Pigment Printing
Of
Textiles
Dr. Sanjiv Kamat
Pidilite Industries Limited
04th Februray Dr Sanjiv Kamat
2010
04th Februray Dr Sanjiv Kamat
2010
04th Februray Dr Sanjiv Kamat
2010
04th Februray Dr Sanjiv Kamat
2010
Pigment Dispersions –
Historical Developments
As old as 3000 years with mineral pigments and natural
polymers as binder and thickeners(starch,glue)
1920’s- Organic Pigment dispersions
1930’s –Emulsion copolymerisation techniques.
1937 –Pigment paste based on water in oil emulsion
1950 – Oil in water systems.
1960- Aqueous self crosslinking dispersions as binders
Early 60’s - Pidilite introduced pigment
dispersion in India.
1990s Ecological improvements(emmission)
Digital printing
04th Februray Dr Sanjiv Kamat
2010
Why Pigment Printing ?
Versatile-Suitable for all substrates and
machines
Low impact on waste water
Low consumption of water, no washing
after printing
Short process cycle –faster output , Print,
dry,fix
Best light fastness
Very High Reliability
Zero printing defects possible
04th Februray Dr Sanjiv Kamat
2010
Relative properties of Printing
styles
Properties Pigment Substantive
Light Excellent Good
Washing Acceptable Very Good
Rubbing Good Very Good
Weathering Very Good Poor
Handle Acceptable Excellent
04th Februray Dr Sanjiv Kamat
2010
Components of Pigment Printing System
• Colour pigment
• Binding agent
• Fixer
• Thickener
• Auxiliaries
- emulsifiers
- softeners
04th Februray Dr Sanjiv Kamat
2010
Composition of the Pigment Dispersion
• Pigment (25-45 %)
• Water
• Auxiliaries
- emulsifiers / dispersing agents
- Co solvent / glycols (few)
- preservative
04th Februray Dr Sanjiv Kamat
2010
Factors influencing Selection of Pigment
Fastness to
Washing
Light
Solvent
Perspiration
Chlorine
Heat
Saliva
Legislations
04th Februray Dr Sanjiv Kamat
2010
Influence of Particle Size of Pigment
Flocculation
Hue/Tint Strength
Hiding/Transparency
Gloss/Flatting and Film appearance
Viscosity
Stability
Weather Resistance
04th Februray Dr Sanjiv Kamat
2010
Pigments
Primary Particles
0.01-5mu
Aggregates
0.05-50mu
Agglomerate
0.1-1000mu
04th Februray Dr Sanjiv Kamat
2010
Pigment dispersion
Large number of aggregates and agglomerates
formed during drying and pulverizing process of
pigment press cake
To obtain better gloss, rheological properties
and color strength pigment applications need
pigment in disperse form
Size of aggregates and agglomerates is reduced
from 10-60 micron to below 1 micron
04th Februray Dr Sanjiv Kamat
2010
Dispersion Process
Size Reduction: Breaking of larger aggregates
and agglomerates into smaller primary particles
by impact and shear force
Wetting Process: Uniform spreading of liquid
medium on the pigment surface making a
contact angle of zero degree. Proper wetting
improves gloss
Stabilization: Dispersed particles are
prevented to come together
04th Februray Dr Sanjiv Kamat
2010
Dispersion Properties Depend upon
Suitability of pigment
Particle size
Particle size distribution
Degree of dispersion
Electrical charge
Specific gravity
Crystal structure & stability
04th Februray Dr Sanjiv Kamat
2010
Texture
Feel and appearance of surface especially how
rough or smooth it is .
Decided by the degree of aggregation of the
primary particles
Soft texture have large agglomerates and few
aggregates
Large number of aggregates give hard texture
Various surface treatments used to improve
texture
04th Februray Dr Sanjiv Kamat
2010
Texture is affected by
pH(fluctuation in the process)
Temperature
Solvent in condensation
Process slow or fast(Rate of addition)
Drying process(Convection,IR,Air suction)
04th Februray Dr Sanjiv Kamat
2010
Texture and structure
SOFT
<Bisazo < Phthalocyanine <
monoazo < betanaphthol <
Benzimidazolone < Quinacridones
< DPP < Perylene < Carbazole <
HARD
04th Februray Dr Sanjiv Kamat
2010
Dispersing Equipment
04th Februray Dr Sanjiv Kamat
2010
Size Reduction
Commonly used Equipments
Equiptment Type Of Action
Ball Mill Impact
Sand Mill Sheer+Impact
Attritors Impact+Sheer
Bead Mill Sheer+Impact
Three Roller Mill
Sheer
Kneader Sheer
Extruder Sheer
04th Februray Dr Sanjiv Kamat
2010
Influence of pigment dispersion particle size
on printing
Small particle size may cause a low colour yield besides clogging of
screens and may also entail thixotropic propensity of print pastes.
Wash fastness may be inferior since the pigment particles may not
be held properly in the layer of binder film.
For instance, 40g/kg shade using a pigment dispersion having a
particle size of 0.1 micron and binder of 0.3 micron, since these
particles are not held appropriately in the binder film, the wash
fastness may be affected. , since with very fine particle size; the
pigments are liable to bleed on washing e.g. Pigment Red 2 with a
lower particle size. Red and Bordeaux pigments have a tendency to
bleed on washing .
Large particle size may entail dull prints.
High viscosity of pigment dispersions may not only lead to thicker
print pastes but also cause inadequate penetration during printing
on the substrate.
04th Februray Dr Sanjiv Kamat
2010
Recent Development in Emulsifiers
No clear technical trend visible
- combination products
- emulsifier/rheolog. additive
- emulsifier/rheolog. additive/fixing agent
- pure emulsifier
• APEO-free
• Non-ionic
04th Februray Dr Sanjiv Kamat
2010
Pigment Printing Binders should
Have good adhesion but no tack
Be resistant to chemical and mechanical
stress
Be flexible
Be non yellowing
Be removable from screens
Be shear stable
Resistance to aging
04th Februray Dr Sanjiv Kamat
2010
Binder Properties Influenced by
Lowest
Fastness
AN Hardest
P
O
S
Styrene
I Harder
T
I
V
E MA Hard
N
E EA Soft Tacky
G
A
T NBA
NBA Softer More Tacky
I
V
E
B Softest Most Tacky
Best
Fastness
04th Februray Dr Sanjiv Kamat
2010
Binders
Monomer Tg (°C)
Ethylene -125
Butadiene -78
Butyl Acrylate -52
Ethyl Acrylate -22
Vinyl Acetate +30
Vinyl Chloride +80
Methyl Methacrylate +105
Styrene/Acrylonitrile +105/130
04th Februray Dr Sanjiv Kamat
2010
Type of Binders
1. not self-cross linking
2. self-cross linking (reactive side groups)
Parameters influencing crosslinking
• Type and number of reactive groups
• Temperature
• Duration
• pH value
Crosslinking results in improved
1. Fastnesses
2. Stability to temperature
3. Permanency of effects
04th Februray Dr Sanjiv Kamat
2010
Binders Functional Groups
Carboxyl functionality –Binders contain acrylic
acid or methacrylic acid as co-polymers.
Provides sites for cross-linking reactions
Amide Functionality – Acrylamide as a part of
the functional group .Binders having
substituted acrylamide groups have self cross
linking properties
SBR Binders-Butadiene monomer provides
elasticity ,while styrene and acrylonitrile give
oil and solvent resistance Disadvantages are
oxidation and discoloration due to residual
double
04th Februraybonds Dr Sanjiv Kamat
2010
Binder Particle Size
Smaller the particle size of the binder
results in brighter prints as total
internal reflection increases.
Bigger particle size binder may increase
coverage but prints may look duller
Very small particle size will lead of
clogging of screens because of
agglomeration
04th Februray Dr Sanjiv Kamat
2010
Recent Development in Binders
• Increasingly softer handle
• Fastnesses improved
• Running properties were improved
• Reduction in residual free monomer content
04th Februray Dr Sanjiv Kamat
2010
Binders Components for self cross
linking
Normal
CH2=CH-CO-NH-CH2-OH N - methylol acrylamide
detaching formaldehyde
reaction partners: - sec. amino groups
- N-methylol groups / N-methylol ether groups
- amide groups
- melamine groups
- dicyan diamide groups
- related groups
Alternative
CH2 - CH- epoxy components (e.g. epichlorhydrin
O formaldehyde-free
reaction partners: - hydroxylic / carboxylic groups
- amino groups, react. methylene groups
04th Februray Dr Sanjiv Kamat
2010
Synthetic Thickeners
-CH2 -CH - CH2 - CH CH2 -CH - CH2 - CH -
OH-
COO - COO - n
COOH COOH
n
•
first synth. thickeners in 1969
• mechanism:
n - addition of alkali (NH4OH) causes an electrostatic repellency
- formation of a three-dimensional network = increase in viscosity
• molecular weights in the range of 1000000
• partially crosslinked
04th Februray Dr Sanjiv Kamat
2010
Thickener properties
Molecular High / Low Viscosity High/Low
Weight
Polymer High /Low Viscosity High/Low
Content
Same High Low
Polymer Molecular Molecular
content Weight Weight
Low Dosage High Dosage
Low Coverage High
Low Fastness Coverage
High Fastness
04th Februray Dr Sanjiv Kamat
2010
Pidicryl SHRP - Rheology
modifier
Rheology change under Shear ( Squeegee Pressure)
Viscosity
100
80
60
40
20
0
Shear force released Time
Sec
Shear force
AQA +SHRP
04th Februray Dr Sanjiv Kamat
2010
Rheology Modifier - Pidicryl SHRP
Reduces Flushing tendency on different
fabrics
Improves colour yield
Improves brightness
Improves leveling highly recommended
in full blotch printing
Lower penetration
Higher coverage Mts/Kg of print paste
Best results at pH > 8
04th Februray Dr Sanjiv Kamat
2010
04th Februray Dr Sanjiv Kamat
2010
Recent Development in Thickeners
Two trends:
a) higher efficiency / price optimization
b) improved technology / multifunctional
• pasty
• lower hydrocarbon content
• non-fuming
• high purity / good and quick swelling behaviour
• good storage stability / little settling
04th Februray Dr Sanjiv Kamat
2010
Recent Development in Thickeners
Two trends:
a) higher efficiency / price optimization
b) improved technology / multifunctional
• pasty
• lower hydrocarbon content
• non-fuming
• high purity / good and quick swelling behaviour
• good storage stability / little settling
04th Februray Dr Sanjiv Kamat
2010
Developments in Fixing Agents
• Melamine resin fixing agent / contains HCHO
higher etherification, thus:
- reduced HCHO content
- less HCHO emission during drying and fixation
- reduced HCHO content on the fabric
- less reactivity
• Isocyanate fixing agent / HCHO-free
-cold fixing / not blocked / shelf life /
high reactivity
- hot fixing / blocked
38
04th Februray Dr Sanjiv Kamat
2010
Ecological Issues
Air
• hydrocarbons (white spirit/thickener/antifoam)
• HCHO (fixing agent/binders/preservative)
• monomers (binding agent/fixing agent/thickener)
• fume (thickener/softener/urea/glycols)
Water
• hydrocarbons (white spirit/thickener/softener/antifoam)
• heavy metals (Pigments)
• APEO (emulsifiers/binders/softener)
Fabric
• HCHO (fixing agent/binders/preservative)
• fastnesses (binding agent/fixing agent/pigments)
• MAK amines (colour pigments (some in the red range))
• APEO (colour pigments,binders),
04th Februray Dr Sanjiv Kamat
2010
Influencing Factors – Pigment Printing
Viscosity: Design, machine
Water Hardness
Screen Mesh
Drying Temperature
Fabric type
pH of printing paste
Particle size of Pigment dispersion and Binder
04th Februray Dr Sanjiv Kamat
2010
Fastness not achieved !
Light Depth of Shade
Perch Pigment selection
High Temp Pigment Selection
Crocking Depth of Shade
Binder Type
Binder Concentration
Curing conditions
Fabric Type and Geometry
04th Februray Dr Sanjiv Kamat
2010
Colour Textile interactions in Ink Jet Printing
Textile/Ink Interaction
Drying time Colour value/yield
Chroma (colour quality) Spreading/wicking
Rub fastness Water fastness Light fastness
Textile
Colour /Ink Formulation
Print Head Technologies
Performance Property
Drop performance Surface tension Viscosity
Ink/Material compatibility Specific gravity pH
Nozzle clogging Conductivity Dye purity
Nozzle crusting Dye purity/solubility
Toxicological properties
Biological growth Particle size Stability
Contamination Accoustic properties Shelf life
Long-term operability
04th Februray Dr Sanjiv Kamat
2010
Printhead Technology
•Thermal Drop on Demand(DOD)
•Piezo Drop on Demand
•Binary Continuous inkjet heads
•Multi-deflection continuous heads
•Air jet deflection
• Valve Jet
04th Februray Dr Sanjiv Kamat
2010
04th Februray Dr Sanjiv Kamat
2010
Thank you
March 2007 Dr Sanjiv Kamat 45
04th Februray
GAP Delhi Dr Sanjiv Kamat
2010
