Pigment Printing

Insoluble pigments which have no affinity for the fiber are fixed to the fabric with binding agents in
specific pattern.

Importance

 Can be used for all types of fibers

 Only colorants which can be used for glass
 No wet treatments
 Extensive color range
 High fastness colors
 Simple application procedure
 Possible to produce good combination shades on blended fiber in one padding operation
 No change of hue of colorant throughout processing
 Less expensive
 A good quality pigment print is characterized by
 Brilliance and high color value relative to the pigment concentration in material
 Minimum stiffening in the handle of the textile
 Generally acceptable fastness properties.

Components of a pigment printing system

A pigment printing system consists of three essential components:

Pigment dispersion: Specific pigments are treated in a grinding mill in the presence of suitable non-
ionic surfactants. A particle size of 0.1-3 μm is typical. Generally, the pigment pastes are aqueous
based and contain the dispersing agent, humectants (to prevent evaporation and drying out) and
chemicals to adjust the pH, commonly ammonia.

Binders and cross-linking agents (polymers): The binders used in pigment printing systems are film-
forming substances made up of long-chain macro molecules which, when heated with a suitable
acid-donating catalyst, form a three-dimensional structure in the pigment.

Thickeners and auxiliary agents: These give the required print thickening power (rheology).

Binder

The binder is a film forming substance made up of long chain macromolecules which, when applied
to textile together with the pigment, produce a three dimensionally linked network.
Binder- CH2-OR + HO-Textile ------- Binder –O- textile + HOR

Where R is H or CH3.

The links are formed during some suitable 'fixing' process, which usually consist of dry heat and a
change in pH value, bringing about either self-crosslinking or reaction with suitable crosslinking
agents.

The degree of cross linking should be limited, to prevent the macromolecules becoming too rigidly
bonded, thus preserving some extensibility. The important criteria, which ensure that the pigment
within the crosslinked binder film is fast to wear and cleaning, are elasticity, cohesion and adhesion
to the substrate, resistance to hydrolysis, as little thermoplasticity as possible and absence of
swelling in the presence of dry cleaning solvents.

Required properties for Binders

 Should be film forming

 Should be water swelling
 Should not be too thermoplastic
 Should have atmospheric stability
 Should be colorless and clear
 Should be of even thickness and smooth; neither too hard nor too stiff.
 Should have good adhesion to substrate without being tacky.
 Should possess good resistance to chemical and mechanical stress
 Should be readily removable from equipments
 Should provide good color yield
 Should be non toxic

Types of Binders

The binder for a water-based print paste is typically a copolymer produced by emulsion
polymerisation of a mixture of monomers such as butyl acrylate and acrylonitrile, or of styrene and
1,3-butadiene.

During drying of the printed zones, the particles of swollen binder gel coagulate on the fabric surface
and coalesce into a coherent film.

By regulating the monomer composition and the degree of polymer crosslinking the binder will give
a film with the desired elasticity and solvent, light and washing fastness.

One method of promoting crosslinking is to incorporate into the polymer a small amount of a
comonomer with a residual reactive group such as N-methylolmethacrylamide. During curing, the N-
methylol groups along the polymer chains undergo intermolecular condensation reactions producing
a number of crosslinks (Figure 23.7). This is called internal crosslinking.
Since the condensation reaction generates water, and is reversible, dry air is used for curing rather
than steam. The crosslinks are, however, reasonably stable to hydrolysis during mild washing and
are not present in sufficient number to produce a rigid film. They ensure good film stability, little
swelling of the film in dry cleaning solvents and improve the adhesion to the fibre surface.

Crosslinking can also occur by adding to the paste an agent capable of reacting with the binder
polymer during curing. These are external crosslinking agents. N-methylolmelamines or their methyl
ethers are typical examples.

The N-methylol groups can react with groups in the binder polymer or with the fibre as well as with
other chemicals in the paste such as thickeners (Figure 23.7).

External crosslinking is better for printing on synthetic fibres because of the improved adhesion of
the film produced.

The condensation of N-methylol compounds requires an acid medium and the pigment print paste
will therefore have an added weak acid such ammonium dihydrogen phosphate. This compound
causes reduction of the pH of the print film during curing, promoting crosslinking.
Types of Binders according to the origin

• Natural: glue, gelatin etc

• Synthetic: acramin binders

According to chemical groups

• Acrylic binders: These are normally an aqueous dispersed co-polymer of butyl acrylate and
styrene, having N-methylol acrylamide groups for cross-linking purposes.

Some of the more important properties of this type of binder are:

• Good resistance to ageing by light

• Good heat stability

• Generally a harsh handle

• Good solvent resistance

• Butadiene co-polymer binders: They are made by emulsion co-polymerisation with

acrylonitrille and N-methylolmethacrylamide. Some of the more important properties of this type of
binder are:

• Poor resistance to ageing by light

• Susceptible to yellowing on heat treatment

• Generally a soft handle, particularly on synthetic fibers

• Generally the highest binding action on synthetic fibers

• good solvent resistance

Colour value and brightness of the print can be affected by the binder.

Important properties of binder are

 Redispersibility – property of the partially dried binder film to rewet and redisperse in the
binder itself.
 Mechanical stability – ability of the binder to withstand the shear during printing without
destroying the emulsion

Thickening Systems

Examples: alginates, natural vegetable gums, synthetic polymers, foams.

These are sensitive to pH, temperature and salt content.

Types according to charge

Ionic: alginates, better color yield

Non-ionic: cellulose ethers, stable to pH variation and electrolyte content.

Natural and semisynthetic hydrophilic thickeners should not be used in pigment printing because:

They are soluble in water and swell in water even after fixation.
They have a large number of polar groups such as hydroxyl group and produce a firm and stiff hand.

They cannot be removed by after treatment as they are trapped in the binder film.

Carbohydrate gums are not usually suitable for use in pigment printing because of the ready reaction
of their hydroxyl groups with N-methylolcompounds.

Emulsion thickener

Emulsion:

Two phases: disperse and continuous

Nature of the emulsifying agent and the ratio of the two immiscible liquids determine the phases of
each liquid.

Emulsifying agent reduces the interfacial tension between the two liquids.

Emulsion stability depends upon

 the degree of dispersion

 type and quality of the emulsifying agent used
 the substance dissolved or dispersed in the dispersed or dispersion medium.

Two types of emulsion thickeners

Oil in water: kerosene/white spirit in water

Oil-in water emulsions give good results. These consist of about 70% white spirit hydrocarbons and
30% water with a small amount of non-ionic emulsifying agent. After drying, there is no solid residue
on the fabric surface as the emulsion thickener completely evaporates during curing. The
hydrocarbons used in oil-in-water emulsions may be released to the environment, however, and
their use is in forced decline.

Water in oil: water in kerosene or white spirit

Synthetic thickeners:

colloidal aqueous solutions of polymers such as polyacrylic acid have similar rheology to the oil-in-
water emulsions provided that the carboxylic acid groups dissociate. Rheology is the science of the
deformation and flow of materials. Addition of ammonia produces the ammonium salt of the
polymer. The repulsion of the negatively charged carboxylate groups causes the polymer chain to
open out and the polymer particles swell considerably because of hydration of the anionic sites. A
small degree of polymer chain crosslinking ensures that a true solution is not possible. These
colloidal solutions exhibit the required pseudoplastic flow. This type of thickener leaves a solid
residue on the fabric surface that can cause a harsh handle. Incorporation of a softening agent
counteracts this.

High viscosity at low concentration

High yield value

Shear thinning

Stability and integrity over a wide temp range

Ease of use.

Efficient at only 1 - 3 % concentration while natural thickeners are used at about 10 % to get
required viscosity in the print paste.

Rapid make up since they do not require time for hydration

Sharp print boundaries

Controlled penetration

Greater colour value and levelness

Printing pastes which are entirely water-based are obtained by replacing the white spirit with water.

The binder could be an acrylate copolymer which is capable of cross-linking in the presence of a
catalyst under heat. Catalysts used are ammonium salts of inorganic acids, e.g. diammonium
phosphate or ammonium thiocyanate.

Plastisol pastes are printing pastes:

• used for direct printing of material and for transfer pastes;

• based on a vinyl resin dispersed in plasticizer;

• characterised by virtually 100 % non-volatility, no solvent is present;

• used frequently for printing on dark or dark-coloured fabrics.

Suitable printing pastes are formulated as:

• PVC homopolymer (i.e. vinyl resin) dispersed in phthalate plasticizer;

• liquid plasticiser (e.g. dialkyl phthalate or di-iso-octyl phthalate);

• heat and light stabilisers (e.g. liquid barium/cadmium/zinc combined with epoxy plasticiser);

• high proportion of extender to improve wet-on-wet properties.

Thickener used in rotary printing are thixotropic, when shear is applied at the interface of the screen
and squeegee, the viscosity drops. This allows the color to flow through the screen easily and print at
high speeds. On removal of the shear, viscosity increases to original state instantaneously.

Generally, thickeners are used at 1.5 % - 3 % concentration by weight.

They are used at neutral to alkaline pH.

Sensitive to electrolytes.

Fastness properties of pigment prints

Lightfastness - determined by pigments, binder (may yellow with exposure to sunlight, noticeable
only with pastel shades),

Dry clean fastness – determined by pigments, generally binders are not affected by dry cleaning
solvents.

Wash fastness – influenced by the binders. Binders that are degraded by sunlight may give rise to
poor wash fastness.

Crock fastness- affected mostly by the binder but some surfactants used in the pigment dispersion
may have a negative effect.

Color value

Handle

Pigment to binder ratio:

Dry resin should be 1.5 – 2 times the amount of dry pigment.

At least 2.5 – 3 % resin content should be in the color formulation no matter how little pigment is
used.

Full strength colors

Actual pigment content of the pigment dispersions: 40 – 50 % dry pigment to 3 % dry pigment

Tinctorial strength.
Building curve of the color.

Maximum amount of color to be used for each color.

Other Auxiliaries

Catalysts

Diammonium phosphate: - most widely used acid catalyst

Used in conc. of 0.5% and 0.8% in screen and roller printing respectively

When used in correct proportion produces a pH of 3 in fabric and brings a cross linking reaction

Ammonium salts: sulphocyanide, sulfate and chloride are suitable. Ammonium nitrate: not
recommended and it turns polyamide fiber yellow

Urea

These are agents that are added to improve “runnability” on printing machines. Owing to their low
volatility these auxiliaries are used sparingly, maximum amounts of 20 parts/1000 being common;
otherwise the fastness properties may be adversely affected.

Softening agents

After curing fixation the resultant “handle” of the printed fabric depends on a number of factors:

- monomer composition of the binder

- presence of water-soluble protective colloids (e.g. alginates, etc.)

- extent and type of cross-linking.

By the addition of certain compounds (usually termed “plasticisers”) improves the handle of printed
goods.

Binders in textile printing

Binders are typically added to printing paste based on pigments in order to:

• coat the pigment and allow printing of very fine dispersions;

• protect the pigment from mechanical abrasion;

• fix the pigment to the fibres;

• gives the paste good drying properties.

Binders used in textile printing are in general self-crosslinking polymers which reticulate during the
fixation step. They are supplied as aqueous polymer dispersions, based mainly on acrylates and less
commonly on butadiene and vinyl acetate, with solid contents of approx. 40-50%. The amount used
depends on the amount of pigment and textile substrate, and usually varies within the range of 50-
150g per kg of print paste. The surface active substances needed to produce a stable dispersion are
responsible for the compatibility of the binder with the other components of the print paste.

The fastness, i.e. the resistance of the binder film (approx. 10 µm) to mechanical stress and its
swelling tendency in water and organic solvents, must be increased to an acceptable level by the
cross-linking reaction of the binder. Whereas the older types of cross-linkable binders reacted with
separate fixing agents during condensation process (hot air at 150 °C), self-cross-linking binders are
now well established. These contain reactive groups, usually from copolymerisation with monomers
such as N-methylolacrylamide or similar compounds. Three-dimensional cross-linking of the binder
film can be achieved by acid catalysis under the usual condensation conditions.

Binder films based on butadiene can age by the action of light and oxygen, i.e. they can become
yellow, and their fastness properties can deteriorate. Butadiene binders are therefore not
recommended for pigment printed textiles that are continuously exposed to light.

Binders made of natural wood resin, wax, stand linseed or safflower oils and chitosan were tested in
order to obtain biodegradable printing paste. Promising results were reported when using chitosan
as binder, no solvent is further necessary.

Cross-linking agents

These agents are universally based on either urea-formaldehyde types (e.g. dimethylolurea) or
melamine-formaldehyde types. They are incorporated into printing compositions in an attempt to
increase various aspects of fastness, particularly rub and scrub fastness with synthetic fibers. A
maximum addition of 10-20 parts/1000 is normally encountered: larger amounts can have a quite
marked effect on the “handle” of the fabric

Pigment Printing Recipe and Procedure

Typical Recipe:

Pigment: 10-20gm

Binder: 40-50 gm

Thickener: 35-50 gm

Catalyst: 5 gm

Dispersing agent 2 gm

Water x ml

Procedure:

Preparation of printing paste using dispersing agents and thickener and catalyst.

Application of pigment paste and binding resin together

Drying at 140 – 150°C

Curing to fix the resin pigment

Pigment discharge printing can also use a "dry" process which utilises hot, dry air to activate the
discharge agent in order to destroy the dyes without subsequent steaming and washing treatments
(compared to discharge printing with vat and reactive dyes, below). The discharge printing paste
employed in the "dry" process consists of a binder system, pigment, discharge agent and other
auxiliaries, which become fixed on the surface of the fabric during the baking stage; the fixed binder
contains destroyed dyes and decomposed discharge agents at the end of the baking stage.

Hence, the dry discharge system requires superior discharge agents which can be sufficiently
activated during baking in order to destroy the dyes present in the ground. There are many benefits
to this process, which include simpler production operations, lower production costs, and lower
effluent levels

Problems of Pigment Printing

 Adverse effect due to binder as it changes texture of fabrics.

 The quality of printing or dyeing depends on the characteristics of binder used to affix the
pigment even more than the properties of pigment.
 Some solvents used in emulsion like kerosene, white spirit cause problem like flammability.
 The chemical and physical influences on the binder and print paste can interfere during
production and processing resulting in sticking especially in roller printing.
 The gumming up of equipment, odor, air and water pollution
 Difficulty in obtaining the necessary wet treatment fastness and abrasion resistance with
certain products, may not be obtained pigment printing or dyeing.