Functions of Dispersing

Additives in Ink

By :
Adesh Katariya
Manager- R&D, Tirupati Inks Ltd
plast.adesh@gmail.com
 Pigment
 A pigment is a coloring particle which is insoluble in the
application media.
 Particle size and crystal structure of pigments determine
the application properties like gloss, tinting strength etc

Primary particles are single

crystallites or sub crystallites which
are strongly connected by their
surface areas. They can not be
destroyed during normal grinding
processes.

2
 Pigment Properties

3
 Pigments in Comparison

Organic Inorganic
Property
Pigment Pigment

Particle size (µm) Small Large

Surface area (m2/g) Large Small
Polarity Non-polar Polar
4
Objective of Pigment Dispersion

 To separate the pigment agglomerates which are formed

(by hydrophilic aggregation) during the drying processes in
pigment manufacture.
As particle size is reduced, the
surface area so created
increases, leading to an
improvement in optical
properties, such as tinctorial
strength, gloss, brightness,
opacity or transparency.

5
 Pigment Dispersion

6
Improved Dispersion and Dispersing Additive

 The improved dispersion means a smaller average particle

size with a narrower particle size distribution.
 Small particles are generally more prone to re-
agglomeration or flocculation.

With dispersing additives reducing

inter-particle attraction, dispersions
are significantly more stable to
flocculation and agglomeration
than those produced by
conventional means.

7
De-flocculation -Flocculation

8
Wetting and Dispersing Process

High brilliance and color strength are characterized by a perfect pigment

dispersion, optimal pigment particle size, and long-term stabilization of
the dispersed particle in the formulation.

9
Pigment wetting:

All of the air and moisture is displaced from the surface

and between the particles of the pigment aggregates and
agglomerates (clusters) and is replaced by the resin
solution.

The solid/gaseous interface (

pigment/air) is transformed into a
solid/liquid interface (pigment/resin
solution).

10
Proper Wetting

11
Wetting and Surface tension

The efficiency of the wetting depends primarily on the

comparative surface tension properties of the pigment and
the vehicle, as well as the viscosity of the resultant mix. The
adsorption mechanism depends on the chemical nature of
the pigment and the types of dispersing agents used.
12
Grinding stage:

Through mechanical energy (impact and shear forces), the

pigment agglomerates are broken up and disrupted into
smaller units and dispersed (uniformly distributed).
Ideally, a fully deflocculated state will arise, in which all
pigment particle agglomerates have been broken up into
their primary particles.

13
Stabilization of pigment suspension :

The pigment dispersion is stabilized by the adsorption of

binder species or molecules at the pigment surface

14
Pigment Stabilization

15
Pigment Stabilization Mechanism

System Stabilization Mechanism

Solvent-based Steric stabilization

Water Based Electrostatic / Steric stabilization

Emulsion Electrostatic stabilization

Polymerics (UV) Steric stabilization

16
WHY Dispersant Required ?

Dispersing Additives have two fundamental roles in surface

coatings;
o they produce improved pigment dispersion
o they reduce inter-particulate attraction within that
dispersion.

17
Dispersing Agent and Rheology

The greater steric repulsion generated by the addition of polymeric

dispersants moves the minimum in the Potential Energy Curve, and thus
reduces the overall viscosity.

18
Dispersants families
In term of chemical structure one can divide dispersing
agents into the two following classes:

1. Polymeric dispersants -Sterical stabilization

2. Surfactants-Electrostatic stabilization

The main differences of those two types of dispersants

being the molecular weight, the stabilization mechanism
and the resulting let down stability.

19
Electrostatic stabilization

A charge is generated on the pigment surface, and a more

diffuse cloud of oppositely charged ions develops around it.

As two particles approach each other the

charge effectively provides a barrier to
closer particle interactions.

20
Sterical stabilization

 Steric Stabilization occurs

by the adsorption of a
layer of resin or polymer
chains on the surface of
the pigment.

 Effective in media of low

dielectric constant.

21
Mechanism of Steric Stabilization

22
Mechanism of Steric Stabilization

23
 Mechanism of Steric Stabilization

24
 Mechanism of Steric Stabilization

25
Mechanism of Steric Stabilization

26
 .

27
 .

28
 .

29
 ..

30
 .

31
 .

32
 .

33
 .

34
 Polymeric dispersants

Polymeric dispersants stabilize ink systems via a steric

stabilization mechanism previously described. They have a
two-component structure which combines the following two
very different requirements:
o It must be capable of being strongly adsorbed into the
particle surface and thereby possess specific anchoring
groups .
o The molecule must contain polymeric chains that give
steric stabilization in the required solvent or resin solution
system.

35
Structure of Wetting and Dispersing
Additives

36
Pigment affinic groups

37
Dispersing Additives :Advantages

 Higher gloss
 Lower haze
 Higher color strength
 Improved hiding power
 Better transparency
 Low viscosity / Newtonian Flow
 No flooding & floating

38
Co-polymer/functional polymer
configurations

39
Dispersing Additives : How to stabilize
the pigments

40
Dispersing Additives : How to stabilize
the pigments

41
Adsorption/Anchoring of Dispersing agent
on Pigment Surface

42
Anchoring Mechanisms

As the nature of the surface of pigments differ, according to their

chemical type, many different chemical groups can be found as anchor
groups for polymeric dispersants.
This wide range of anchoring possibility enables polymeric dispersants
to disperse inorganic pigments as well as pigments with polar surfaces.
The actual anchoring can then take place through a variety of
mechanisms;.
1. Through Ionic or Acidic/Basic Groups.
2. Through Hydrogen-Bonding Groups
3. Through Polarizing Groups
4. Through Solvent-Insoluble Polymer Blocks

43
Anchoring Through Ionic or Acidic/Basic
Groups

When a pigment particle has a relatively reactive surface

(eg: inorganic pigments) it is possible to form an ion-pair
bond between a charged site on the particle surface and
an oppositely charged atom or functional group on the
dispersant.

44
Anchoring Through Hydrogen-Bonding
Groups

A strong interaction may

be developed between the
pigment particle and a
polymeric dispersant
containing many
hydrogen-bond donors
and acceptors in its
anchor chain

45
Anchoring Through Polarizing Groups

An interaction can also take place

between polarized or polarizable
groups on an organic pigment
particle surface, and similarly
polarized or polarizable groups on
the anchoring function of the
polymeric dispersant. Again, these
interactions will often be relatively
weak, but strong interaction may be
developed with a polymeric
dispersant possessing an anchor
chain composed of several of these
groups.
46
Anchoring Through Solvent-Insoluble
Polymer Blocks

It is possible to anchor a
polymeric dispersant onto a
pigment particle surface
simply via van der Waals
interactions and without
recourse to ionic, hydrogen-
bonding, or polarizing effects.

The polymeric block within

the dispersant must simply be
insoluble in the medium

47
TiO2: Surface Treatments

48
TiO2: Surface Treatments

49
Groups on Carbon black Surfaces

50
Interaction W/D Additives with other
Pigments

51
Wetting and Dispersing Additives: Class

52
Low molecular weight dispersants

 Found in anionic, cationic,

electro-neutral or non-ionic Stage
 The molecular weight of these
products is low, usually between
300 and 2,000 g/mol.
 Example : mono functional oleo-
alkylene oxide block copolymers.

53
Oligomeric dispersants
 Based upon fatty acid
chemistry, having polar
heads based on tertiary
amines.
 Typically, these
molecules are oligo-
functional, meaning that
more than two amino
anchoring groups are
present.
 The molecular weight
ranges from 1,000 to
3,000 g/mol.
54
High molecular wt dispersants
 High molecular weight dispersing agents can be linear or branched
molecules with molecular weights between 5,000 and 20,000
g/mol.
 Excellent stabilization, due to a high number of anchoring groups
along the polymer backbone which bind to numerous sites on the
pigment surface.

55
 Polyurethanes

Best suited dispersants for viscosity depression ,higher

pigment loads, more economical mill base formulations
and lower VOCs.
PU dispersants usually have a
branched backbone with a three
dimensional network structure.
Different anchoring groups are
introduced at various points on this
network structure.

56
Star-shaped dispersing polymers

 Having core-shell morphology.

 During the dispersing step the
polymer segments in the core
adsorb on the pigment surface.
 The very high density of
pigment affinic groups results in
a very strong adhesion on the
pigment surface.
 The polymer chains in the shell
orient into the solvent and
stabilize the pigment very
effectively.

57
Block copolymers Dispersant
 Based on Controlled free Radical Polymerization (CFRP) technology
, enables the precise design of polymer structures.

 With the CFRP technology, well-defined block copolymers can be

prepared that are designed to optimally fit pigment and resin
chemistry.
 Typically, a longer stabilizer block is synthesized first, which has to
be compatible with the relevant ink systems. The anchoring block
contains functional groups which interact strongly with the pigment
surface to allow for efficient and stable adsorption. For demanding
applications like organic pigments, the anchoring block typically
contains aminic groups, which can optionally be modified further.

58
CFRP Technology based Dispersant's
structure

59
 Polyacrylates
Polyacrylic dispersing agents have linear structures with a
C-C backbone that bears various functional side groups
and short side chains.
The main difference to polyurethane-based dispersants is
their higher molecular weight.

60
Co-polymer dispersants :

Anionic dispersing agents based on poly-carboxylic co-polymers .

Their narrow molecular

weight distributions provide
optimum dispersion
efficiency, translating into
maximum performance at
the lowest possible
formulation cost.

Anionic dispersants are

especially effective in
stabilizing inorganic
pigments and fillers

61
 Comparison in Poly Acrylic and
Polycorboxylic co-polymer base D.A.

62
Surfactants
Surfactant molecules are able to modify the
properties and, in particular, they lower the
interfacial tension between the pigment and
the resin solution.
This surface activity arises because the
surfactants' structure consists of two groups
of contrasting solubility or polarity.
In aqueous systems, the polar group is
known as a hydrophilic group and the non-
polar group as hydrophobic or lipophilic.
In non-aqueous systems, the polar group is
known as the oleophobic group and the non-
polar group as oleophilic.

63
Surfactants
Surfactants are classified according to their chemical structure and, more
specifically, their polar group: anionic, cationic, electroneutral and non-ionic .

64
 Surfactants : Points

 Surfactant’s effectiveness is determined by:

o The absorption of the polar group onto the pigment
surface. The anchoring groups can be amino,
carboxylic, sulfonic, phosphoric acids or their salts.
o The behavior of the nonpolar chain in the medium
surrounding the particle. This part of the molecule
(aliphatic or aliphatic-aromatic segments) must be
highly compatible with the binder system.
 The stabilization mechanism is electrostatic.
 Due to the Brownian movement the pigment particles
frequently encounter each other in the liquid medium
thus having a strong tendency to re-flocculate on the let
down stage
65
 Types of Surfactants

o Fatty acid derivatives

o Phosphate esters
o Sodium polyacrylates / polyacrylic acid
o Acetylene diols
o Soya lecithin

66
 Fatty Acid Derivatives

 Nonionic fatty acid derivatives such as the alkyl phenol ethoxylates

(APEs) and fatty alcohol ethoxylates (FAEs)

67
 Phosphate Esters

• .

68
Polyacrylic acid/ Sodium polyacrylate

Polyacrylic acid (PAC) and salts of polyacrylates are

anionic surfactants.

Polyacrylic Acid structure and conversion to sodium

polyacrylate

69
Acetylene Diols

To reduce the side effects of standard surfactant types of dispersing

agent such as foaming, oligomeric acetylenic ethoxylate glycols have
been developed with multi-functional properties and especially
defoaming property .

Ethoxylated acetylene diols

70
THANK YOU