PRINTING PASTE INGREDIENTS

Essential ingredients of a printing paste:

1. Dyestuffs, Pigments or dyestuff precursors

2. Wetting agents
3. Solvents, solution aids, dispersing agents and humectants
4. Thickeners
5. Defoamers
6. Oxidizing and reducing agents
7. Acids and alkalis
8. Catalysts and oxygen carriers
9. Carriers and swelling agents
10. Miscellaneous agents

All these constituents are not used simultaneously in any one printing paste. Depending on the class of dye
used and style of printing employed, suitable components are selected in making the printing paste e.g.
starch is suitable for direct dyes but not for reactive dyes, as it reacts with part of the reactive dye which
gets washed off, resulting in wastage of this dye. As a result, lighter prints are produced (reduced colour
value is obtained). Sodium Alginate is used as a thickener in reactive printing.

1. Dyestuffs, Pigments or dyestuff precursors

As far as the dyestuff is concerned, the choice of the dyestuff would depend on the fibre which is to be
printed and the selected dye stuff should have affinity to the fibre. For a given fibre there may be number of
dye classes which would be suitable for eg. Cotton, we can choose dye class such as direct dye, reactive,
vat, solubilised vat etc. whereas if we are interested in printing wool and silk then we may choose dye
classes such as acid, metal complex, reactive and to some extent direct dyes. From the affinity point of
view, the acid and metal complex dyes will not be suitable for cotton. This is the essential prerequisite that
the dye class, which we have selected, should have affinity to the fibre. If we are printing the synthetic
fibres like nylon, we can choose acid, metal complex and disperse dyes, for acrylic, we can have the choice
of basic dyes and for polyester, disperse dyes. Therefore, these are the different dye class, which we can
choose according to the nature of fibre that we want to print.

2. Wetting Agents

Surfaces that can be wetted with water easily are called hydrophilic (Water-loving) surfaces. Opposite are
Hydrophobic (water hating) surfaces. Surface tension of water is a force, which resists the wetting of
hydrophobic surface with water. Water is found to have the surface tension of 72 dyes/cm2. By dissolving
soap in water the surface tension can be brought down to 28 dyes/cm2.

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Substances that reduce the surface tension of water, thereby allowing it to wet a surface easily, which are
otherwise non-wettable or difficulty wettable are known as wetting agents or surface-active agents.

During the preparation of print paste, the dye powder is dissolved in small amount of water. In the case of
direct, acid, basic and reactive dyes, which are water – soluble, lump formation can take place if water is
poured over the dye powder or dye powder added to water. The correct procedure is to add a little amount
of water to the dye powder and make a paste with proper stirring. When all the dye is pasted, further
quantity of water is added and heated to the required temperature and stirred till complete solution is
obtained.

If pasting is not proper prior to the addition of water, small lumps of dye powder which remains un-
dissolved produce dark spots during printing. The high surface tension of water prevents the wetting of the
dyestuff particles. The use of wetting agents is beneficial in dissolving the dye powder.

This problem is more acute in the case of naphthols and vat dyes, which are insoluble in water. In the case
of naphthols, their conversion into soluble sodium naphtholate form has to be carried out by the addition of
NaOH and heating to the required temperature.

In the case of vat dyes, vatting with NaOH and Na2S2O4 (sodium hydrosulphite) is necessary. NaOH and
Na2S2O4 have to come into intimate contact with the external surface of the dyestuff particles, which is
hindered by the high surface tension of water containing NaOH and Na2S2O4. In actual practice the dye
powder is pasted with wetting agent before water and NaOH and Na2S2O4 added.

Turkey Red Oil (TRO) is common wetting agent used for pasting naphthols and vat dyes. TRO is made by
treating Castor oil with Conc. H2SO4 with constant stirring over a prolonged period, followed by
neutralizing with NaOH. TRO is anionic in nature, due to the presence of –OSO3Na groups and hence are
fully compatible with anionic dyes and chemicals, but are not so with cationic or basic dyes and other
cationic products.

3. Solvents, Solution aids, Dispersing agents and Humectants

Solvents or dispersing agents are used to prevent aggregation of the dyestuff molecules in the highly
concentrated paste of the dye. Commonly used solvents include acetin, diethylene glycol, thiodiethylene
glycol etc.

Urea is another substance, which is a colourless crystalline solid, very soluble in water and has dye solvent
and hygroscopic properties. This is useful as an additive to many types of printing pastes. Urea assist in
getting more complete fixation of the dyes so that a deeper shades is produced. It also facilitates the
subsequent washing out of the thickener film from the fabric.

A 40/60 mixture of Urea’s/ form amide is a hydrotropic agent ( which increases the solubility of dyes in
water) used mainly in printing of chrome mordant dyes, acid dyes, direct dyes and solubilised vat dyes.
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Glycerin (Glycol) – BP 290oC with partial decomposition, very hygroscopic, syrupy liquid and mixes freely
with water or alcohol. This is used as hygroscopic agent in the printing paste.

These hygroscopic agents are needed to absorb the condensed steam during steaming. It is essential to use
optimum quantities of the hygroscopic agents; when lower quantities are employed, all the dye present in
the thickener film may not dissolve in the insufficient amount of water absorbed by the thickener film,
resulting poor colour yields (lighter prints)
With larger amounts of hygroscopic agents present, more water is supplied to the thickener film, which may
result in the spreading of the solution beyond the boundaries of the design (print sharpness is lost).

Hygroscopic agent (water-absorbing agents) or solution aid

In order to provide the required amount of moisture to the printed areas of fabric during steaming which
dissolve the dye and the other chemicals, to effect the transfer of dyes into fabric form the thickener film,
various hygroscopic agents used e.g. Glycerin, Urea’s, triethanolamine etc.

Hydrotropic agent: Compounds which increase the solubility of substances which are either insoluble or
sparingly soluble in water are known as hydrotropic agent. Sodium Benzyl sulphanilate, commercially
called solution salt B, is hydrotropic agent for solubilised vat dyes used in the printing paste. 40/60 mixture
of urea / form amide is hydrotropic agent used mainly for printing of chrome mordant / acid / direct and
solubilised vat dyes.

Humectants: A Hydrophilic substance, with stabilizing action on the water content of a material works as
humectants. It keeps within narrow range of moisture content caused by humidity fluctuations; Glycerin is
an example of humectants.

Mechanism of dye fixation – transfer of dye from thickener to the fabric

Consider steaming as a method of fixation, which is very common in textile printing.
For Fixation of dyestuff there should be interaction between dye and fibre. The interaction could be of
different nature depending on the nature of fibre and nature of dyestuff. So it is not the mere penetration of
dye within the fiber that is the requirement but in addition to the penetration, there should be interaction
between dye and fibre so that the printed fabric when subjected to various agencies, the dye will remain
more or less permanent within the fibre.

Sequence: Print  Dry  Fix  Wash  Soap  Wash  Dry

While printing dye, auxiliaries and thickener are in paste form in sufficiently high quantity of water. During
drying almost all the water is evaporated (not 100%); the dye stuff, thickener and other ingredient which
were soluble in print paste will now get precipitated because there is no more water to keep them in the
soluble form. So the first thing to happen is precipitation of dyestuff, thickener and other ingredient in the
print paste on the fabric. Thickener will spread onto printed area in the form of continuous film. The
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dyestuff and other ingredients will be located in the thickener film. At this stage, the dyestuff and other
ingredients will be only on the fibre surface.
During steaming (Fixation), when dried printed fabric is subjected to the steaming operation, the first thing
which happens is the condensation of water at the printed and on non printed portions. At the printed
portions the amount of water which is condensed will be larger than the water because of presence of the
hygrsoscopic agent used in the print paste. Due to this condensed water, the thickener film will swell and
the moment it swells the continuity of the film will be lost i.e. the thickener film gets destructed. So the
moment we get the destruction of the thickener film it become discontinuous and it will allow the passage
for the dyestuff and other chemicals to the fibre. Simultaneously the dyestuff and other ingredients will get
dissolved if are water soluble.
The total effect of this would be a formation of highly concentrated dye solution within the thickener. Now
the transfer of dye from discontinuous thickener film to the fibre takes place by the mechanism what is
known as concentration gradient. The concentration of dye solution is much higher at the surface whereas at
the interior, the concentration of dye stuff is less and therefore there will be tendency of a dye to move from
the region of high concentration to the region of low concentration. This will continue till the equilibrium is
reached. Subsequently the fixation would take place because of forces of attraction between dye and fibre.

Thus the steps in steaming (fixation) are;

1. Condensation of steam on the printed areas
2. Solubilisation of dyestuff and other chemicals in the condensed water
3. Formation of concentrated solution of dye and other chemicals within the thickener film
4. Fibre swelling
5. Concentration gradient between dye in thickener and fibre
6. Penetration of dye in fibre due to affinity
7. Retention of dye in the fibre due to dye-fibre interaction
8. Washing off of unfixed dye, thickener and other chemicals.

Suppose this the thickener film in which dyestuff and other ingredients are embedded. Pink line is fibre(say)
on which the thickener film is deposited. Transfer of dyestuff through the thickener film will be hindered by
the continuity of the film. For the easy transfer of the dyestuff from the thickener to the fibre the thickener
film should be discontinuous.

4. Thickener
This term thickener as far as textile printing is concerned means a water-soluble or water swellable polymer
which when dissolved in water or swelled in water would produce high viscosity solution or gel.

These thickeners could be of natural origin and the simplest example will be starch. They could be semi
synthetic, means the original thickener is natural but it has been chemically modified e.g. hydroxy ethyl
cellulose or Carboxy methylcellulose (CMC). Synthetic thickener, typical example is the one which is used
in pigment printing generally co-polymers of acrylic acid.

Choice of thickeners is based on;

1. Type of the fibre material to be printed
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2. Nature of dye stuff
3. Method of printing
4. Conditions of dye fixation

Essential qualities of thickener;

1. Should be compatible with other ingredients of the print paste.
2. Print paste on printing should sink on the fabric as quickly as possible. This is desirable for wet on
wet printing. The print paste should not float onto the surface of the fibre. It should get absorbed in
the fibre. It is very essential particularly in case of automatic flat bed screen-printing and the rotary
screen-printing where the printing is carried out on wet on wet i.e. colours one after the other
without intermediate drying). If the print paste floats or it does not sink on the fabric then, wet print
will stain the surface of the subsequent screen, which will create the printing fault.
3. Should be free from insoluble impurities to avoid screen chocking and to avoid uneven printing of
fine outlines.
4. After printing and drying the thickener, film must produce satisfactory adhesion to the fabric of the
dried film. Dried film should not be brittle so as to flake-off from the fabric surface.
5. The thickener paste should be shear thinning and thixotropic i.e.When you apply the squeegee
pressure there should be drop in viscosity of print paste. This drop in viscosity will allow the easy
passage of the print paste through the screen. After the printing operation, it should be behave as
thixotropic and regain viscosity after the removal of applied pressure. This would be helpful to
restrict the spreading of the colour beyond the printed portion to maintain the sharpness of the
design.
6. Thickener should not have affinity towards dye and other chemicals in the print paste so as to allow
its penetration into fibre. During fixation or steaming operation, there should be transfer of dye from
thickener film to the fiber and this is possible only when there is no affinity between dye and
thickener.
7. The thickener should be easily removed from the fabric during washing operation. Residual
thickener will impart harsh feel to the fabric.

5. Defoaming Agents

In the case of roller printing the use of wetting agent in the printing paste coupled with continuous agitation
of the paste occurring in the colour box in which the printing paste is kept, produces considerable amount of
foam in the colour box. This produces faulty prints and to avoid this fault, defoamers should be
incorporated in the printing paste e.g. Silicone defoamers, readily emulsifiable hydrocarbons, sulphated oils,
etc. may be used for the purpose.

6. Oxidizing and Reducing Agents

 Oxidizing agents
In order to develop the final colour in steaming (or) in subsequent after-treatment as in printing solubilised
vat dyes, aniline black, some oxidizing agents are added to the printing paste. The oxidizing agent should be
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such that it is not active in the printing paste; otherwise premature development of the colour may take
place in the print paste itself and its subsequent fixation may not be possible.

Sodium chlorate and potassium chlorate are such oxidizing agents. They do not possess oxidizing power in
neutral or alkaline media and hence they may be incorporated in the printing paste along with volatile base
like ammonia. The paste also contains an acid-liberating agent like ammonium chloride. During the
steaming conditions (100oC or higher) ammonia volatilizes, leaving hydrochloric acid making the paste
distinctly acidic. The acidity activates the chlorates at the elevated temperature and oxidizing conditions
needed for the development of the colour are created.

NaNO2 on treatment with acid produces nitrous acid which is an oxidizing agent.

2NaNO 2 + H2SO 4 Na 2SO 4 + 2HNO 2

2HNO 2 NO + NO 2 + H 2O

Similarly Na or K chromate which is not an oxidizing agent produces the corresponding dichromate on
acidification.

2Na2 CrO 4 + H 2SO 4 Na2Cr2O7 + Na 2SO 4 + H 2O

NaNO2 and Na2CrO4 may be added to printing paste, after printing and drying the cloth which is further
treated with an acid, required oxidizing conditions are created for the development of the colour.
In certain cases, especially azo dyes, the prints are susceptible to reducing influences during steaming,
which may result in loss of colour value, by partial destruction of the dyes. In order to prevent this, mild
oxidizing agents are used in the printing paste. Sodium m-nitrobenzene sulphonate (Ludigol, Resist Salt
etc.) is widely used for the purpose. This oxidizing agent is effective under alkaline conditions. It does not
exhibit sufficient oxidizing power in acidic media. If the dye should be protected from the reducing
influence under acidic conditions Sodium chlorate is used instead of Ludigol.

Mild Oxidizing Agent

Sodium m-nitrobenzene sulphonate available in the form of white to light yellow powder, readily soluble in
water to give a colourless to pale yellow solution, has mild oxidizing properties. This is used in the scouring
of desized cotton fabrics containing colour yarns (dyed with vat or azoic colours). This will counteract the
reducing atmosphere created in the kier by starch degradation products. In printing, when vat discharge
effects are produced on direct dye ground, the reducing fumes in the steamer partly destroy the ground
direct dye. This is prevented by pre-padding with mild oxidizing agent solution and drying without washing

 Reducing agents

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Sodium hydrosulphite ( Na2S2O4) is a very powerful reducing agent; it dissolves in about 5 times its weight
of water at room temperature. Solutions should be made only as required and should be protected form
exposure to air to avoid loss in strength due to oxidation. The stability of solution is improved by adding a
small amount of alkali.

NaHSO3 + NaOH Na2SO3 + H2O

When hydrose is exposed to the atmosphere, the strength rapidly falls from 90% to 75% at which it remains
for sometime before there is a further drop; stabilizing effect of sodium sulphite resulting from the first
phase of decomposition.

Sodium hydrosulphite mainly used in vatting of vat dyes in the printing paste prepared by the pre-reduction
method.

When HCHO is added to a solution of Na2S2O4

Na 2 S 2 O4 + 2HCHO + H2O NaHSO2.CH2O + NaHSO3.CH2O

(Sodium sulphoxylate formaldehyde) (Sodium Bi-sulphite formaldehyde)

Both these products are stable at room temperature and do not exhibit reducing properties.
Rangolite C – Sodium sulphoxylate formaldehyde
Formosul G – Zinc sulphoxylate formaldehyde
Hydrosulphite NF – Sodium sulphoxylate formaldehyde
Zaykaylite – Sodium sulphoxyalate formaldehyde

Rangolite C solution is boiled or when prints with a paste containing Rangolite C is steamed, the
sulphoxylate formaldehyde splits up into

NaHSO2. CH2O.2H2O NaHSO2 + CH2O + 2H2O

NaHSO2 + 2H2O NaHSO4 + 4H

Cold solutions of Rangolite C, being stable, are added to the print pastes, which remain stable over
prolonged periods. The solution should never be boiled, due to the decomposition; sufficient amount of
reducing agent will not be available. Other reducing agents SnCl2 is useful especially in discharge printing
on PET fibre fabrics.

7. Catalysts and Oxygen Carriers

A number of catalysts are used in printing pastes, especially when oxidation is involved in the subsequent
steaming. In the case of aniline black, solubilised vat dyes etc, there is a danger of the oxidizing agent

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attacking the fibre at elevated temperature of steaming, a catalyst is used so that the development of the
colour by oxidation is hastened.

Potassium Ferro cyanide, Copper sulphide and Ammonium vanadate are used as catalysts (or oxygen
carriers) used in aniline black dyeing or printing. Ammonium Vanadate is used as a catalyst in the
development of Solubilised vat dyes.

8. Acids and Alkalis

Acids
Whenever acidic conditions have to be created during steaming an acid liberating agent is added to the
printing paste. This acid is need for the development of certain classes of dyes, like solubilised vat dyes and
to activate a potential oxidizing agent like Sodium Chlorate for aniline black and solubilised vat dyes during
steaming. The acid is also needed during the curing stage for fixing the pigments and binders in pigment
printing. The free acid, however, should no be added to the print paste; otherwise premature development of
the colour may take place in the printing paste itself. In all these cases acid-liberating agent (acid donor) is
used. Two types are used;
1. Esters of organic acid
2. Ammonium salts of mineral or organic acids
In both the cases, the compounds do not react initially and during the steaming acidity is generated by
splitting of the ester into acid and alcohol (which vaporizes) or dissociation of ammonium salt into a acid
and ammonia (which escapes in the atmosphere).

An aqueous solution of diethyl tartarate liberates tartaric acid and ethyl alcohol at high temperatures:

CH (OH) COOC2H5 CH (OH) COOH

+ 2C2H5 OH
CH (OH) COOC2H5 CH (OH) COOH
This is better acid-liberating agent than ammonium tartarate especially in the case of Solubilised Vat dyes
since some of these dyes may form sparingly soluble ammonium salts in printing paste.

Acid Liberating Agents

Ammonium Sulphocyanide (NH4CNS), ammonium Chloride (NH4Cl), diammonium hydrogen phosphate
[(NH4)2 H PO4], ammonium gluconage (H2N-OOC-(CHOH)4-CH2OH], ammonium sulphate, ammonium
nitrate etc are used in printing.

(NH4)2SO4  2NH3 + H2SO4

Note: Some amount of ammonium Hydroxide is added to prevent the acidity being formed in the paste, so
that the backward reaction is favoured. As a result solution is free from acid.
In some cases weak organic acids are used in their Free State e.g. Citric acid, Lactic acid, acetic acid,
tartaric acid, glycolic acid etc.
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Alkalis
NaOH and KOH are strong alkalis used in printing paste. Milder alkalis used include Na2CO3, K2CO3,
NaHCO3, Sodium Silicate, Disodium hydrogen phosphate, trisodium phosphate, sodium acetate,
triethanolamine, ammonium hydroxide etc.

9. Carriers and Swelling agents

It is known that certain hydrocarbons, substituted hydrocarbons, phenols etc. accelerate the rate of dyeing of
polyester fibres with disperse dyes from an aqueous medium at about 100oC. Some of the carriers are

Diphenyl o-phenyl phenol p-phenyl phenol

OH

OH

Dichlorobenzene Trichlorobenzene

Cl Cl Cl

Cl Cl

Diphenyl has been found to be the best carrier to fix the dye by pressure steaming at 120 oC - 130oC for
fixation of disperse dye prints on polyester fibre.

Cellulose triacetate which is also a hydrophobic fibre, diethelene glycol-diacetate (DEGDA), polyethylene
glycol (HO (CH2CH2O) nH), ammonium sulphocyanide (NH4CNS), ethyl lactate CH3CH (OH) COOC2H5,
phenols etc act as swelling agent.

Phenol Resorcinol both acts as swelling agents for polyamide fibres, in addition to acting as dye solvents
for acid and metal complex dyes.

10. Miscellaneous Chemicals

In case of Vat dyes of good dischargeability, certain complexing agents are incorporated in the printing
paste containing Rangolite C and printing as Vat dyed fabrics. The dye at the printed portion is reduced and
solubilised and this form of the dye reacts with the complexing agent. The resulting compound is not
deoxidized and is soluble in boiling alkali solution sot that it can be subsequently be removed by an alkali
after-treatment to produce white discharge effects or a coloured ground.

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 H3C CH3
-
O3S CH2 - N SO3
+

Co

+ -
O3S CH2 - N SO3

H3C CH3

Leucotrope W

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