Printing of Synthetic fabric Dr. B.H.

Patel,

Printing of Man-Made Textiles

Introduction

Pretreatment of Synthetic Textiles

Pretreatment of synthetic fabric, before printing, is necessary to remove added impurities, to
achieve desirable whiteness and to remove any protruding fibres on the surface.

(i) Singeing : In singeing the protruding fibres from the fabric surface are removed to produce an
even and smooth surface. This is necessary to produce sharp design prints. Since singeing leads
to harsh feel of fabric, it is sometimes omitted to retain the soft handle of the fabric.

(ii) Scouring: During scouring the added impurities of the spin finish and sizing chemicals are
removed from the fabric and required wettability for subsequent process i.e. printing has been
achieved. After scouring the fabric is washed thoroughly to neutral pH.

(iii) Bleaching: Half or mild bleaching of synthetic textiles is preferred as per the requirement
of print quality.

(iv) Heat setting : Heat setting of synthetic fabric is carried out to improve dimensional stability,
crease resistance and resistance to pilling. Heat setting is carried out at suitable temperature as
per the class of fiber to be printed on pin stenter.

Formulation of Printing Paste

The printing paste may contain, apart from dyes, ingredient such as wetting, agents, dispersing
agents, solvents, hygroscopic agents, antifoaming agents, acids and alkalis, oxidizing and
reducing agents, carriers, mild oxidants, thickeners, and binders.

Ingredients

Dyes: The dyes are selected from a chemical class depending on the type of fiber to be printed.
In general, dyes in paste form are preferred for printing because they give fewer agglomeration
problems than dyes in granular form.

Wetting Agents:

In the preparation, of printing paste, dye is usually pasted with a small amount of a wetting ·gent
followed by the addition of water.
The function of the wetting agent is to get a smooth paste without the formation of lumps of dye
powder. If lumps are formed they get deposited on the fabric and produce dark specks. The
wetting agent functions by lowering the surface tension of the water, thus facilitating better
dissolution or dispersion of dyes in the printing paste. Turkey Red Oil was used as wetting agent

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Printing of Synthetic fabric Dr. B.H.Patel,

for centuries. A number of anionic and nonionic surfactants are presently available for use as
wetting agents in a printing paste.

Dispersing Agents and Solvents

The printing paste is a highly concentrated dispersion or solution of a dye. It is essential to use a
dispersing agent and/or a solvent to prevent dye agglomeration, crystallization, or precipitation in
the printing paste. Dispersing agents compatible with the dye and other ingredients in the paste
are use in the minimum necessary quantities.
Solvents like diethylene glycol, cellosolve (thiodiglycol), and sodium benzyl sulfanilate
(Solution Salt SV) help to keep the dye in solution. Hydrotropic compounds such as urea
facilitate the dissolution process.

Hygroscopic Agents

The function of hygroscopic agents in the printing paste is to take up a sufficient amount of
water during steaming. This gives mobility to dye molecules in the printed dried paste and
enables them to diffuse into the fiber. Glycerine, diethylene glycol, and urea are used as
hygroscopic agents.

Antifoaming Agents

Many printing pastes have a tendency to froth during printing because of the presence of wetting
agents and continuous agitation by the printing roller and brush furnisher. This causes the paste
to overflow onto the floor or into another color box. The print becomes specky and lighter in
shade. Frothing can be reduced by adding antifoaming agents to the printing paste. Benzene,
pyridine, turpentine, and some silicone compounds are employed as antifoaming agents.
(Benzene, being carcinogenic, should be avoided.)

Acids and Alkalies

Depending on the class of dyes used and the type of fiber to be printed, acid or alkali is added to
the printing paste. The acids commonly used in printing paste are organic acids such as citric
acid, lactic acid, acetic acid, formic acid, and tartaric acid.
Strong acids are used as their ammonium salts, such as ammonium chloride, sulfate, nitrate,
cyanide, and dihydrogen phosphate. These salts liberate corresponding acids after ammonia
evolves out during steaming or dry-heat treatment. '
The alkali used in printing includes sodium or potassium hydroxides, bicarbonate, or silicate,
ammonium hydroxide, and triethanolamine.

Oxidizing and Reducing Agents

Oxidizing and reducing agents are required for printing certain dyes and in discharge and resist
styles of classes of printing. The most commonly used oxidizing agents are chlorates, chromates,

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Printing of Synthetic fabric Dr. B.H.Patel,

dichromate, nitrates, nitrites of sodium and potassium, and potassium ferrocyanide. The
commonest reducing agents are those based on sodium hydrosulfite.
Sodium hydrosulfite decomposes and gets deactivated at temperatures prevailing in pressure
steaming. Its derivative sodium sulfoxylate formaldehyde which is widely used in the printing of
cotton, has a limited utility in the discharge printing of synthetic fibers because of its sensitivity
to acids. It also hygroscopic and causes haloes. Hence, zinc sulfoxylate formaldehyde (water-
soluble type), for example, Arostit ZET (Sandoz), is generally used for discharge printing on
synthetic fibers. It is non hygroscopic and effective at high temperatures. Because its limited
solubility of water, in there is no danger of halo formation. Thiourea dioxide is another reducing
agent suitable for synthetic fibers, but it is much milder in its reducing action. It cannot be
employed with success on dark grounds. A mixture of thiourea dioxide and Arostit ZET ( 11:1 ))
is an ideal reducing agent, particularly where wool is involved. Stannous chloride or tin salt is
also used for producing discharge prints on synthetic fabrics. Stannous chloride is highly acidic
and can adversely affect the brightness of some colors used in color discharges. It is therefore
necessary to add sodium acetate as a buffer. Tin salt has a tendency to cause a yellowish
discoloration in the printed areas. This yellowing can be minimized by adding a suitable
nonvolatile organic acid like citric or tartaric acid alone or preferably mixed with sodium or
potassium thiocyanate. Potassium sulfite, sodium bisulfite, glucose, and ferrous sulfate are also
used as reducing agents.

Carriers

In the printing of polyester fiber, carriers are often employed to facilitate the uptake of dye by the
fiber. Carriers like benzvl alcohol are employed in the printing of acrylic fiber with cationic
dyes.

Mild Oxidants

In the alkaline printing pastes, a mild oxidizing agent, sodium-m-nitrobenzene sulfonate (sold
commercially as Resist Salt or Ludigol), is incorporated to prevent the reduction of dyes during
steaming. Mild oxidant is also used in discharge printing with a reducing agent. If the dyed cloth
to be printed is padded with a solution of Resist Salt, it prevents the adverse effect of the
reducing agent on the unprinted dyed ground during steaming. Sodium chlorate can be used to
protect the brightness of prints against any reduction of disperse dyes under prolonged steaming
conditions at elevated temperatures.

Thickeners

The main functions of a thickener in a printing paste are (a) to act as a vehicle for carrying the
dye on to the fabric and (b) to prevent the spreading of the color on the fabric by capillary action
beyond the limits of the defined portion in the pattern.
The essential qualities of a thickener are:

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Printing of Synthetic fabric Dr. B.H.Patel,

1. It should have the desired physical and chemical properties such as viscosity, flow
property, and ability to wet and to adhere to the internal surface of the etchings of the
engraved roller.
2. The storage stability of the thickener paste must be good.
3. It should be compatible and inert to dyes and other ingredients of the printing paste.
4. It should absorb water during steaming without causing flushing.
5. It should have good thermal stability. The thickener film should not break during high-
temperature steaming or thermo soling.
6. The removal of the thickener from the fabric after fixation of the prints should be easy.
7. It should be biodegradable.
8. It should be available at reasonable price.
A large number of thickeners are available for printing. The choice of thickener will depend on
the class of dyes to be printed and the style of printing. The following materials are commonly
used as thickeners.
Starches and Cellulose Derivatives
Starches: The starch is cooked in water to get a thick paste. This is suitable for printing pastes
that are not acidic in nature. Maize starch withstands alkali better than wheat starch. The latter
has a good binding quality but it imparts a harsh feel to the printed fabric. This drawback is
overcome by mixing gum tragacanth with the starch.
Modified Starches
The most commonly used starch derivative in printing is dextrin or dark British gum. It is a
modified product obtained by heating starch with mineral acid or roasting it at l60°C until it
becomes completely soluble in water. In the case of light British gum or yellow dextrin, the
roasting process is stopped before complete solubilization takes place. The main features of these
gums are their good leveling properties and solubilities, which make them easily washable after
the fixation of prints.
Starch ethers and esters are also used as thickeners. Many starch derivatives are readily soluble
in cold water, have good storage stability, and are stable under alkaline or acidic conditions in
the printing paste.
Methyl Cellulose: It is prepared by reacting soda cellulose with methyl halide. The most
important property of methyl cellulose is that it is soluble in cold water but insoluble in boiling
water and in the presence of alkali. The removal of methyl cellulose after the fixation of prints is
thus very easy. About S--6% methyl cellulose usually gives a workable paste. It has a good
storage stability.
Carboxymethyl Cellulose. It is prepare by reacting alkali cellulose with monochloro acetic acid.
CMC is stable to alkali and can be used for printing vat dyes. It gives sharp prints and can be
readily washed away after the fixation of prints.
Hydroxyethyl Cellulose. It is obtained by treating soda cellulose with monochlorohydrin. It is
soluble in water and gives prints with sharp outlines.
Gums

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Printing of Synthetic fabric Dr. B.H.Patel,

Gum Tragacanth: It is obtained from leguminous plants like As tragalus Gummifer as a dried-up
exudate. It is soluble in water and gives a thick smooth paste. About 4--6% gum is used in the
printing paste. Gum tragacanth (or Gum Dragon) is stable under mild alkaline conditions. It
gives a soft handle to the fabric. Gum tragacanth works well with the starch.
Gum Arabic: It is obtained as an exudate from the Acasia plant. A 30-50% solution of the gum is
used for preparing printing paste. It gives prints with sharp outlines and most level blotches.
Gum arabic (or gum'senagal) is stable under both strongly alkaline and strongly acidic
conditions. It can be easily removed from fabric after the fixation of prints.
Gum Karaya: This gum is obtained from the Karaya tree. It is acidic in nature and relatively
insoluble in water. About a 40--50% solution of gum Karaya is used in preparing the printing
paste. The printing paste has good storage stability.
Nafka Crystal Cum: This is a highly purified form of natural gum with a high thickening power.
It is soluble in cold water. The Nafka crystal gum paste is very stable under acidic and alkaline
conditions. The gum gives clear prints.
Locust Bean Cum: It is obtained from the seeds of the locust bean of the carob tree. Only a 2-3%
solution of the gum gives a print paste of required viscosity. Derivatives of locust bean gum are
extensively used in the printing of synthetic fibers. These gums (marketed as Indalca gum) are
nonionic and exhibit an outstanding compatibility with dyes over a wide pH range. However, the
supply of locust bean gum is very limited because it originates from a slow-growing tree. The
price of these gums is therefore quit high.
Gar Gum: Locust bean gum and uar gum have closely related properties, both being
galactomannans. Guar gum was developed in 1953 as a substitute for locust bean gum. The
supply of guar gum is abundant because the gum originates from an annual Guar plant. Its
capacity of solution of guar gum gives satisfactory viscosity. The paste is stable for many days.
However, guar gum is generally modified to improve its flow properties and dispersibility. The
type of reactions that are commonly used to modify guar gum include etherification,
esterification, oxidation, reduction, and formation of cyclic derivatives.
Derivatives of guar gum are extensively used in the printing of synthetic fibers. The
Meyprogums belong to this class. These gums are nonionic in nature and are stable over both
acid and alkaline conditions. The gums are unaffected by the presence of electrolytes in the
paste.
Sodium Alginate_: The sodium salt of alginic acid is extracted from seaweed.' It is soluble in
water and hence, preparation of its paste is easy. About a 4-6% solution of sodium alginate gives
a paste with satisfactory viscosity. Because of its good adhesion properties, the dry film of
sodium alginate does not get detached from the fiber or cracked in the mechanical handling of
the dried fabric. Sodium alginate has good wetting power and thus gives better penetration of the
dye in the fabric. This makes sodium alginate particularly suitable for the printing of
hydrophobic synthetic fibers. Removal of sodium alginate from the fabric after printing is easy
and it gives fabric with soft hand. Sodium alginate does not react with reactive dyes and hence, is
an ideal thickener for printing these dyes. Being anionic in nature, sodium alginate is unsuitable

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Printing of Synthetic fabric Dr. B.H.Patel,

for printing with cationic dyes or in the presence of cationic surfactants. It may get precipitated
with acids.
Sodium alginate is not compatible with soluble calcium salts or with salts of heavy metals such
as iron, zinc, and chromium. If these salts are present, it is necessary to add a sequestering agent
in the print paste. The major problem with sodium alginate is its limited availability and high
price.
Emulsion Thickeners
Emulsion thickeners came into existence with the rapid development of pigment colors.
However, they are also employed for printing other classes of dyes. In an emulsion system, there
is a dispersed phase and a continuous dispersing medium. When very stable emulsions are
required, emulsification is brought about in the presence of a third component called the
emulsifier.
For textile printing, oil-in-water types of emulsions are used. Kerosene-water emulsions have
also been widely accepted. Different types of emulsifiers arc available such as anionic, cationic,
and nonionic; the nonionic type of emulsifier is preferred and alkyl phenol ethylene oxide
condensates have proved most useful. It is possible to get printing pastes with the desired
viscosity with these thickeners at very low solid contents. Better penetration of dyes and higher
color yields are therefore obtained. These thickeners dry very rapidly after printing because of
the low solid content and the volatile nature of the oil phase. This characteristic is an important
advantage in screen printing. Materials printed with emulsion thickening are very soft after
drying and are much less liable to crack or mark off.
Removal of thickener after printing is very easy and thus the handle of the fabric is soft.
The drawbacks of the emulsion thickening are (a) considerable fire hazard, (b) serious problem
of air pollution, and (c) increasing price. of hydrocarbon oils.
Synthetic Thickeners
The impetus for the development of synthetic thickeners has come partly to augment the
continuously dwindling supply of natural gums and thickeners and partly because of the
substandard rheological properties of natural thickening agents and their modified products. The
need to replace mineral ol in the pigment printing emulsions and sodium alginate in the printing
of disperse and reactive dyes are also cause for this development. With the development of
sophisticated machines like the rotary printing machines and the need for printing photographic
designs using fine lines and dot screens, the demand for consistent purity and rheological
properties of the thickening agents has become very severe. Apart from the technical properties,
ecological factors such as biodegradability and toxicity have to be considered. In this respect,
however, natural thickeners and gums have an advantage.
Synthetic thickeners are long chain polymer derivatives obtained from substituted vinyl
compounds that are easily polymerized by a free-radical mechanism or by the addition of an
ionic substance. They are compatible with disperse, reactive, acid, and cationic dyes. The paste
of synthetic thickeners can be prepared in 5-10 min and there is no need to add any preservative
because the paste has good storage stability. Synthetic thickeners give a paste of suitable

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Printing of Synthetic fabric Dr. B.H.Patel,

viscosity at low concentration and give better definition of the prints, even at low solid content.
Synthetic thickeners have good thermal stability and can be used for all types of fixation
processes such as high temperature steaming and thermosoling. They usually give about 15--
20% higher color yield compared to that of natural thickeners. Removal of these thickeners after
the fixation of prints is very easy.
Synthetic thickeners suffer from two major drawbacks: (a) they are not biodegradable, and (b)
their viscosity severely decreases in the presence of electrolytes. Since most of the conventional
dyes contain electrolytes, it is necessary to develop special electrolyte-free dyes.
Pectin
Pectin is a polyuronide that occurs in all plant tissues. In some cases it accounts for as much as
one-third of the dry matter as in the peels of citrous fruits. Pectin has a low viscosity and does
not react with reactive dyes. The feel of the fabric is not affected by pectin. Since it is obtained
from agricultural waste, a regular supply is ensured and it is quite cheap. Pectin gels at pH above
9 and hence, cannot be used under highly alkaline conditions.
Binders
A binder used in pigment printing is a substance that can form a film on the printed portion. The
fastness properties of a binder film largely determine the fastness of the pigment prints and the
quality of a print thus depends on the quality of the binder. The binder film formed on the fiber
surface must be colorless and clear, of even thickness, smooth, and neither too hard nor too soft.
It should be elastic and have good adhesion to the substrate without being tacky. Furthermore, it
should have good resistance to mechanical and chemical stresses, but should be readily
removable from the printing rollers, screens, back-greys, and blanket during the printing
operation or shortly afterwards. Albumin, casein, and glue were used earlier as binders-cum-
thickeners. They were replaced by cellulose esters such as cellulose acetate and cellulose nitrate.
The fastness properties of all these binders are not very good. A large number of synthetic
binders have been developed, the most important among them being vinyl resins, acrylic resins,
melamine-formaldehyde and urea-formaldehyde precondensates, and chlorinated rubber.
Helizarin Binder UD (BASF) is formed from acrylic esters with styrene and gives prints with
excellent fastness properties. Helizarin Binder NTA (BASF) is a butadiene copolymer. The
newest development in the field of pigment printing is the production of substances that combine
the functions of binders, thickening agent, white spirit, emulsifier, leveling agent, and the
catalyst. The typical trade products are Lutexal HD (BASF) and Acramin CA 3241 (3BY).
Special binders are developed for printing polyester-cotton blend fabrics. They are based on
styrene-butadiene and acrylonitrile-butadiene and have good adhesion power even for polyester.

Fixation of Prints

After printing, the goods are dried and the prints are fixed. Four methods are available for
fixation of the prints on the fabric.
Steaming without Pressure:

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Printing of Synthetic fabric Dr. B.H.Patel,

This is the oldest method of fixation of prints. It consists of treating the fabric with saturated
steam at a temperature of 100- 101C under atmospheric pressure, 'The method is extensively
used for the fixation of acid dyes on nylon and cationic dyes on acrylic fibers. In the case of
polyester, it is essential to incorporate a carrier in the printing paste. Even after prolonged
steaming treatment, the color yield is not satisfactory. Hence, this method is not used for the
fixation of disperse dyes on polyesters.
Steaming under Pressure:
Saturated steam at a pressure of 0.5-2 kg/cm2 is used for the fixation of dyes in this method. Very
good fixation of print is obtained when polyester fabric printed with disperse dyes is steamed for
20-30 min. The feel of the fabric is also not affected since there is no tension on the fabric during
steaming. The pressure steaming is usually done on a batch wise cottage steamer. Fabric
interleaved with a grey fabric to prevent marking off is arranged in the form of loops and
suspended from wooden rollers carried on the framework of a portable wagon that is on rails into
the cottage. The wagon is charged into the cottage steamer, which is then closed, and the fabric is
steamed under pressure. Continuous pressure steamers are also available for high production. For
the fixation of disperse dyes on nylon, steam at 0.5 kg/cm2 pressure is used for 30 min. Disperse
and cationic dyes on acrylic fiber can be fixed at a steam pressure of 0.2-0.5 kg/ cm2 and time of
steaming is 20 30 min. The method is also suitable for the fixation of disperse dyes on cellulose
triacetate.
Dry-Heat Fixation: This method of continuous fixation of prints is used mainly for polyester.
The prints of disperse dyes are fixed by the dry-heat treatment at 180—200 ⁰C for 30-120 sec in
a pin stenter or in other thermosoling equipment. The method gives high productivity and does
not produce flushing of the prints. However, the brightness of the prints is not as good as that
obtained by the steaming methods. The feel of the fabric is harsh. There is also a severe
restriction on the use of disperse dyes. Dyes with low sublimation fastness stain the white
ground.
Superheated Steam Fixation: The dry steam is passed through a heat exchanger to raise its
temperature from 150°C to 220°C to get dry high temperature or superheated steam. The
pressure of the steam after superheating may drop down to atmospheric pressure, and for its use
for fixation, a pressure chamber is not required. Thus, the construction of a superheated steamer
is simple because the problem of constructing seals for the fabric inlet and outlet which prevail in
pressure steamers do not arise. Continuous superheated steamers give high productivity.-3
Compared with dry-heat fixation with hot air, superheated steam fixation requires lower
temperatures (170--180°C) for the fixation of disperse dyes. Thus, there is less restriction on the
selection o disperse dyes and dyes of medium sublimation fastness can also be used. The method
is of particular interest for textured materials because low temperatures are used and there is no
tension on the fabric during steaming. The addition of urea or other auxiliary such as Luprinton
ATP or Luprinton HDE in the printing paste is recommended to get good color yield.
High-temperature dry steaming can also be used for fixation of disperse dyes on triacetate. Acid
dyes on nylon can also be fixed using high temperature dry steaming but the color yield is

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Printing of Synthetic fabric Dr. B.H.Patel,

slightly lower than that obtained by using saturated steam at 102°C. Cationic dyes on acrylic
fiber do not give good color yield when fixed by the superheated steam.