Cellulosic dyeing

Dyeing of cotton fibre textiles:

• Direct dyeing
• Classification of direct dyes
• Direct dyes substantivity
• Factors affecting direct dyeing process
• Wash fastness of direct dyes and need for
after-treatment
 Introduction
• Direct cotton dyes have inherent substantivity for
cotton, and for other cellulosic fibres.
• Their aqueous solutions dye cotton usually in the
presence of an electrolyte such as NaCl or Na2SO4.
• Direct dyes do not require the use of a mordant
and, as their name implies, the dyeing procedure is
quite simple.
• The goods go into the bath followed by the dissolved
dyes. The bath is then gradually heated, usually to
the boil, and additions of salt promote dyeing.
 Direct dye
• These dyestuffs are water soluble and a complete range of shades
can be obtained at a low cost of dyeing.

• the major problem of direct dyes have poor fastness to washing;

• The interaction bond with in the dye and cotton fiber is Hydrogen
bond
• Therefore, their use is restricted to the dyeing of cheaper qualities
of fabrics or those fabrics, which are rarely subjected to washing
during their use.

• The fastness properties could be improved to some extent by

chemical after treatments of the dyed fabric .
Dye with fiber interaction and formation of
Hydrogen bond with in the fiber and the dye
Classification of direct dye according to
dyeing properties(characterstics)
• The most common classification of direct
dyes is that of the Society of Dyers and
Colourists (SDC), based on their levelling
ability(migration) and their response to
increase in the dyeing temperature and to
added salt during exhaust dyeing.
• i.e its depending on the effect of electrolye
and temperature
 Class of Direct dye based on levelling
(1) Class A direct dyes– dyes that are self-levelling, i.e. dyes
of good migration or levelling properties.
(2) Class B direct dyes – dyes that are not self-levelling, but
which can be controlled by addition of salt to give level
results; they are described as salt-controllable.
(3) Class C direct dyes – dyes that are not self-levelling and
which are highly sensitive to salt, the exhaustion of these
dyes cannot adequately be controlled by addition of salt
alone and they require additional control by
temperature; they are described as temperature-
controllable.
Class A direct dyes
• These are self-levelling dyes with good migration,
even in the presence of salt.
• They usually require considerable amounts of salt
for good exhaustion because of their lower
substantivity.
• These dyes are relatively low molecular weight
mono- and bis-azo dyes with several anionic
sulphonate groups per molecule.
• They therefore have good water-solubility and do
not aggregate to a significant degree in solution.
 Cont…
• Dyeing is started at 50 °C in the presence of added salt,
the bath heated to the boil over 30– 40 min, and dyeing
continued at the boil for up to an hour.
• Several further salt additions, of increasing size, are
required to promote exhaustion, the total amount of salt
(5–20% owf NaCl) depending upon the depth of shade
and the liquor ratio.
• Although these dyes would give greater exhaustion by
dyeing at lower temperatures, dyeing at the boil allows
good levelling and adequate penetration of the dyes into
the fibre.
Class B direct dyes
• These are salt-sensitive or salt-controllable dyes,
with poor levelling characteristics.
• They are of higher molecular weight than Class A
dyes, often bis- and tris-azo dyes with just a few
sulphonate groups per molecule.
• They have low to moderate substantivity in the
absence of salt but give much increased exhaustion
on addition of small amounts of salt to the dyebath.
• The dyeing method is the same as for Class A dyes
but the initial salt is omitted. Gradual addition of
dissolved salt, at the boil, controls the exhaustion.
Class C direct dyes
• These very salt-sensitive dyes exhibit poor migration.
• Level dyeing depends on the gradual increase of the dyeing
temperature and subsequent additions of limited amounts
of salt.
• Levelling agents may be required.
• These dyes are temperature-controllable.
• Dyeing is started at low temperature without added salt.
The bath is slowly heated, with particular care in the
temperature region where exhaustion is most rapid. Some
salt may be added during further dyeing at the boil. These
dyes are often polyazo dyes with few sulphonate groups
and of high substantivity for cellulose
 Cont…
• At lower dyeing temperatures, they are very prone
to aggregation in solution and sensitive to salt
addition.
• Salt in the dyebath impedes exhaustion at low
temperatures because it promotes even more
aggregation.
• The higher the degree of aggregation of the dye, the
lower the concentration of individual dye molecules
in the solution that can diffuse into the fibre, and
therefore the lower the rate of dyeing. Dye
aggregates are too large to penetrate into the pores
of cellulosic fibres.
 Cont…
• Class C dyes therefore generally have better
washing fastness than Class B dyes, with
Class A dyes having even lower fastness
 Direct dye substantivity for cellulose
• Direct dyes invariably have extended, conjugated,
coplanar molecules, with widely spaced hydrogen
bonding groups and some sulphonate groups to
provide solubility in water.
• The greater the number of sulphonate groups in the
dye molecule, the higher the water solubility but the
lower the fastness to wet treatments, and the lower
the dye substantivity.
• Molecular coplanarity is, however, a specific
requirement for substantivity
 Cont…
• Substantivity may also involve the surface active
properties of direct dyes
• Substantivity may therefore depend more on van der
Waals and dispersion forces between the dye and fibre
molecules.
• cellulosic fibres are extremely porous, they have an
extended internal surface and surface activity effects
could account for a considerable degree of dye
adsorption.
• Direct dyes aggregate in solution and in the fibre, another
facet of their surface activity. There is circumstantial
evidence that aggregation of the dye molecules in the
cellulose fibre is the cause of the dye’s substantivity.
 Cont…
• Despite the considerable literature on the effects
of varying molecular structure on the
substantivity of dyes for cotton, the origins of
such substantivity are poorly understood. Are
both dye–fibre and dye–dye interactions as well
as surface activity involved in promoting
substantivity of direct dyes for cellulosic fibres?
The best answer one can give is – possibly. How
little we understand of this technology.
Dyebath variables that influence dyeing
behaviour (affects direct dyeing process
The principal parameters affecting the absorption
of direct dyes by cellulose from aqueous solutions
are
 Temperature,
 Time of dyeing,
 Liquor ratio,
 Solubility of the individual dye,
 salt controllability and to a lesser degree the
influence of auxiliary agents.
The influence of added salt
• The influence of added salt is the most important factor in the
dyeing of cellulosic fibres with direct dyes.
• In dyeing, there are two objectives: good exhaustion and
good colour uniformity. Both depend on the salt-
controllability of the dyes, or how the gradual salt additions
during dyeing influence the rate of exhaustion. Unfortunately
salt-controllability is very dependent on the dyeing
temperature.
• For practical purposes, it is useful to have some idea of the
degree of exhaustion at different salt concentrations for each
dye, possibly at different dyeing temperatures
 Cont…
• For two dyes having about the same substantivity,
salt should have a greater influence on the
exhaustion of the one with the larger number of
sulphonate groups, and therefore the larger negative
molecular charge. The fibre’s negative surface
potential repels the more highly charged dye
molecules to a greater extent so this dye will respond
more to salt additions. This conclusion, however, is
not necessarily of great practical value because
commercial direct dyes already contain much
electrolyte.
 Cont…
• For two dyes having about the same substantivity,
salt should have a greater influence on the
exhaustion of the one with the larger number of
sulphonate groups, and therefore the larger negative
molecular charge.
• The fibre’s negative surface potential repels the more
highly charged dye molecules to a greater extent so
this dye will respond more to salt additions.
• This conclusion, however, is not necessarily of great
practical value because commercial direct dyes
already contain much electrolyte
The effect of temperature
• Increasing temperature increases the rate of dyeing
and of dye migration.
• The exhaustion will decrease as the dyeing
temperature increases, as for some direct dyes on
cellulosic fibres.
• Increasing temperature also promotes dye de-
aggregation in the dyeing solution liberating more
individual dye molecules to enter the fibre.
• The temperature should be controlled depends on
the behaviour of dyes and
 The influence of dyeing pH
• Dyeing with direct dyes is usually carried out in
neutral solution. Under alkaline conditions,
cellulose fibres have an even greater negative
potential, partly because of increasing
dissociation of a number of cellulose hydroxyl
groups, and exhaustion is lower.
 The effect of liquor ratio
• Dyebath exhaustion should increase with
decrease in the dyeing liquor ratio. This is
certainly the case for direct dyes.
• This means that dyeing at low liquor ratio
decreases the amount of waste dye in the
effluent.
• It also consumes less water and steam, and
allows a given salt concentration with less added
salt.
 Cont…

• There has been a strong trend towards dyeing

at as low a liquor ratio as is practicable. It
should always be remembered, however, that
the required amount of dye must then be
dissolved in a bath of reduced volume.
• It is important to ensure that the dye is, in
fact, in solution at the beginning of dyeing
when the temperature is relatively low and
after addition of salt.
 cont...
• of dye must then be dissolved in a bath of
reduced volume. It is important to ensure that
the dye is, in fact, in solution at the beginning
of dyeing when the temperature is relatively
low and after addition of salt.
 Cont…
• Under alkaline conditions, reducing end groups,
particularly prominent in low molecular weight
celluloses such as viscose, reduce some azo direct
dyes, decreasing the colour yield.
• In general, however, if dyeing of cellulosic fibres is in
acidic solution, only weak acids are used and the
residual acid in the goods is thoroughly rinsed out
before drying.
• Strongly acidic dyeing conditions favour the acid-
catalysed hydrolysis of cellulose. Any traces of
residual mineral acid dried into the material can cause
considerable damage.
 Color fastness properties of Direct dyed
materials
• Generally these dyes are used where high
wash fastness is not required.
• Wash fastness:- poor unless treated with
suitable dye fixing agent
• Light fastness:- Good
• Rubbing fastness:- Moderate to Good.
AFTERTREATMENT PROCESSES FOR DIRECT
DYEINGS
• The wet fastness properties (particularly washing,
water and perspiration) of virtually all dyeings of
direct dyes are inadequate(poor) for many end uses.
• but notable improvements can be brought about by
aftertreatments. Based on principle like increase
the molecular weight of dye and decreasing the
solubility of dye.
• All such treatments, however, incur increased
processing costs because of the extra time, energy,
labour and chemicals involved.
 Cont…
• after treatments of the dyed fabric with
potassium dichromate, copper sulphute,
HCHO, cationic dye fixing agents etc. However,
these agents are not environment friendly and
their use is restricted.
 Metal complex formation
• In this type of aftertreatment, cupric or chromic ions
convert the dye into a metal complex.
• Coppering involves treating the dyeing with acetic acid
and copper sulphate solution and heating to 70–80 °C.
Complexation usually increases the light fastness.
• The process results in a change in hue and may be
reversible on repeated washing due to de-metallisation.
This results in a gradual decrease in washing fastness.
• Both copper and chromium are environmentally
undesirable. Copper aftertreatment is still used for a
few brown, navy and black shades.
Generalize direct dye
 Recipe for direct dye
• Direct dye stuff –X%
• Common salt the concentration which is totally
depend on the type of shade which is given to the
cotton fabric.
E.g 5% for light shade
10% for medium shade
20% for dark shade
• Tempurature- Boil
• Time – 30 to 45 mint.
 Application
Dyeing process involves two process:
1. Preparation of dye bath
2. Dyeing