purpose to use
Paint
Preparation
9. Non ionic Premix Non ionic surfactants are also based on hydrophobic and hydrophilic group. Here the functionality varies with hydrophobe &
Surfactant ethylene oxide chain length. The non ionic surfactant usually stabilises dispersion by steric hindrance through the long chain
(Dispersion hydrocarbon part which enhances the stability of the dispersion and contribute excellent optical performance.
Stabiliser)
10. Pigments Grinding/ Pigments like TiO2 attribute optical performance like hiding, contrast ratio, exterior durability etc
Milling
11. Extenders Extender pigments are added in order to reduce the cost of a paint formulation. They are also used to modify the flow
(viscosity), sedimentation stability and film strength. Most extender pigments appear white and possess a refractive index
similar to commonly used binders. Most of the extender pigments occur naturally and others can be produced synthetically.
Aluminium silicate, magnesium silicate (talc), silica, calcium carbonate (synthetic and natural) and barium sulfate are some
commonly used extender in paints and coatings
12. Coalescing Let Down Coalescing agents are used in dispersion paints for optimizing the film formation process of the polymeric binder particles. The
Agent film formation process in dispersion paints involves the coalescence of the polymeric particles, during and after the evaporation
of the diluents (notably water), thereby permitting contact and fusion of adjacent polymeric dispersion particles. Coalescing
agents typically reduce the minimal formation temperature and as a consequence to optimize film coherence and properties
such as scrub resistance, mechanical properties as well as appearance.
13. Binder Binders are basically providing film forming matrix which can hold all the solid particles present in the paint recipe and attribute
mechanical, chemical, barrier and durability properties.
14. Rheological Typically associative thickeners are used in the formulation which has been added after adding emulsion to attribute association
Additive property and develop a good range of viscosity in low shear range. Associative thickening involves non-specific interactions of
hydrophobic end groups of a thickener molecule both with themselves and with components of the coating. The thickener
produces a reversible, dynamic network of thickener molecules and other components of the coating. The thickening effect is
caused by interactions of the hydrophobic end groups of the thickener with other components of the formulation.
 Detailed Discussion of
Various Ingredients used
in Paint Formulation
Biocide
Need At
At every
every stage
stage of
of their
their service
service lives,
lives, latex
latex emulsions
emulsions and
and coatings
coatings are
are susceptible
susceptible to
to contamination
contamination and
and degradation
degradation by
by aa variety
variety of
of microorganisms.
microorganisms.

Bacteria
Bacteria Fungi
Fungi •Algae
•Algae
-Aerobic
-Aerobic // Anaerobic
Anaerobic -Filamentous
-Filamentous fungi
fungi -Green
-Green Algae
Algae
-Sphere
-Sphere shaped
shaped // rod
rod shaped
shaped // spiral
spiral -Yeast
-Yeast (e.g.
(e.g. Aspergillusniger,
Aspergillusniger, -Brown
-Brown Algae
Algae
(e.g.
(e.g. Pseudomonas
Pseudomonas aeruginosa,
aeruginosa, Penicilliumsps.,
Penicilliumsps., -Red
-Red Algae
Algae
E.coli, Enterobacteraerogenes)
E.coli, Enterobacteraerogenes) Cladosporium)
Cladosporium) -Blue
-Blue Green
Green Algae
Algae (e.g.
(e.g.
Nostocmuscorum,
Nostocmuscorum,
Chlorella
Chlorella sp.,
sp.,
Oscillatoriatenius
Oscillatoriatenius

 Inadequate
Inadequate preservation
preservation of
of paints
paints and
and surface
surface coatings
coatings will
will lead
lead to
to visual
visual To
To protect
protect against
against the
the microorganisms
microorganisms that
that can
can cause
cause problems,
problems,
contamination. Incan
contamination. Incan bacterial
bacterial contamination
contamination can
can lead
lead to
to undesired
undesired liquefaction,
liquefaction, paint
paint manufacturers
manufacturers must
must customarily
customarily use
use biocides.
biocides.
odors,
odors, gassing
gassing and
and discoloration.
discoloration. At
At this
this stage
stage the
the paint
paint is
is generally
generally beyond
beyond
recovery. To
recovery. To avoid
avoid this,
this, the
the addition
addition of
of preserving
preserving biocides
biocides is
is absolutely
absolutely necessary.
necessary. Biocides
Biocides are
are chemical
chemical substances
substances or or microorganisms
microorganisms which
which can
can
 Facades deter,
deter, render
render harmless,
harmless, or
or exert
exert aa controlling
controlling effect
effect on
on any
any harmful
harmful
Facades are
are usually
usually made
made ofof mineral
mineral materials
materials such
such as
as stucco
stucco and
and gypsum,
gypsum, asas well
well
organism
organism by
by chemical
chemical or
or biological
biological means.
means.
as wood
as wood materials
materials which
which favor
favor the
the growth
growth of
of micro-organisms.
micro-organisms.
 Once
Once aa painted
painted surface
surface is
is colonized
colonized by
by micro-organisms,
micro-organisms, the
the integrity
integrity of
of the
the paint
paint is
is
According
According to to the
the type
type ofof micro-organism
micro-organism controlled
controlled in
in paint,
paint,
compromised,
compromised, and
and it
it may
may result
result in
in undesirable
undesirable color
color changes
changes and
and loss
loss of
of adhesion.
adhesion. biocides
biocides areare classified
classified into
into three
three types
types
Substrates
Substrates are
are then
then vulnerable
vulnerable and
and breakdowns
breakdowns may
may result.
result. Therefore
Therefore surface
surface  Bateriacide
Bateriacide -- Mainly
Mainly used
used to
to preserve
preserve water
water based
based paints
paints in
in the
the
coatings
coatings such
such as
as exterior
exterior paint
paint or
or interior
interior paints
paints for
for special
special applications
applications such
such as
as can.
can.
 Fungicides
Fungicides –– Mainly
Mainly toto protect
protect exterior
exterior paint
paint films
films against
against
bathrooms
bathrooms or
or kitchens
kitchens require
require dry
dry film
film protection.
protection.
disfigurement from moulds, fungi and lichen
disfigurement from moulds, fungi and lichen
 The
The choice
choice of
of the
the correct
correct biocide
biocide will
will depend
depend on
on pH
pH of
of the
the formulation
formulation as
as well
well as
as on
on  Algicides
Algicides -- Mainly
Mainly to to protect
protect exterior
exterior paint
paint films
films against
against
regulatory requirements
regulatory requirements such
such as
as VOC
VOC contribution
contribution or
or Ecolabels.
Ecolabels. disfigurement
disfigurement from
from algiae
algiae
Common Biocide used in Paint
Type Biocide Active name Chemical structure
In Can 5-Chloro-2-methyl-4-Iso-thiazolin-3-one
(CMIT )
2-Methyl-4-Isothiazolin-3-one (MIT)

Antifungal Methyl -N-(2-Benzimidazolyl)Carbamate

(Carbendazim)

2-Octyl-2H-isothiazol-3-one
(OIT)

3-Iodopropynyly-butyl-carbamate
(IPBC)

Antialgal N’(3,4- dichlorophenyl)-N,N-dimethylurea

(Diuron)
Defoamers
A stable dispersion of gas in liquid is called Foam. If a stream of air is introduced in liquid, the bubbles produced assume a spherical shape.

The
The cause
cause of
of Foam
Foam is
is the
the introduction
introduction of
of gas
gas into
into the
the liquid
liquid material.
material. This
This can
can occur
occur by:
by:
 Mechanical introduction of air during manufacture by stirring and
Mechanical introduction of air during manufacture by stirring and mixing mixing
 Displacement
Displacement of
of air
air during
during wetting
wetting of
of pigment
pigment and
and filler
filler
 Mechanical
Mechanical introduction
introduction ofof air
air during
during application
application such
such asas rolling,
rolling, spraying
spraying or
or printing
printing Micro Macro
 Displacement
Displacement of
of air
air when
when coating
coating porous
porous substrate
substrate Foam Foam

In
In liquids
liquids paints
paints containing
containing surfactants,
surfactants, the
the gas
gas bubbles
bubbles are
are stabilized
stabilized by
by the
the surfactants.
surfactants. Fig. Rise and bursting of air Fig. Rise and stabilization of
A
A surfactant film forms around gas bubbles which is also coated with surfactants. A
surfactant film forms around gas bubbles which is also coated with surfactants. A bubbles in surfactant free air bubbles in liquid
surfactant stabilized double layer or duplex film is formed.
surfactant stabilized double layer or duplex film is formed. liquids containing surfactants

The
The occurrence
occurrence ofof foam
foam must
must therefore
therefore be
be considered
considered as
as undesirable
undesirable but
but unavoidable
unavoidable phenomenon
phenomenon in
in coating.
coating. To
To prevent
prevent and
and destroy
destroy any
any foam
foam present,
present, defoamers
defoamers
have
have to to be
be added
added to to the
the formulation
formulation
Fundamentally,
Fundamentally, aa defoamer
defoamer mustmust
be
be insoluble in the formulation to
insoluble in the formulation to
Mechanism be deformed where it
be deformed where it should beshould be
present
present in in the
the form
form of of finely
finely
Defoamers
Defoamers work work by by penetrating
penetrating the
the foam
foam lamella,
lamella, destabilizing
destabilizing divided
divided droplets.
droplets. Furthermore
Furthermore it it
it and making it
it and making it burst.burst. is necessary for it to be
is necessary for it to be
sufficiently
sufficiently compatible
compatible with with the
the
Requirement
Requirement for for Defoamers:
Defoamers: medium to be defoamed.
medium to be defoamed. The The
 Insoluble
Insoluble in
in the
the formulation
formulation toto be
be defoamed
defoamed
choice
choice of
of defoamer
defoamer is is therefore
therefore
 Low
Low surface
surface tension
tension always
 Positive always compromise
compromise between between
Positive penetration
penetration co-efficient
co-efficient defoaming
 Positive defoaming performance and
performance and
Positive spreading
spreading co-efficient
co-efficient and
and dewetting
dewetting characteristics
characteristics compatibility/insolubility
compatibility/insolubility
Defoamer - Mechanism
The working mechanism of a defoamer can be characterized in three steps:
Step 1: A defoamer droplet has to enter the foam lamella. Due to it’s highly
surface active properties the defoamer droplet has a strong tendency to
migrate to the air/water/surfactant interface
Step 2: The defoamer droplet spreads and pushes aside the stabilizing
surfactant. Without the stabilizing surfactant the foam lamella locally becomes
much less elastic (“reverse Maragoni effect”) A weak spot is formed
Step 3: This kind of destabilization facilitates rupture of the foam lamella
Fig. Schematic drawing of entering, spreading and destabilizing a
surfactant layer by a defoamer droplet

To increase defoamer efficiency, it is a common approach to add finely

divided hydrophobic particles such as hydrophobic silica or waxes to the
formulation. The hydrophobic solid particles are able to destabilize the
foam lamella by a dewetting process.
In simple terms, the surfactant film which stabilizes the foam lamella is
not able to wet the hydrophobic solids and “shrinks back”. An unstable
area results where the lamella is thus destabilized.

A defoamer’s point of action is the foam lamella. Therefore, it must be

insoluble in the paint system and the defoamer droplet must be rather
mobile so they can enter the lamella and develop the defoaming
Fig. Schematic drawing of de-wetting properties of hydrophobic particles
action.
in a defoamer formulation
Types of Defoamer
Polysiloxane Star Polymer Based Defoamer
Basically,
Basically, Organically
Organically modified
modified polydimethylsiloxane
polydimethylsiloxane (PDMS)
(PDMS)
Star Polymer
Star Polymer isis aa hyper-
hyper-
PDMS
PDMS is is aa particularly
particularly efficient
efficient defoamer
defoamer branched polymer
branched polymer withwith
ingredients
ingredients because
because of of its
its low
low surface
surface aa 3D
3D star-shaped
star-shaped
tension,
tension, spreading
spreading capability,
capability, thermal
thermal structure,
structure, containing
containing
stability,
stability, chemical inertness and water
chemical inertness and water hydrophilic as
hydrophilic as well
well as
as
insolubility. Organic modification of
insolubility. Organic modification of PDMS PDMS hydrophobic element.
hydrophobic element.
with
with polyethers
polyethers or or other
other organic
organic groups
groups
renders
renders thethe product
product more
more compatible
compatible andand
allows
allows thethe formulation
formulation of of highly
highly efficient
efficient Unlike conventional
Unlike conventional mineral
mineral oil
oil andand silicone
silicone defoamer,
defoamer, itit
defoamers with excellent
defoamers with excellent compatibilitycompatibility
defoam on
defoam on aa molecular
molecular level.
level. ItIt act
act as
as aa unique
unique surfactant
surfactant
characteristics
characteristics for
for high
high performance
performance interacting with
interacting with the
the foam
foam stabilizing
stabilizing surfactant
surfactant and
and destabilze
destabilze
applications
applications the foam
the foam bubbles.
bubbles. When When combine
combine with with conventional
conventional
defoamer types
defoamer types itit yields
yields faster
faster bubble
bubble break
break times
times andand
Mineral Oil improves the
improves the overall
overall efficiency.
efficiency. Bubble
Bubble break
break time
time isis the
the time
time
in seconds
in seconds needed
needed to to break
break all
all macro
macro bubbles
bubbles inin aa paint
paint film;
film;
the shorter
the shorter the
the time
time the
the better
better the
the defoamer.
defoamer.
Mineral
Mineral Oil
Oil with
with their
their high
high spreading
spreading power
power and
and
high
high incompatibility have long been used as
incompatibility have long been used as
defoaming agent. It attribute excellent
Advantages
defoaming agent. It attribute excellent
cost/performance
cost/performance ratio as well. Due to
ratio as well. Due to  Multifunctional
Multifunctional (Defoaming
(Defoaming and
and wetting)
wetting)
environmental
environmental and and physiological
physiological consideration,
consideration,  Improved
Improved bubble break time compared to
bubble break time compared to conventional
conventional
aliphatic
aliphatic mineral
mineral oils
oils are
are used
used predominantly
predominantly inin defoamer
defoamer
comparison wth aromatic version. This
comparison wth aromatic version. This defoamerdefoamer  Excellent
Excellent defoaming
defoaming persistence
persistence
find
find limited
limited application
application when
when demands
demands areare made
made  Effective
Effective against
against microfoam
microfoam
to achieve glossy finish.
to achieve glossy finish.  Easy
Easy to
to incorporate
incorporate
Rheological additive
Organic thickeners for waterborne coatings can be largely classified as: 1. associative thickeners and 2. Non-associative thickeners.

Associative thickening involves non-specific interactions of hydrophobic endgroups of a thickener molecule both with themselves and with components of the
coating. The thickener produces a reversible, dynamic network of thickener molecules and other components of the coating. The thickening effect is caused by
interactions of the hydrophobic end groups of the thickener with other components of the formulation. Associative thickeners also consist of hydrophilic water-
soluble or water-emulsifiable polymer components and can simultaneously act in a non-associative manner. Both thickening modes are exhibited by associative
thickeners. Associative thickening can produce rheology ranging from Newtonian to pseudoplastic. Associative thickeners are often used to adjust application
properties such as spattering or brushing resistance. Formulations with associative thickeners often exhibit high gloss and good levelling.
Non-associative thickening is
thickening by an entanglement of
water-soluble, high molecular weight
polymer chains. The effectiveness of
a thickener is mainly determined by
the molecular weight of the polymer.
Formulations thickened
nonassociatively have pseudoplastic
rheology with highly elastic
properties. This produces good
stabilization against settling out and
low sagging even with high build
coatings. Non-associatively thickened
systems often have limited
flowability. The high molecular weight
of the thickeners can sometimes lead
to compatibility problems such as
depletion flocculation.
Mechanism of HEC Thickener
The largest group of materials of this type, which is solely dependent on viscosity development
of the water phase, is the series of cellulose-based thickeners. Cellulose itself is very interesting
material. Constituting the skeleton of trees and a wide variety of plants, it is a fantastic source
of renewable furnish. The polymer itself contains hydroxyl groups making the material very
hydrophilic. Because of hydrogen bonding effects the polymer chains are to a large extent
aligned in a crystalline setting. Consequently, cellulose itself is not water-soluble. The structure,
however, will either swell or break up under alkaline conditions. This breakdown of the
crystallinity can be made permanent by (partly) substituting the hydroxyls, thus making a
return to the original situation impossible (Fig.2). The level and type of substituent introduced
largely determines the solubility parameters of the resulting cellulose derivative.

The following overview covers the types of cellulose ethers that are widely used in waterborne
coatings.
HEC/EHEC Substitution of the hydroxyls by hydroxyethoxyl groups, eventually combined with
ethyl substituents, not only enhances the permanent non-crystallinity of the cellulose
backbone, but at the same time keeps the material in a hydrophilic state. The material is
therefore very suitable for the purpose and thus often used as a paint thickener.

HM(E)HEC This group also incorporate hydrophobic agents, which make the materials very
attractive in formulations leading to enhanced performance as will be explained later.

MC Substitution by methylgroups is also a means to bring about solubility. However to ensure

proper solution properties under application conditions the methyl groups are usually
combined with hydroxyethoxyl or hydroxypropoxyl groups.

CMC Another substituent that is used in paint applications is carboxymethoxyl. The resulting
thickener is usually available in its sodium salt form and thus exhibits an anionic character.
Needless to say, this charged material is extremely hydrophilic.

HEC thickeners are being used in wide range of paints starting from med to high PVC liquid paint. Higher quantity of HEC thickener in the formulation helps to improve application performance.
However, it affects the water sensitivity of the film. Hence, hydrophobically modified HEC thickener could be a good option to handle the situation.
Bio stable Cellulosics
Once a system has been thickened, the material should retain its rheology unchanged until it is applied. However, there are some specific species that can adversely affect the final coating
over time. Problems of viscosity loss often have their origin in the very early part of the paint production. Bacteria, fungi or yeasts may be incorporated as unwanted components of the
formulation, entering via raw materials, water, or through the production environment in general. In addition to the fact that this usually causes deficiencies like odour and discolouration,
the system might reduce in viscosity due to degradation of the cellulose ether caused by enzymes produced by the bacteria. Usually paints are well preserved, but enzymes already present
before the preservation step can be a potential threat. So-called cellulytic enzymes are able to reduce the molecular weight once they are present. The point of enzymatic attack is those
glycosidic linkages adjacent to unsubstituted anhydroglucose units. The enzymes are able to break these linkages, resulting in viscosity loss.

The way to increase the enzyme resistance of cellulose ethers is to limit the amount of unsubstituted anhydroglucose units by adjusting the reaction conditions accordingly. In other
words, to increase the degree of substitution rather than the molecular substitution, as is shown in this Fig. 6. The resulting cellulose ether is known as biostable or "B"-grade material.
REDUCED SPATTER CELLULOSIC THICKENERS
Spatter is caused by elasticity, and elasticity in its turn is strongly related to the molecular weight of the thickener. The higher the molecular weight, the more spatter. Unfortunately the
higher molecular weight thickeners like HEC are at the same time also the most efficient ones, so the challenge is to have an efficient thickener providing good spatter performance once
formulated into paint.
To meet this challenge, hydrophobically modified hydroxyethyl celluloses, abbreviated as HMHEC, were developed and launched. These materials have an architecture similar to HEC, being
extended by the addition of hydrophobic groups. By making use of other viscosity increasing mechanisms than just by thickening the water phase, the molecular weight could be decreased, and
thus the elasticity, without affecting the thickening efficiency."Regular" cellulose ethers increase the viscosity of the water phase by the formation of hydrogen bonding with water molecules and
by means of coil overlap and entanglement.However, HMHEC utilizes additional mechanisms. In addition to the formation of hydrogen bonding with water molecules, coil overlap and
entanglement the material is also able to increase viscosity by network building via inter- and intramolecular bonds, which makes it a versatile polymer

HMHEC is also able to associate via its hydrophobic side chains with major components in the
paints that are also hydrophobic in nature, such as latex particles. It thus is able to form a
network structure, thereby enhancing its contribution to the increased viscosity of the paint

Lowering the molecular weight is not only an effective remedy to control the level of elasticity,
but it also changes the flow profile towards a less pseudoplastic character, as has been
explained earlier. This in its turn has also a positive effect on other paint properties. In addition
to an outstanding spatter resistance, the material provides higher brushing viscosity but also
better levelling when compared with higher molecular weight HEC, at equal thickening
efficiency
Mechanism of HASE Thickener

Hydrophobically Modified AlkaliSwellable Emulsion

Thickeners (HASE) Hydrophobically modified alkali-
swellable rheological additives provide thickening and
rheological performance in waterborne systems by
molecular chains extension into water phase under
alkaline condition. The hydrophobic groups along the HASE
polymer chains associate with other components (e.g.
binder, pigment, surfactant, etc.) in paint formulations.
They provide predictable viscosity development, ease of
handling and the flexibility of being post-added in the
manufacturing process.

Through innovative polymer design, these thickeners are

able to provide a wide range of rheological behavior from
highly shear thinning to near Newtonian flow.

They also enhance spatter resistance while improving

flow and leveling. Some of these products are suitable The usage of HASE thickener is found to be more in
replacement (partially or completely) for HEC and putty, primer, stiff paint and high PVC liquid paint
HMHEC. Furthermore, HASE are enzyme resistant unlike
HEC/HMHEC.
Non-Ionic Synthetic Associative Thickeners (NISAT)
The structure of Non-ionic synthetic associative thickeners can be schematically
represented as two hydrophobic heads and a hydrophilic backbone. The analogy
with the traditional representation of a surfactant is obvious and indeed these
materials behave in many respects just like surfactants in coatings formulations.
The properties of these associative thickeners are controlled by changing the
frequency and chemistry of the hydrophobic units. More hydrophobic caps give
stronger association and shear thinning flow. If the caps are less hydrophobic,
association is weak and the additive gives a more Newtonian flow behavior