DYES.

INTRODUCTION
Synthetic dye was accidentally discovered by William Perkins
1856, who is an English chemist while he was experimenting with
synthesizing quinine in aniline. Before that time, all dyeing
materials were taken out from the barks, roots, seeds, leaves and
shellfish as well. Most synthetic dyestuffs are repaired from coal-
tar derivatives. Their making is a highly complicated technical
operation, which is constantly changing In the early times the
colouring materials were extracted from natural sources like
plants and insects. Nowadays thousands of such substances are
synthesised in factories on a large scale. Dyes are the organic
compounds that are used to impart colour to textiles, foodstuffs,
silk, wool and other objects. Dyes are capable of getting fixed to
the fabrics/objects permanently and are resistant to the action of
water, soap, light, acid, and alkalise.

Every coloured compound cannot be used as a dye. A good dye

must have most of the following properties:
1. It must have a suitable colour.
2. It must be able to fix itself or capable of being fixed to the fabric
from the solution.
3. When fixed, it must be fast resistant to the action of light, water,
soap, detergents, etc. during washing or to the organic solvents
during dry cleaning.

Why do dyes or dyed articles appear to have a

characteristic colour?
If a molecule absorbs light in the visible region (400 nm to 750 nm)
corresponding to green colour, then it will appear violet, which is
the complementary colour of green. Similarity, if a dye absorbs a
blue colour, it will appear yellow which is the complementary
colour of blue. Thus, the dyes impart colour to the fabric by
absorbing the complementary colour.
Constitution of Dyes

The colour of a compound is due to the presence of certain groups

containing multiple bonds. These groups which impart colour to a
compound are called chromophores.
Some examples of chromophores are
–NO2 (Nitro), –N = O (nitroso), –N = N – (azo), quinonoid structures,
etc.
At the same time, there are certain groups which they are not
chromophores themselves they deepen the colour when present
with coloured compounds. The groups that deepen the colour of a
coloured compound are called auxochromes. Some examples of
common auxochromes are:

–OH, –NH2, –NHR, –NR2, –Cl, –CO2H, etc.

Difference between Dyes and Pigments

Concerning their solubility, organic colourants fall into two

classes, i.e. dyes and Pigments. The difference between the dyes
and the pigments is that dyes are soluble in water and are also
soluble in organic solvents. On the other hand, pigments are
usually insoluble in both. Dyes can be used to color any
substance but pigments are used only to colour polymeric
substrate because the mechanism of pigment differs from that of
dyes. This involves only colouration because pigment can mix
with the polymer before the formation of the article. Pigments do
not interact with the substrate and hence do not destroy the
crystal structure of the substrate
34.1.3 Classification of Dyes
A large number of dyes are used for various purposes. These are
classified based on their
(i) constitution
(ii) application

Classification based on the constitution:

Depending upon the characteristic structural units, the dyes,

are classified as given in Table:
Classification of Dyes based on their applications.
Dyes are classified into the following types based on their
applications.
(i) Acid dyes (ii) Basic dyes(iii) Direct dyes (iv) Disperse dyes
(v) Fibre reactive dyes (vi) Vat dyes(vii) Insoluble azo dyes (viii)
Mordant dyes

i) Acid Dyes
These are azodyes used in the form of their sodium salt of
sulphonic acid (–SO3H), carboxylic acid (– COOH) or phenol. The
dye can be applied to wool, silk and nylon. These do not have much
affinity for cotton and therefore, cannot be used to dye cotton.

Acidic dyes are water-soluble dyes containing sulphonic acid

groups (usually present as sodium sulphonate salts). These
produce a negative charge on the molecule of dye and increase its
solubility in water.

1 These are soluble in water and are applied under acidic

conditions.
2 The acid dyestuff is mostly used for wool and silk and to a less
extent nylon and
acrylic fibres.
3 The maximum quantity of dye absorbed depends on the amount
of H2SO4present in the bath.
4 Acid dyes are inexpensive dyes.
5 They are fast to light, but they are not fast to washing.

Basic dyes

Basic dye is a cationic stain and reacts with negatively charged

material. Basic dyes comprise of amino or alkyl amino group. As
their colour base is indissoluble in water, this can be achieved by
the conversion of a base into salt

These dyes contain basic groups like the (-NH2) group or (-NR2)
group therefore these are called basic dyes. These dyes attack the
anionic sites present on the fabrics and get attached to them.
These are used to dye modified nylons, polyester, wool, cotton,
leather, paper, etc. Aniline yellow, malachite green and crystal
violet are the basic dyes.

The first coal tar dye was basic.

1 It is applied to wool, silk, cotton, acrylic, and modacrylic
fibres.
2 When acrylic fibres were first marketed, they were very difficult
to dye due to the lack of specific dye sites in the fibres. Such groups
were introduced into the fibre and brilliant colours can now be
obtained with these dyes.
3 They give good fastness and bright shades to acrylics
(iii) Direct Dyes

As the name suggests these dyes can be directly applied to the

fabrics from their aqueous
solution. The direct dyes attach to the fibre using hydrogen
bonding. These are
very effective for dying cotton, wool and rayon.
Martius yellow (Table 34.1) and Congo red are common examples
of direct dyes.

Direct dyes are cheap and easy to apply but of poor fastness
quality.
1: These dyes are also known as ‘salt dyes or cotton colours, which
dye
cotton, other vegetable fibres and viscose rayon.
2: They are readily soluble in water. The colours of cotton fabrics
dyed with direct dyes are not fast.
3: They are applied to Cellulose fibres from aqueous liquor in
which an electrolyte is
added, which is usually Sodium Chloride as it accelerates the rate
at which the
dye is picked up by the fibre.
4; They generally bleed. To make them fast on fabric add Sodium
Bicarbonate for warm colours, and Copper Sulphate for cool
colours.
(iv) Ingrain dyes
These dyes are very important because over 60% of the dyes used
are azodyes or ingrain dyes. The fabric to be dyed is soaked in an
alkaline solution of phenol or naphthol and is then treated with a
solution of diazotised amine. These are used for cotton, silk,
polyester and nylon. The colour is not very fast because the
interaction is only on the surface. For

example, para-red is an ingrain dye.

• The Azoic colours are applied to cotton in two stages. The first
consists of treatment with naphthol and the second by treatment
of the naphtholated material with diazotized base or diazotized
salt. The development takes place in situ by the coupling
the reaction between naphthol and diazo components.
• They are quite fast to wash and have poor to excellent light
fastness.
• Azoic colours are used mostly on cotton and for special purposes
on nylon
• Azoic colours are sometimes referred to as ice dyes because ice
is frequently
used to bring the dyes to low temperatures.
• Azoic colours give bright, high-intensity colours, much more so
than the common
dye classes.
Fig. 2.13 Azoic colours
(v) Disperse Dyes
These dyes are usually applied in the form of a dispersion of finely divided dye.
The dyes are dispersed in a soap solution in the presence of phenol, cresol or
benzoic acid. These are used for nylon, polyester and polyacrylonitrile.
Some common examples of disperse dyes are celliton fast pink B and celliton fast
blue B

The fibres that are most commonly dyed with dispersed dyes are
cellulose diacetate, cellulose triacetate and polyester fibres (Fig.
2.16). To a lesser extent acrylic and nylon fibres are also dyed with
disperse dyes.

• Polyester fibres being hydrophobic and with significant

crystalline content, the assistance of high temperature, high
pressure and carriers (which swell the fibre)
is taken to achieve satisfactory dyeing.

(vi) Reactive dyes

• They were first developed in 1956 by I.C.I., U.K.

• The dye is retained through a chemical reaction between the dye
and the fibre. As such their fastness properties are excellent.
• The fibres most readily coloured with reactive dyes are natural
and man-made cellulosic fibres, natural protein fibres and
polyamide fibres.
• With some reactive dyes, the dyeing can be carried out at room
temperature.
However, with most reactive dyes, the dyeing is carried out at high
temperatures
(up to the boil).

These dyes attach to the fibre themselves by irreversible chemical reactions.

These dyes induce fast colour on the fibres which is retained for a longer time.
These dyes are used to dye fibres like cotton, wool or silk. Dyes which are
derivatives of 2, 4 dichloro –1, 3, 5 – triazine are important examples of fibre-
reactive dyes.
(vii) Vat dyes

• They are insoluble in water, but they are made soluble by the use
of a strong reducing agent, such as Sodium hydrosulphite
dissolved in sodium hydroxide.
• These are the fastest dyes for cotton, linen and rayon.
• They also may be applied to wool, nylon, polyester etc.
• Vat dyes are hot water dyes.
• Hot water dyes are available in both powder and liquid form.
• The first synthetic Vat dye was an Indigo created in 1879.
• VAT dyes are expensive because of the initial cost as well as the
method of
application.

Vat dyes are water insoluble dyes Vat dyes are insoluble in water and have to
be dissolved in water by using sodium hydroxide and sodium hydrogen sulphite
usually at 50 degrees for 15‐20 minutes. Vat dyes are most important dyes for
dyeing and printing on cotton and cellulosic fibres They have excellent all-
round fastness, which includes‐ washing, light, perspiration, chlorine and
rubbing fastnesses. Vat dyes are especially fast to light and washing. Brilliant
colors can be obtained in most shades. Originated in medieval Europe, vat dyes
were so named because of the vats used in the reduction of indigo plants
through fermentation
(viii) Mordant Dyes
These dyes require an additional substance (generally a metal
ion) for fixing to the fibre. These are used mainly for dyeing wool.
The method involves the precipitation of certain mordant material
(binding agent) on the fabrics which then combines with the dye
to form an insoluble coloured complex called lake. For acid dyes,
metal ions are used as mordants but for basic dyes, tannic acid
is used as the mordant.

For example, alizarin is a mordant dye (Table 34.1). It gives a

rose red colour with Al3+ and a blue colour with Ba2+, a
brownish red colour with chromium (Cr3+) and a black violet
with iron mordant.
Chemistry of Dyeing
 The process of applying colour to fiber stock, yarn or fabric is
called dyeing. There may or may not be thorough penetration of
the colorant into the fibers or yarns.
The dyeing of a textile fibre is carried out in a solution,
generally aqueous, known as the dye liquor or dye bath.
For true dyeing to have taken place, coloration of fabric and
absorption are important determinants.
Coloration: The coloration must be relatively permanent: that
is not readily removed by rinsing in water or by normal washing
procedures. Moreover, the dyeing must not fade rapidly on
exposure to light.
Absorption: The process of attachment of the dye molecule to
the fibre is one of absorption: that is the dye molecules
concentrate on the fibre surface. There are four kinds of forces by
which dye molecules are bound to the fibre:
1)Ionic forces 2) Hydrogen bonding 3) Vander Wals' forces and 4)
Covalent chemical linkages.
 Exhaustion: In any dyeing process, whatever the chemical
class of dye being used, heat must be
Levelness: An Important Quality, evenness of dyeing, known as
levelness is an important quality in the dyeing of all forms of
natural and synthetic fibers. It may be attained by the control of
dyeing conditions.
Conditions to attain Levelness By agitation to ensure proper
contact between dye liquor and substance being dyed and by use
of restraining agents to control rate of dyeing or strike. Solvent
Dyeing Serious consideration has recently been given to the
methods of dyeing in which water as the medium is replaced by
solvents such as the chlorinated hydrocarbons used in dry
cleaning. The technological advantages in solvent dyeing are:
1. Rapid wetting of textiles
2. Less swelling
3. Increased speed of dyeing per given amount of material
4. Savings in energy, as less heat is required to heat or evaporate
per-chloro-ethylene.
Thus, it eliminates the effluent (pollution) problems associated
with the conventional methods of dyeing and finishing. supplied
to the dye bath; energy is used in transferring dye molecules from
the solution to the fibre as well as in swelling the fibre to render
it more receptive. The technical term for this process is
exhaustion