Dyes

A dye is an organic compound composed

of a chronopher, the coloured portion of
the dye molecule, and an auxochrome,
which slightly alters the colour.
Dyes are molecules that can be dissolved
in water or some other carrier so that
they will penetrate into the fibre.

Pigments
Pigments are insoluble colour particles
that are held on the surface of a fabric
by binding agent.
Their application is quick, simple, and
economical. Any colour can be used on
any fibre, because the pigments are held
mechanically.

NATURAL DYES
Before, all dyes were derived directly from
natural sources such as the leaves, flowers,
berries, stems or roots of plants, from insects
and shellfish, and even a number of minerals.
The colouring of the fibres results from the
chemical reaction of the functional groups
within the fibres and those within the dye stuff.
The difficulty with most natural dyes is that
they lack colour fastness.

 However the treatment of the fabrics with certain natural

acids or oxides (metallic salts) improves their colour fastness.
These substances are called mordants, they react both with
the dyestuff and the fibre to form an insoluble compound
thus fixing the colour within and on the fibre.
Natural dyes were not replaced immediately because some
were still faster than some of the new synthetic ones. Today
over eight thousand different dyes are being manufactured.

Dyeing of Textile

Textile dyeing is concerned with organic (i.e. carbonbased) compounds that can be dissolved in appropriate
solvents, usually water.
The dyes in solution are absorbed on the surface of the
textile fibre then passed into the interior of the material
by a process called diffusion.
The process of transferring the dye from solution to the
fibre is called exhaustion, with 100% exhaustion meaning
that there is no dye left in the dye bath solution.
An important property of dyeing is its levelness, in other
words when the same depth of colour can be seen all
over the material.

 Another factor is good penetration, when the dye

has penetrated deeply into the structure of the fibre,
colouring it from the outer surface of the fibre to its
interior
Dye molecules are attracted by physical forces at the
molecular level to the textile. The amount of this
attraction is known as 'substantivity': the higher the
substantivity the greater the attraction of the dye for
the fibre.
These include two main types:
Protein fibres of animal origin, such as wool and
silk
Cellulosic fibres of plant origin, such as cotton, flax
and jute

Man-made fibres:

These include three main types:

Synthetic polymers, such as polyester,
nylon and acrylic
Regenerated cellulose, such as viscose and
lyocell
Cellulose acetates, such as diacetate and
triacetate

Dye-Fibre association:
Dyeing can take place at various stages of
textile production,
Pre-fibre,
fibres,
yarns,
fabrics and
garments.

 In all dyeing processes the first step is to

impregnate the textile material with dye
solution.
An important requirement is the movement of
the dye into the structure of the fibre.
In addition, the ability of certain types of dye
to interact with the polymer material that
makes up the fibre determines whether or not
that type of dye is suitable for a particular
fibre.

 Organic dyes are classified into groups

according to their ability to dye various
fibres, and some of the main dye classes and
their suitability for different fibres are shown
below.
Cellulosic: Direct, reactive, vat, sulphur
Wool : Acid, pre-metallised, reactive (some)
Polyamide: Acid, premetallised, reactive
(some)
Acrylic: Basic, disperse (some)
Polyester: Disperse

Direct dyes

The first direct dye was called Congo red and was introduced in
1884. It was called a direct dye because it was the first dye to
become available for colouring cellulose 'directly', without the
use of a mordant. Direct dyes are applied in a boiling dye-bath
in the presence of salt.
Direct dyes are water soluble. These are sodium salts of
aromatic sulphonic acids and when dissolved in water, ionize
into the dye anion (negatively charged ion) and sodium cation.
(an ion that has a positive electric charge and is attracted toward
the cathode (negative electrode) in electrolysis). Therefore a
simple diffusion into the fibre from the aqueous solution

Direct dyes
They have an affinity for cellulosic fibres (cotton
and linen), viscose and silk.
Some of the dyes need soda ash to completely
dissolve in water.
During dyeing, the dye stuff molecules are taken
up by the fibre from the dye bath and retained in
it.
It has a relatively poor fastness to light, washing
and perspiration. It can however be improved by
after-treatments

Direct dyes ..
Advantages:
Cheap
Simple to apply
Wide range of colours
Very good fastness to light

Disadvantages:
Poor wet fastness
Moderate brightnes

Reactive dyes
Developed in the 1950s, these were the first
dyes produced capable of reacting chemically
with the fibre (usually cellulose) under alkaline
conditions.
The dye thereby becomes part of the fibres,
rather than merely remaining as an independent
chemical entity within the fibre.
Reactive dyes are applied at relatively low
temperatures, with controlled amounts of salt
and alkali e.g. soda ash, caustic soda, sodium
silicate
etc.

Reactive dyes .
The application of these dyes to cotton involves two
distinct steps: i.e. (1) dyeing in the presence of salt to
effects as much exhaustion as possible and (2)
chemically reacting the dye with the fibre in the
presence of an alkali which helps in the fixation
(chemical reaction of the dye with the fibre) of the dye
These dyes are water soluble.
In the first stage of dyeing, reactive dyes resemble
direct dyes in that its exhaustion can be brought about
by adding salt but it has much lower affinity to cotton
than direct dyes.
In the second stage when the alkali is added to the
dyebath for fixation, the dye gets deactivated
(hydrolized) and can not further react with the cotton
fibre.

Reactive dyes
Therefore in the dyeing and fixing of the reactive
dyes, 5 30% of the dye gets deactivated
(hydrolised) and can not further react with the
cotton fibre.
The deactivated dye however does have some
affinity (low) for cotton hence is absorbed and
retained by the cotton.
However due to the low affinity of the deactivated

 Advantages:
Simple to apply
Wide range of bright colours
Good fastness to light and washing
Disadvantage:
Relatively expensive

Disperse dyes
Disperse dyes were introduced in the 1920s to
dye acetate fibres, which were otherwise undyeable, although nowadays they are mainly
used for polyester fibres. They can also dye
nylon.
They are substantially water-insoluble dyes
and are applied to the fibre in the form of a
fine aqueous dispersion. They are diffused into
the fibre at high temperature. (they are however
soluble in hot water to some extent, the solubility increases
with temperature and therefore due to this solubility the
dyeing of synthetic fibres is facilitated at elevated
temperatures).

Disperse dyes

The dye is mechanically ground to a very small

particle size and with the help of a dispersing agent,
they can be dispersed in the dye-bath.
When a man-made fibre e.g. polyester, nylon or
acetate is entered into the dye-bath and the
temperature raised, the solubility of the dye in the
water is increased and the dissolved dye is taken up
and retained by the fibre. This continues till either all
the dispersed dye is taken up by the fibre or the fibre
is saturated by the dye.
Cellulose acetate is dyed in the presence of a
dispersing agent e.g. soap.
Polyester and polyamides is difficult since the
structures of these fibres are very compact and hence
the dye molecule has difficulty penetrating the fibre.

Disperse dyes
The fibres are therefore softened at elevated
temperature (130 200C) and the dye molecules
penetrate well inside the fibre and when the dyed
fibre is cooled the dye is trapped inside the fibre.
OR
Carrier dyeing is used whereby the dyeing is carried
out in a boiling dispersion (100C) of the dye in water
in the presence of a carrier like phenyl phenols,
dyphenyl, chlorobenzenes etc. during the dyeing the
polyester fibres absorb the carrier which swells the
fibre and opens up the fibre structure, thereby
creating wide pores in the fibre. The dye molecules
enter into these pores and get fixed in the fibre. After
dyeing the carrier is removed from the fibre. (when
the fibre structure collapses, the dye is trapped in
the fibre structure. (disperse dyes are applied at high
temperatures in pressurized vessels).

 The principal forces of dye-fibre

association in the case of disperse
dyes are hydrogen bonding and vander Waals forces.

Acid dyes
The term 'acid' referring to the fact that acid or an
acid-producing compound is used in the dye bath.

Suitable for wool, silk and nylon fibres. They have no

affinity for cellulosic fibres.
The fibres are dyed in the presence of acids like
sulphuric, acetic or formic acid.
A wide range of brilliant shades can be produced.
Acid dyes are soluble in water and produce coloured
anions and sodium cations.

Acid dyes
When dyeing protein fibres (wool, silk) in the
presence of an acid, the amino group of the
fibre acquires a positive charge by protonation.
Thus the acid produces cationic sites in the
fibre which attract and retain the dye anion.
The higher the concentration of the acid in the
dyebath, more cationic sites are produced in
the fibre thus more dye is taken up i.e. the
acids act as exhausting agents when dyeing
with acid dyes on wool.

There are different types including:

Levelling acid dyes: these are
available in a range of bright colours
and have good light fastness, but their
wash fastness is only moderate
Milling acid dyes: these are also
available in a range of bright colours
and have good light and wash
fastness, but are more difficult to
apply correctly than levelling dyes

Azoic dyes
Suitable substrates are: cotton, linen
and viscose
Azoic dyeing involves the production of
an insoluble azo dye on a fibre by the
interaction of a diazotised amine and a
coupling component. i.e. after diffusion
into the fibre, two different chemicals are
made to react together to form the insoluble
colour.
Therefore these are not ready made dyes
but the dyer has to make them in the fibre.
(they are therefore supplied as naphthols
and bases.)

Azoic
dyes
A naphthol may produce different colour with different
bases.
1.The application of azoic colours involves two steps:
Naphtholation: dyeing with naphthol. Naphthols are
insoluble but are solubilized in the presence of sodium
hydroxide to form (sodium naphtholate)at high
temperatures. The soluble form has an affinity for
cotton fibres. (salt is used as an exhaustion agent).
The cotton is immersed in this solution and then
removed from this naphtholate solution and squeezed.
1.Development: the coupling of the diazotized base
with naphthol. The cotton is then entered into the
solution of the diazotized base whereby the naphthol
taken up during the naphtholation stage reacts with
the diazotized base and forms the coloured pigment
which is not firmly held/fixed in the cotton but loosely
deposited on the fibre surface. (thus it can be easily
rubbed off from the dyed material.

Vat Dyes

These are water-insoluble dyes

usually containing keto (RC=O)
groups, which are applied in the
soluble
reduced
form
and
subsequently oxidized in the fibre to
the insoluble form.
Vat dyes are made into a soluble
form by the vating process: using
sodium hydroxide and sodium
hydrosulphite, usually at 50C for 15
20min.

Vat Dyes
In their soluble form, they behave like direct dyes,
hence can be dyed on cotton.
They remain in the soluble form only in the
presence of sodium hydrosulphate and sodium
hydroxide, thus during the entire dyeing process,
these chemicals should be present in the dye-bath
in sufficient amounts to keep the dye in the
soluble form.

Sulphur dyes
These are used on cellulosic fibres to
produce dark colours such as black,
brown, olive and green.
Like vat dyes, they are waterinsoluble mixtures that are present in
the dye bath as leuco derivatives.
These are then oxidised on the fibre
to give the desired colour, which is
normally very fast to washing.

Basic (cationic) dyes

These are used to dye
polypropenonitrile (acrylic) fibres with
an acidic character.
The mechanism by which basic dyes
are absorbed onto the acrylic fibres is
believed to one of ion exchange, similar
to the mechanism, whereby the cations of acidic fibres are replaced by the
dye cat-ions

PRE-TREATMENTS
Most textiles require pre-treatments in
order to prepare them to accept the
colour substance.
These include:
singing,
desizing,
scouring and
bleaching.

Singing
This process burns any fibre ends projecting from
the surface of the fabric.
These protruding ends cause roughness, dullness
and pilling and interfere with colour application.

The fabric is passed between two gas flame bars

or hot plates to singe in both the sides in one
step.

Fabrics containing heat sensitive fibres such as

cotton/polyester blends must be singed carefully
and often are singed after the dyeing because
the melted ends of the polyster may cause
uneven dyeing.

Desizing
In this the sizing added to the warp
yarns us the slashing step is
removed.
Desizing is necessary so that dyes
will bond with both warp filling yarns.
Physical, biological, or chemical
desizing may be done depending on
the sizing agents and the fibre
content of the fabric.

Scouring
General term referring to removal of
foreign matter or soil from the fabric
prior to dyeing.
The specific procedure is related to
the fibre content of the fabric.
The foreign matter involved may be
processing of oils, starches, natural
waxes, gum (in case of silk), tints or
colours added to aid in the fibre
identification during production.
Scouring usually involves the use of
detergents and alkaline solutions.

 Degumming of silk is usually done in

boiling water with detergent,
although acid degumming and
enzyme degumming are also used.
Kier boiling or boiling-ff of cotton is
done in an alkaline solution at high
temperature and under pressure in
large vessels called kier.
Scouring of wool is a gentler washing
process under less alkaline
conditions

Bleaching
It is a process of whitening fibres,
yarns, or fabrics by removing irregular
natural colour.
Most bleach are oxidizing agents, the
actual bleaching is done by active
oxygen.
A few bleaches are reducing agents
and are used to strip colour from
poorly dyed fabrics.

 The goal of bleaching is uniform

removal of hydrophobic fabric
impurities and a high uniform degree
of whiteness in order to achieve clear
uniform colours when dyeing, which is
especially important for pastel colours.
All bleaches are not suitable for all
fibres. Because chemical reactions
differ between fibres, bleaches are
selected with regards to fibre content.