Introduction

Dye is a chemical compound used to produce long lasting colour in

materials. Dyes are used in textile, paper and plastic industries, for leather, ink,
food, etc.
A dye may not be capable of attaching itself to the material to be dyed, but also
retain its colour on prolonged exposure to air, sunlight, temperature, soap or
water.
Presence of certain groups in the molecules of dyes impart colour to them,
because the electrons in these compounds get excited, absorbing some colour
from the visible region of light and the complementary colour is shown. Examples
of such groups are -N=N-(azo) groups, -N=O(nitro) group and NH
2
(amino)
groups.
A dye can generally be described as a colored substance that has an affinity to
the substrate to which it is being applied. The dye is generally applied in
an aqueous solution, and may require amordant to improve the fastness of the
dye on the fiber.
Both dyes and pigments appear to be colored because they absorb some
wavelengths of light preferentially. In contrast with a dye, a pigment generally is
insoluble, and has no affinity for the substrate. Some dyes can
be precipitated with an inert salt to produce a lake pigment, and based on the salt
used they could be aluminum lake, calcium lake or barium lake pigments.
Dyed flax fibers have been found in the Republic of Georgia dated back in a
prehistoric cave to 36,000 BP. Archaeological evidence shows that, particularly
in India and Phoenicia, dyeing has been extensively carried out for over 5000
years. The dyes were obtained from animal, vegetable or mineral origin, with no
or very little processing. By far the greatest source of dyes has been from
the plant kingdom, notably roots, berries, bark, leaves and wood, but only a few
have ever been used on a commercial scale.
Classification

These dyes have been classified into two categories
Classification based on constitution: Depending upon the characteristic structural
units the dyes are classified as follows.

Sl. No. Type of Dye Structural Unit Examples
1. Nitro dyes
N
O
O
(Nitro group)

Martius yellow,
Naphthol yellow
2. Azo dyes
N = N
(azo group)
Orange-I, Orange-II,
Congo red
3.
Triphenyl methane
dyes
(C
6
H
5
)
3
C
Malachite green,
Rosaniline
4. Phthalein dyes

Phenolphthalein,
Mercurochrome
C
O
C
O
O
(Phthalein group)
5.
Anthraquinone
dyes

Alizarin
6. Indigoid dyes

Indigo, Tyrian purple

Structures

O H
NO
2
NO
2
(Orange-I)
SO
3
Na
+
N
N O H
(Martius yellow)


C
C
O
O
(anthraquinone group)
C
C
C
O
O
Indigoid group
(Phenolphthalein)
O
O
OH
OH
(Alizarine)
C
O
C
O
O H
OH
(Indigo)
C
N
+
(CH
3
)
2
N(CH
3
)
2
C
C
N
C
N
C
O H
H O
(Malachite green)

Diphenyl Methane Dye
Auromine - 0
Classification Based on Application
A particular dye may be suitable for one kind of fibre and may be unsuitable for
the other. For example, a dye suitable for wool and silk may not be applied or
used for dyeing cotton or rayon. Thus based on the class, shade and other
properties like resistance to acids, alkalies, and fastness to light a classification of
dyes is done, as given below:
a) Acid dyes b) Basic dyes
c) Direct dyes d) Disperse dyes
e) Fibre reactive dyes f) Vat dyes
g) Insoluble azodyes h) Mordant dyes
a) Acid dyes: These dyes are characterised by the presence of acid group like
sulphonic acid ( SO
3
H), carboxylic acid ( COOH) and phenolic group. The
presence of such groups make the dyes more soluble and also serve as the
reactive points for fixing the dye to the fibre.
Application: These dyes are applied to wool, silk and nylon. These have no
affinity for cotton.
N
C
(H
3
C)
2
NH
2
N
+
(CH
3
)
2
Examples: Orange-I and Orange-II can be obtained by the action of
sulphonic compounds with naphthols or by coupling sulphonic compounds
with naphthols.
Na
+
O
3
-
S N N
+
Cl
-
+
O H
-naphthol
O H
SO
3
-
Na
+
N
N
Orange-I


b) Basic Dyes: These dyes contain (NH
2
) group or (NR
2
) group as
chromophore (colour bearing group) or auxochrome (colour enhancing
group). In acidic solutions these form water soluble cations. These dyes use
the anionic side on the fabric to get themselves attached.
Application: This type of dyes is used to dye nylon, polyester, wool, cotton,
leather, paper, etc.
SO
3
-
Na
+
N N Cl
-
+
+
-naphthol
O H
O H
SO
3
-
Na
+
N
N
Orange-II
Example
1. Aniline
yellow

2. Butter yellow

3. Crysodine G


c) Direct Dyes: These dyes also belong to the class of azo dyes and are used to
dye the fabrics directly by placing it in aqueous solution of the dye. The
direct dyes attack the fibre by means of hydrogen bonding.
Application: These are very effective for dying cotton, wool and rayon
Example:
1. Martius yellow
2. Congo Red

NH
2
O H
N
N N
N
H
2
N
SO
3
-
Na
+

c) Disperse Dyes: These dyes, as the name signifies, are usually applied in the
form of a dispersion of finely divided dye in a soap solution in the presence
of phenol, cresol or benzoic acid.
N
N NH
2
N
N N
CH
3
CH
3
N
N NH
2
NH
2
Application: These are mainly used to dye rayon, dacron nylon, synthetic
fibres, polysters and poly acrylonitrile.
Examples:
1. Celliton fast pink B

2. Cellition fast blue B

d) Fibre Reactive Dyes: These dyes are used to dye fibres like cotton, wool or
silk. These are linked to the fibre by virtue of the hydroxy or amino group
present on the fibre. These dyes induce fast colour on fibres which is
retained for a longer time.
e) Insoluble azo dyes: The dyes belonging to this class are directly synthesised
on the fibre. The fabric to be coloured is soaked in an alkaline solution of
phenol or naphthol and is than treated with a solution of diazotised amine
to produced the azo dye on the surface of the fabric.
Application: These dyes can be used to dye cotton silk, polyester, nylon,
etc.
Example:

O
O
O H
NH
2
O
O
N H
NH
CH
3
CH
3
O
2
N
N
N
O H
(Nitroaniline red)
f) Vat Dyes: Before being introduced on to fabric these dyes are first reduced
to colourless leuco compounds in wooden vats by alkaline reducing agent.
The fibre is then soaked in the solution of the dye. After proper absorption
of the dye, the fibre is then exposed to air or to an oxidising agent. By doing
so the dye gets oxidised to yield insoluble coloured dye on the fabric.
Example: Indigo dye
g) Mordant Dyes: A dye which imparts different colours to the fabric in the
presence of different metal ions (called mordants) is referred to as mordant
dye. Nowadays it is rarely used
Application: These dyes are used for dyeing of wool. The method involves
the precipitation of certain substances on the fabrics which then combine
with the dye with the dye to form an insoluble coloured complex called
lake. Depending on the kind of mordant used different colours. For
example, Alizarin, a mordant dye, gives red colour with aluminium and tin
salts, where as brownish red colour chromium mordant and black violet
with iron mordant.

HISTORY:

Dyed flax fibers have been found in the Republic of Georgia dated back in a
prehistoric cave to 36,000 BP. Archaeological evidence shows that, particularly in
India and Phoenicia, dyeing has been extensively carried out for over 5000 years.
The dyes were obtained from animal, vegetable or mineral origin, with no or very
little processing.

Earlier, all dyes were made from natural resources like plants and animals. During
the Late 1800s and early 1900s, chemists developed synthetic dyes. Synthetic
dyes are available with a variety of colour shades, are fast and cheaper in cost.
CHARACTERISTICS OF A DYE


It must have a suitable colour.
It must be capable of being fixed to the material.
When fixed it must be fast to detergents, soaps, water, dry cleaning
solvents, light and dilute acids.

Acid Dyes:
The term acid dye derives from the dyeing process, which is carried out in an acidic aqueous
solution (pH 2.6).The acid used in the dye bath is often vinegar (acetic acid) or citric acid Protein fibres
contain amino and carboxyl groups, which are ionized mostly to NH3
+
and COO

. In the acid dye bath the

carboxylate ions are converted to undissociated carboxyl groups owing to the addition of acid HX
(sulfuric or formic acid), which causes the positively charged wool to take up an equivalent amount of
acid anions X.
General Formula:
Its general formula is DSO3

Na
+

Fibre Application:
These water-soluble anionic dyes are applied to
Man Made Fibres
o Nylon
Natural Fibres
o Wool, silk
They are also used to some extent for paper, leather, ink-jet printing, food, and cosmetics.
Classification:
Acid dyes are divided into three groups based on their differences in affinity, which is
primarily a function of the molecular size:
Levelling dyes are relatively small molecules which form a salt linkage bond with the protein
fibre.
Milling dyes are large-volume dye molecules, for which salt formation with the fibre plays only a
secondary role and the adsorption forces between the hydrophobic regions of the dye molecule
and those of the protein fibre predominate.
Dyes with intermediate molecular size not only form a salt linkage bond with the wool fibre but
are also bonded to the fibre by intermolecular forces and have properties lying in an
intermediate position between those of the levelling and the milling dyes.
Acid dyes are thought to fix to fibres by
Hydrogen bonding
Van Der Waals forces
Ionic bonding.
They are normally sold as the Sodium salt therefore they are in solution anionic.
Animal protein fibres and synthetic Nylon fibres contain many cationic sites therefore there is an
attraction of anionic dye molecule to a cationic site on the fibre. The strength (fastness) of this
bond is related to the desire/ chemistry of the dye to remain dissolved in water over fixation to
the fibre.

Structures
The chemistry of acid dyes is quite complex. Dyes are normally very large aromatic
molecules consisting of many linked rings. Acid dyes usually have a sulphonyl or amino group
on the molecule making them soluble in water. Water is the medium in which dyeing takes place.
Most acid dyes are related in basic structure to the following:
Anthraquinone Type:
Many acid dyes are synthesised from chemical
intermediates which form anthraquinone-like structures as their
final state. Many blue dyes have this structure as their basic
shape. The structure predominates in the levelling class of acid
dye.

Azo dyes:
The structure of azo dyes is based on
azobenzene, Ph-N=N-Ph. Although Azo dyes are a separate
class of dyesuff mainly used in the dyeing of cotton (cellulose) fibres many acid dyes have a
similar structure, most are red in color.

Triphenylmethane Related:
Anthraquinon
e
Triphenylmethane Acid dyes having structures related to triphenylmethane predominate in
the milling class of dye. There are many yellow and green dyes commercially applied to fibres that are
related to triphenylmethane.





Application:
These dyes are applied in the following way,
1. The dye is dissolved in the water and it dissociates as follows,
DSO
3
Na + H
2
O DSO
3

+ Na
+

2. WoolNH
2
+H
+
WoolNH
3
+

This H+ was liberated by the acid used for the acidic medium
3. Then the bond formation occurs as follows,
DSO
3

+ Wool NH
3
+
WoolNH
3
SO
3
D
In case of the silk and nylon wool is replaced by them in the equation and the other reaction
remains same.
o
o
Exhausting Agent:
Na2SO4 is used as an exhausting agent.
This c ll o DSO
3

group more towards the fibres because of SO3- group present

in it.
Retarding Agent:
Triphenylmethane
Usually NaCl is used as the retarding agent.
It is used for the following purposes,
For even distribution of the dye.
For controlling the rate of reaction.
For avoiding the shades in the fabrics.
Fibre requirements:
WOOL is usually dyed at 1% for a full shade except for blacks, navy blues, and maroons,
which usually requires 3%. It may be boiled but should not be allowed to go to a rolling boil. Temperature
change must be gradual to avoid felting. It should be processed at least 1 hour to 1.5 hour for good
fastness.
SILK is also dyed at 1% but will have richer concentration at this shade than wool. It must be
dyed at lower temperature than wool no
NYLON is dyed at 2% depth of shade for one hour or more and is brought to full boil. It does
not absorb the dyes readily as wool and the silk do because of its molecular structure.
Properties of Acid Dyes:
Light Fastness:
Light Fastness is the degree to which a dye resists fading due to light exposure. All dyes have
some susceptibility to light damage, simply because their strong colours are indications that they absorb
the wavelengths that they don't reflect back. Light Fastness is checked on BLUE SCALE. Acid dyes are
resistant to sunlight and there light fastness rating is 4-5.
Washing Fastness:
Washing fastness of the acid dyes is also good. Its rating is from 4-5.
This is checked on the GREY SCALE.
Rubbing fastness:
Acid dyes have also good rubbing fastness.




Basic Dyes:
These are also called as CATIONIC Dyes.
Basic dyes are cationic, which means that the coloured part has a positive charge,
when they are dissolved in water. They will bond to either carboxyl or sulfonic acid groups on a
fibre, via the formation of salt links with these anionic groups in the fibre. The number of anionic
sites in the fibre determine the saturation value SF, i.e. the maximum amount of dye which can
be taken up by the fibre.
Basic dyes can be used to dye wool or cotton, but they do not perform well, tending
to fade in sunlight quite badly. So this dyeing stopped with the passage of time because these
fibres were dyed much better with the other dyes. The first synthetic dye, Mauvein also known as
aniline purple, discovered by William Henry Perkin in 1856, was a basic dye, almost a century
before the development of acrylic fibre by DuPont, in 1944.
General formula:
Its general formula is D
+
.
Fibre Application:
Basic dyes are applied on
Acrylic Fibres
Modified Acrylic Fibres:
These are the acrylic fibres that are produced by mixing another monomer to them.
o o o o oo o l o
o l es heating at high temperature. By this mixing
the Glass Transition Temperature falls to 80-
The monomers that are usually added to them are Vinyl Chloride and Vinyl Pyridine. 15-20 %
of these monomers are added.
Application:
When the dye is dissolved in the water this ionize and the dyeing portion of the dye is
positively charged. While the fabric has the negative charged sited on it.
Following reaction takes place in the dyeing process.
ASO
3

+ D
+
ASO
3

D
+

If we dye the fabric below 80- o o wll l lo wll o
o o low B o lo o 9
rate of dyeing becomes fast and the linkages will become fast. But as a result the levelling of the
dye will not be uniform.
Under such conditions the retarding agent is required that will level the dyeing process on the
fabric. Usually NaCl is used for this function.
The acidic pH condition is achieved by using the acid usually CH3COOH.
Also a buffer solution is used to control the pH to a proper value. CH3COONa is used for this
purpose.
Dyeing mechanism:
The cationic chromophore is first absorbed by the negatively charged fibre surface and then
diffuses, at elevated temperature, into the interior of the fibre; there it binds to active acid groups, the
number of which is limited and the accessibility of which depends on temperature and fibre
constitution. Therefore, the dyeing characteristics of a cationic dye are determined by
affinity and diffusibility.
The affinity of cationic dyes is enhanced by increasing the size of the molecule and especially
by introducing aromatic residues. The phenyl-substituted dye is absorbed onto polyacrylonitrile materials
at a higher rate than the dye that is methine substituted as shown.












Phenyl-substituted Basic dye





Properties:
Basic dyes have following properties/
Water Soluble
Toxic in nature
Produce Brilliant Shades
Work under acidic conditions i.e. pH=4-5
Very Stable
The light fastness of these dyes is excellent. The rating of there light fastness is 6-7. This means
that these are very much stable in the light of sun.
Wash fastness is also very good and the colour is not fade with the washing of the fabrics dyed
with these dyes. The rating of wash fastness in about 5-6.
The rubbing fastness of these dyes is also much better.

Other names for acrylic fibres:
Acrylic is sold under names such as Orlon, Courtelle, Dralon, Leacryl, Acrilan, and
Nitron. It is composed of poly(propenonitrile) (acrylonitrile) with small amounts of a
comonomer.
Modacrylic is sold under names such as BHS, Creslon, PAN, and Teklan, and also as
Lycra. Modacrylic fibres are between 35% and 85% acrylonitrile, and are made from resins that
are copolymers (combinations) of acrylonitrile and other materials such as vinyl chloride,
vinylidene chloride or vinyl bromide. Modacrylic can probably be dyed just like acrylic.





Methine Substituted Basic
Dye
Disperse Dyes.
These are substantially water-insoluble non ionic dyes for application to hydrophobic fibres
from aqueous dispersion. They are used predominantly on polyester and to a lesser extent on nylon,
cellulose, cellulose acetate, and acrylic fibres. Thermal transfer printing and dye diffusion thermal
transfer processes for electronic photography represent niche markets for selected members of this class.
Disperse dyes are colorants with low water solubility i.e. in the disperse colloidal form, are
suitable for dyeing and printing hydrophobic fibres and fabrics.
Since polyester fibres are hydrophobic, water-soluble dyes do not attach. In contrast,
polyester fibres can be dyed easily with water-insoluble, small molecular dyes originally developed for
dyeing cellulose acetate. Since the preferred dyeing medium is an aqueous liquor, the poorly water-
soluble dyes must be dispersed before application.
Fibre Application:
Disperse dyes are applied on
Polyester
Nylon
Acetate Rayon
Chemical Constitution:
Industrially applied disperse dyes are based on numerous chromophore systems.
Approximately 60 % of all products are azo dyes, and ca. 25 % are anthraquinone dyes, with the
remainder distributed among quinophthalone, methine,
naphthalimide, naphthoquinone, and nitro dyes.
Azo dyes are currently employed to create almost the entire range of shades; Anthraquinone
derivatives are used for red, violet, blue, and turquoise. The remaining dye classes are used mainly to
produce yellow shades.
Dyeing Methods:
Disperse dyes are applied on the fibre in the following methods.
1) Carrier Dyeing Method
2) High Temperature Dyeing Method
3) Thermosol process

Carrier Dyeing Method:
The difficulty with polyester dyeing is that it requires a lot of heat to get the dye into the
fibre. Boiling water is not hot enough to do the job by itself, so a noxious-smelling carrier chemical must
be added, for immersion dyeing, unless newer low-energy disperse dyes are used.
The carrier often used is Phenol/Phenyl.
It swells the chains in the fibre at 60- o
fibres.
Following is the process for this way of dyeing.
Take the dye and disperse it into water
Add dispersing agent for the even distribution off the dye
Add acetic acid for attaining pH up to 5-6
Add buffer solution i.e. CH3COONa for stable pH
Add the carrier compound
Raise temperature gradually to 90-
Dye for 30-35 minutes
Then drain the dye liquor and wash the fabric with detergent at 60- washing will drain
out all the carrier molecules.
Reduction Clearing Treatment is then performed which removes all the dye molecules
present in the surface of the fabric. Usually NaHSO3+NaOH are used at 50-
There are some limitations in the Carrier dyeing method because of following draw backs.
Some Carriers are very expensive.
Polyester and carrier are both organic in nature so it is difficult to remove completely from fabric.
It uses the dispersing agent which also increases the cost and if not used then spotting may be
caused.
When drained into water causes pollution in it.
Light fastness becomes poor with time by this dyeing process.
High Temperature Dyeing Method:
In this method no carrier is required and the polyester is dyed at an elevated temperature
and high pressure.
= 3
Pressure = 30 lb/inch2
The other parameters and the reagents are same as used in the carrier dyeing method.
Machines used in the High temperature dyeing process are
High temperature Dyeing Jigger
Here the fabric is dyed in the open width in the machine.
JAT Dyeing Machine
Here the fabric is dyed in the rope form and passed through a pipe for dyeing.
Thermosol Process:
In dyeing polyester fibres, the dyeing time can be shortened significantly by increasing
dyeing temperature. The rate of dyeing increases exponentially above the glass transition temperature; a
temperature increase of 10 C doubles the rate. For this reason, at 200 C fast coloured fibres can be
obtained with disperse dyes within seconds especially for polyester Cellulose mixtures. This property is
used to dye polyester fibres continuously in a pad-fix process, which was introduced by Du Pont as the
thermosol process. Application of the dye from an aqueous dispersion is followed by drying and fixing.
Properties:
Organic colouring substances
Non ionic compounds
Hydrophobic in nature
Low water solubility that increases with the temperature
Dispersed in the dye liquor
Convert into fine particles in presence of the dispersing agent
Forms H-Bonds when applied on the polyester
Models for the dyeing of polyester fibres with disperse dyes have been developed. When the
dye is applied from aqueous medium, it is adsorbed from the molecularly dispersed aqueous solution
onto the fibre surface and then diffuses into the interior of the fibre.
The following parameters determine the rate of dyeing and, to some extent, the levelling
properties:
The dissolution rate during the transition from the dispersed crystalline state of the dye into the
molecularly dispersed phase.
The diffusion rate at the fibre surface and, especially, in the interior of the fibre.


Origin of colour in dyes
The colour of dyes is attributed to their ability to absorb some wavelengths of
visible region of electromagnetic spectrum (380 nm to 760 nm). The part of the
colour which reflected back gives the colour of the dye i.e. complementary to the
colour absorbed. The colour of visible light absorbed and the complementary
colour reflected are listed in table.

Wave length (nm) Colour absorbed Complementary colour
400 435 Violet Yellow, Green
435 480 Blue Yellow
480 490 Greenish Blue Orange
490 500 Bluish Green Red
500 560 Green Purple
560 580 Yellowish Green Violet
580 595 Yellow Blue
595 605 Orange Greenish Blue
605 750 Red Blue, Green
In the earlier days fabrics were coloured by the dyes mainly from Alizarin (red
dye) and indigo (blue dye).

Health and safety


Any dyes including acid dyes have the ability to induce sensitization in
humans due to their complex molecular structure and the way in which they are
metabolised in the body. This is extremely rare nowadays as we have a much
greater understanding through experience and knowledge of dyestuffs
themselves. Some acid dyes are used to colour food. We wear fabrics every day
exposing our skin to dyes.

The greatest risk of disease or injury due to dyes is by ingestion or exposure to
dye dust. These scenarios are normally confined to textile workers. Whereby the
dye itself is normally non toxic, the molecules are metabolised (usually in the
liver) where they may be broken back down to the original intermediates used in
manufacture. Thus many intermediate chemicals used in dye manufacture have
been identified as toxic and their use retricted.

For example: the dye CI Acid red 128 was found to metabolise in the body back to
ortho-toluidine, one of its chemical intermediates. Many intermediates used in
dye manufacture such as o-toluidine, benzidine etc. were found to be
carcinogenic.