Acknowledgement

Index
1. Introduction
2. History of Dyes
 Natural Dyes
 Synthetic Dyes
3. Structure and colour
4. General features
 Fibre Structure
 Fibre Porosity
 Dye retention
5. Types Of Dyes
6. Dyeing Techniques
 Direct Dyeing
 Disperse Dyeing
 Vat Dyeing
 Azo Dyeing
 Reactive Dyeing
 Dyes
I. Introduction
Dye is substance used to impart colour to textiles, paper, leather, and
other materials such that the colouring is not readily altered by washing,
heat, light, or other factors to which the material is likely to be exposed.
Dyes differ from pigments, which are finely ground solids dispersed in a
liquid, such as paint or ink, or blended with other materials. Most dyes
are organic compounds (i.e., they contain carbon), whereas pigments
may be inorganic compounds (i.e., they do not contain carbon) or
organic compounds. Pigments generally give brighter colours and may be
dyes that are insoluble in the medium employed.

Colour has always fascinated humankind, for both aesthetic and social

reasons. Throughout history dyes and pigments have been major articles
of commerce. Manufacture of virtually all commercial products involves
colour at some stage, and today some 9,000 colorants with more than
50,000 trade names are used. The large number is a consequence of the
range of tints and hues desired, the chemical nature of the materials to
be coloured, and the fact that colour is directly related to the molecular
structure of the dye.
II. History of Dyes
 Natural Dyes
Until the 1850s virtually all dyes were obtained from natural sources,
most commonly from vegetables, such as plants, trees, and lichens, with
a few from insects. Solid evidence that dyeing methods are more than
4,000 years old has been provided by dyed fabrics found in Egyptian
tombs. Ancient hieroglyphs describe extraction and application of
natural dyes. Countless attempts have been made to extract dyes from
brightly coloured plants and flowers; yet only a dozen or so natural dyes
found widespread use. Undoubtedly most attempts failed because most
natural dyes are not highly stable and occur as components
of complex mixtures, the successful separation of which would be
unlikely by the crude methods employed in ancient times. Nevertheless,
studies of these dyes in the 1800s provided a base for development
of synthetic dyes, which dominated the market by 1900.

The heterocyclic dye known as indigo is a naturally occurring compound that can be obtained from plants in the
genus Indigofera.
Two natural dyes, alizarin and indigo, have major significance. Alizarin is
a red dye extracted from the roots of the madder plant, Rubia
tinctorium. Two other red dyes were obtained from scale insects. These
include kermes, obtained from Coccus ilicis (or Kermes ilicis), which
infects the Kermes oak, and cochineal, obtained from Dactylopius
coccus, which lives on prickly pear cactus in Mexico. One kilogram (2.2
pounds) of cochineal dye can be obtained from an estimated 200,000
insects. The principal coloured components in these dyes are kermesic
and carminic acids, respectively, whose similarity was established by
1920. In their natural state many colorants are rendered water-soluble
through the presence of sugar residues. These sugars, however, are often
lost during dye isolation procedures.

Probably the oldest known dye is the blue dye indigo, obtained in Europe
from the leaves of the dyerswoad herb, Isatis tinctoria, and in Asia from
the indigo plant, Indigofera tinctoria. Even by modern standards, both
alizarin and indigo have very good dyeing properties, and indigo remains
a favoured dye for denim, although synthetic indigo has replaced the
natural material.

Dyerswoad, Isatis tinctoria, is a source of indigo, considered the oldest known dye.Shunji Watari
With a process developed by the Phoenicians, a derivative of
indigo, Tyrian purple, was extracted in very small amounts from the
glands of a snail, Murex brandaris, indigenous to the Mediterranean
Sea. Experiments in 1909 yielded 1.4 grams (0.05 ounce) from 12,000
snails. Historically, this dye was also called royal purple because kings,
emperors, and high priests had the exclusive right to wear garments dyed
with it, as is well documented in the Hebrew Bible and illustrated for
Roman emperors on mosaics in Ravenna, Italy. By the 1450s, with the
decline of the Eastern Roman Empire, the Mediterranean
purple industry died out.
Logwood is the only natural dye used today. Heartwood extracts of the
logwood tree, Haematoxylon campechianum, yield hematoxylin, which
oxidizes to hematein during isolation. The latter is red but in
combination with chromium gives shades of charcoal, gray, and black; it
is used mainly to dye silk and leather.

 Mordants
Highly skilled craftsmen with closely guarded secret formulas rendered
dyeing a well-protected trade. The formation of different colours by
mixing red, blue, and yellow dyes was well known in ancient times, as
was the use of metal salts to aid the retention of dyes on the desired
material and to vary the resultant colours. Natural dyes cannot be
applied directly to cotton, in contrast to wool and silk, although cotton
can be dyed by vatting or by pretreatment with inorganic salts known
as mordants (from Latin mordere, meaning “to bite”).
These are adsorbed on the fibre and react with the dye to produce a less
soluble form that is held to the fabric. Alum, KAl(SO4)2 × H2O, as well
as iron, copper, and tin salts were common ancient mordants. No doubt
the secret processes included other ingredients to improve the final
results. Mordants also were used to vary the colours produced from a
single dye. For example, treatment with aluminum hydroxide, Al(OH) 3,
before dyeing with alizarin produces Turkey red, the traditional red of
British and French army uniforms. Alizarin gives violet colours
with magnesium mordants, purple-red with calcium mordants, blue
with barium mordants, and black-violet with ferrous salts. Around 1850,
chromium salts, used as mordants, were found to provide superior dye
retention and, in time, largely displaced the others; chromium mordants
are still widely used for wool and, to some extent, for silk and nylon.

 Decline of Natural Dyes

Until 1857 the dye industry utilized natural dyes almost exclusively;
however, by 1900 nearly 90 percent of industrial dyes were synthetic.
Several factors contributed to the commercial decline of natural dyes. By
1850 the Industrial Revolution in Europe led to a
burgeoning textile industry, which created increased demand for readily
available, inexpensive, and easily applied dyes and revealed the
important economic limitations of natural dyes. Since most dyes were
imported from distant sources, transportation delays were likely to slow
the production of dyed materials. Dye quality was affected by the whims
of nature and the dye maker’s skills. In addition, inefficient processes
were often required for optimum results; for example, Turkey red dyeing
could involve more than 20 steps to produce the desired bright, fast
colour. Advances in organic chemistry, both practical and theoretical,
spurred by studies of the many new compounds found in coal tar,
increased interest in finding ways to utilize this by-product
of coke production. The dye industry played a major role in the
development of structural organic chemistry, which in turn provided a
sound scientific foundation for the dye industry.

 Synthetic Dyes
In 1856 the first commercially successful synthetic dye, mauve, was
serendipitously discovered by British chemist William H. Perkin, who
recognized and quickly exploited its commercial significance. The
introduction of mauve in 1857 triggered the decline in the dominance of
natural dyes in world markets. Mauve had a short commercial lifetime
(lasting about seven years), but its success catalyzed activities that
quickly led to the discovery of better dyes. Today only one natural
dye, logwood, is used commercially, to a small degree, to dye silk, leather,
and nylon black.

Recognition of the tetravalency of carbon and the nature of the benzene

ring were key factors required to deduce the molecular structures of the
well-known natural dyes (e.g., indigo and alizarin) and the
 new synthetics (e.g., mauve, magenta, and the azo dyes). These structural
questions were resolved, and industrial processes based on chemical
principles were developed by the beginning of the 20th century. For
example, Badische Anilin- & Soda-Fabrik (BASF) of Germany placed
synthetic indigo on the market in 1897; development of the synthetic
process of this compound was financed by profits from synthetic alizarin,
first marketed in 1869. With the onset of World War I, British and U.S.
industry were ill-prepared to provide products theretofore obtainable
from Germany. The British government was forced to aid rejuvenation of
its own dye industry; one measure brought several companies together,
later to become part of Imperial Chemical Industries (ICI), modeled after
the Bayer and BASF combines in Germany. In the United States a strong
coal tar chemical industry quickly developed. After the war, leadership in
organic chemistry began to shift from Germany to Switzerland, Britain,
and the United States. In contrast to the combines of Europe,
independent firms developed the U.S. research-oriented chemical
industry.
A few new dye types were introduced in the 20th century, and major
challenges were posed by the introduction of synthetic fibres, which held
a major share of the world market, and by technological advances.

III. Dye Structure and Colour

Advances in structural theory led to investigations of correlations

between chemical constitution and colour. In 1868 German
chemists Carl Graebe and Carl Liebermann recognized that dyes contain
sequences of conjugated double bonds: X=C―C=C―C=C―…, where X
is carbon, oxygen, or nitrogen. In 1876 German chemist Otto Witt
proposed that dyes contained conjugated systems of benzene rings
bearing simple unsaturated groups (e.g., ―NO 2, ―N=N―, ―C=O), which
he called chromophores, and polar groups (e.g., ―NH 2, ―OH), which he
named auxochromes. These ideas remain valid, although they have been
broadened by better recognition of the role of specific structural features.
He had also claimed that auxochromes impart dyeing properties to these
compounds, but it later became clear that colour and dyeing properties
are not directly related. Witt suggested the term chromogen for specific
chromophore-auxochrome combinations.

The colours of dyes and pigments are due to the absorption of

visible light by the compounds. The electromagnetic spectrum spans
a wavelength range of 1012 metres, from long radio waves (about 10 km
[6.2 miles]) to short X-rays (about 1 nm [1 nm = 10–9 metre]), but human
eyes detect radiation over only the small visible range of 400–700
nm. Organic compounds absorb electromagnetic energy, but only those
with several conjugated double bonds appear coloured by the absorption
of visible light (see spectroscopy: Molecular spectroscopy). Without
substituents, chromophores do not absorb visible light, but the
auxochromes shift the absorption of these chromogens into the visible
region. In effect, the auxochromes extend the conjugated system.
Absorption spectra (plots of absorption intensity versus wavelength) are
used to characterize specific compounds. In visible spectra, the
absorption patterns tend to be broad bands with maxima at longer
wavelengths corresponding to more extended conjugation. The position
and shape of the absorption band affect the appearance of the observed
colour. Many compounds absorb in the ultraviolet region, with some
absorptions extending into the violet (400–430 nm) region. Thus, these
compounds appear yellowish to the eye—i.e., the perceived colour is
 complementary to the absorbed colour. Progressive absorption into the
visible region gives orange (430–480 nm), red (480–550 nm), violet
(550–600 nm), and blue (600–700 nm); absorption at 400–450 and
580–700 nm gives green. Black objects absorb all visible light; white
objects reflect all visible light. The brilliance of a colour increases with
decreasing bandwidth. Synthetic dyes tend to give brilliant colours. This
undoubtedly led to their rapid rise in popularity because, by comparison,
natural dyes give rather drab, diffuse colorations. Examples of dyes, each
containing a different  chromophore, include azobenzene, xanthene and 
triphenylmethane. Alizarin contains the anthraquinone chromophore.
These four dyes were commercial products in the late 1800s.

IV. General Features

In dyeing operations, the dye must become closely and evenly associated
with a specific material to give level (even) colouring with some measure
of resistance to moisture, heat, and light—i.e., fastness. These factors
involve both chemical and physical interactions between the dye and the
fabric. The dyeing process must place dye molecules within the
microstructure of the fibre. The dye molecules can be anchored securely
through the formation of covalent bonds that result from chemical
reactions between substituents on the molecules of the dye and the fibre.
These are the reactive dyes, a type introduced in 1956. Many dye-fibre
interactions, however, do not involve covalent bond formation. While
some dyeing methods have several steps, many dyes can be successfully
applied simply by immersing the fabric in an aqueous solution of the dye;
these are called direct dyes. In other cases, auxiliary compounds and
additional steps are required to obtain the desired fastness. In any event,
questions arise as to how and how well the dye is retained within the
fibre. The structure of the fibres from which the common fabrics are
made provides some guidance for the selection of useful colorants.

1. Fibre Structure :
Fibre molecules are polymeric chains of repeating units of five major
chemical types. Wool, silk, and leather are proteins, which are polymers
of α-amino acids, RCH(NH2)COOH (where R is an organic group). Each
chain consists of a series of amide linkages (―CO―NH―) separated by
one carbon to which the R group, characteristic of each amino acid, is
bonded. These groups may contain basic or acidic substituents, which
can serve as sites for electrostatic interactions with dyes having,
respectively, acidic or basic groups. Polyamides (nylons)
are synthetic analogs of proteins having the amide groups separated
by hydrocarbon chains, (CH2)n, and can be made with an excess of either
terminal amino (―NH2) or terminal carboxyl groups (―COOH). These
and the amide groups are sites for polar interactions with dyes. Polyester
poly(ethylene terephthalate), or PET, is the main synthetic fibre,
accounting for more than 50 percent of worldwide production of
synthetic fibres. The terminal hydroxyl groups (―OH) can serve as
dyeing sites, but PET is difficult to dye because the individual chains
pack tightly. 
Acrylics have hydrocarbon chains bearing polar groups, mainly nitriles,
made by copolymerization of acrylonitrile (at least 85 percent) with small
amounts (10–15 percent) of components such as acrylamide and
vinyl acetate to produce a fibre with improved dyeability. Fibres with 35–
85 percent acrylonitrile are termed modacrylics. Cellulose is found in
plants as a linear polymer of a few thousand glucose units, each with
three free hydroxyl groups that can be extensively hydrogen-
bonded. Cotton fibres are essentially pure cellulose. Wood contains 40–
50 percent cellulose that is isolated as chemical cellulose by a process
known as pulping. In fibre manufacture, the insolubility of cellulose
caused processing problems that were overcome by the development of
the viscose process, which produces regenerated cellulose with 300–400
glucose units. This semisynthetic cellulosic is rayon, which is very similar
to cotton. The semisynthetic acetate rayon, produced by acetylation of
chemical cellulose, has 200–300 glucose units with 75 percent of the
hydroxyl groups converted to acetates. The smaller number of free
hydroxyls precludes extensive hydrogen bonding, and dyes differing
from those for cotton and rayon are needed.

2. Fibre Porosity :
Fibres are made by various spinning techniques that produce bundles of
up to several hundred roughly aligned strands of polymer chains with
length-to-diameter ratios in the thousands. For the dyeing process, an
important characteristic of fibres is their porosity. There is a huge
number of submicroscopic pores aligned mainly on the longitudinal axis
of the fibres such that there are roughly 10 million pores in a cross-
section of a normal fibre. The internal surface area therefore is enormous
—about 45,000 square metres per kilogram (5 acres per pound) for
cotton and wool—some thousand times greater than the outer surface
area. To produce deep coloration, a layer of 1,000–10,000 dye molecules
in thickness is needed. Upon immersion in a dyebath, the fabric absorbs
the aqueous dye solution, and the dye molecules can move into pores
that are sufficiently large to accommodate them. Although many pores
may be too small, there is an ample number of adequate size to give
satisfactory depths of colour.

3. Dye Retention :
Various attractive forces play a role in the retention of particular dyes on
specific fibres. These include polar or ionic attractions, hydrogen
bonding, Van der Waals forces, and solubilities. The affinity of a dye for a
given substrate through such interactions is termed its substantivity.
Dyes can be classified by their substantivity, which depends, in part, on
the nature of the substituents in the dye molecule.
Attractive ionic interactions are operative in the case of anionic (acid)
and cationic (basic) dyes, which have negatively and positively charged
groups, respectively. These charged groups are attracted to sites of
opposite polarity on the fibre. Mordant dyes are a related type. In the
mordanting process, the fabric is pretreated with metallic salts,
which complex with polar groups of the fibre to form more highly
polarized sites for better subsequent interaction with the dye molecules.
Nonionic groups can also be involved in attractive interactions. Since
the electronegativities of oxygen, nitrogen, and sulfur are greater than
those of carbon and hydrogen, when these elements are part of
a compound, the electron densities at their atomic sites
 are enhanced and those at neighbouring atoms are decreased. An O―H
bond is therefore polar, and an attractive interaction between the
hydrogen of one bond and the oxygen of a neighbouring bond can occur.
Hydrogen bonding may be exhibited by any weakly acidic hydrogen.
Although there is no chemical bond, strong attractive forces are involved.
Phenolic hydroxyl groups are more highly polarized and, in dyes, can act
as auxochromes and as good hydrogen-bonding sites.
Similar, but weaker, attractive forces are operative between other closely
spaced polarized groups. These are the Van der Waals interactions,
which are effective for dye adsorption if the separation between
molecules is small. Such interactions are particularly important for
cellulosics, which tend to have relatively large planar areas to which dye
molecules are favourably attracted.
Although most dyes are applied as aqueous solutions, the finished goods
should not be prone to dye loss through washing or other exposure to
moisture. An exception is in the common use of highly soluble dyes to
identify different fibres for weaving processes. These are called fugitive
tints and are readily removed with water.

V. Types Of Dyes
1) Acid Dyes : Acid dyes are highly water soluble, and have better light
fastness than basic dyes.The textile acid dyes are effective for protein
fibers such as silk, wool, nylon and modified acrylics. They contain
sulphonic acid groups, which are usually present as sodium sulphonate
salts. These increase solubility in water, and give the dye molecules a
negative charge. In an acidic solution, the -NH2 functionalities of the
fibres are protonated to give a positive charge: -NH3+. This charge
interacts with the negative dye charge, allowing the formation of ionic
interactions. As well as this, Van-der-Waals bonds, dipolar bonds and
hydrogen bonds are formed between dye and fibre. As a group, acid dyes
can be divided into two sub-groups: acid-leveling or acid-milling.
 Acid Red -88
 Properties
The main properties of acid dyes are ,
1)These dyes are anionic in nature.
2) These dyes are suitable for wool, silk, polyamide and modified
acrylics.
3) These are applied from a strongly acidic to neutral pH bath.
4) These dyes have no affinity for cotton cellulose’s , hence not
suitable for cellulosics.
5) These dyes combine with the fiber by hydrogen bonds , vander
waals forces or through ionic linkages.

 Uses
 Fibers
In the laboratory, home, or art studio, the acid used in the dye-bath is
often vinegar (acetic acid) or citric acid. The uptake rate of the dye is
controlled with the use of sodium chloride. In textiles, acid dyes are
effective on protein fibers, i.e. animal hair fibers like wool, alpaca,
and mohair. They are also effective on silk. They are effective in
dyeing the synthetic fiber nylon, but of minimum interest in dyeing
any other synthetic fibers.
 Medicine
 In staining during microscopic examination for diagnosis or
research, acid dyes are used to color basic tissue proteins. In
contrast, basic dyes are used to stain cell nuclei and some other acidic
components of tissues.[8] Regarding cellular structures, acid dyes will
stain acidophillic structures that have a net positive charge due to the
fact that they have a negatively charged chromophore. Acidophillic
structures include the cytoplasm, collagen and mitochondria. The
two have an affinity for each other due to the conflicting charges.
Examples of acid dyes used in medicine include:

Lee's stain used in gallbladder cells. PTAH stain used in Human squamous
epithelial cells.

 Lee's stain (stains reddish-pink).

 Phosphotungstic Acid Hematoxylin (PTAH) stain (stains blue).
 Eosin stain (stains pinkish-orange).

 Food Industry
Acid dyes can also be used as food colouring, helping to increase the
attractiveness of certain foods, and thus becoming more appealing to
customers. Some examples include erythrosine, tartrazine, sunset
yellow and allura red, to name a few, many of which are azo dyes.
These dyes can be used in frosting, cookies, bread, condiments or
drinks. In order to prevent health hazards, a dye must be approved
for consumption before it can be marked as edible. Some separation
methods that can be used to identify unapproved dyes include
 the solid phase extraction process, the overpressured thin layer
chromatography process, and the use of reversed-phase plates.

2) Basic Dyes : Basic dyes, these dyes are also known as cationic dyes.
This a class of synthetic dyes, that act as bases and when made soluble in
water, they form a colored cationic salt, which can react with the anionic
sites on the surface of the substrate. The basic dyes produce bright
shades with high tinctorial values, on textile materials.

 Properties
Basic Dyes are cationic soluble salts of coloured bases. Basic dyes are
applied to substrate with anionic character where electrostatic
attractions are formed. Basic dyes are not used on cotton as the
structures are neither planar nor large enough for sufficient
substantivity or affinity. Basic dyes are called cationic dyes because the
chromophore in basic dye molecules contains a positive charge. The
basic dyes react on the basic side of the isoelectric points. Basic dyes are
salts, usually chlorides, in which the dyestuff is the basic or positive
radical. Basic dyes are powerful colouring agents.It’s applied to wool,
silk, cotton and modified acrylic fibres. Usually acetic acid is added to
the dyebath to help the take up of the dye onto the fibre. Basic dyes are
also used in the coloration of paper.

Ionic nature:- The ionic nature of these dyes is cationic.

Shade range:- These dyes exhibit an unlimited shade range with high

tinctorial strength, brightness and many colors are having fluorescent
properties.

Solubility:- The solubility of these dyes is very good in water ,in the

presence of glacial acetic acid.

Leveling properties:- These dyes have a very high strike rate , therefore

leveling is poor.

Exhaustion :- cationic dyes exhaust at a variable rates, K values are used

to define the exhaustion characteristics of the cationic dyes. K=1 means
the fastest exhaustion , while K=5 means the slowest exhaustion. So
while making the combination shades the dyes of similar K values must
be used.

Affinity:- These dyes shows a very affinity towards wool , silk and

cationic dye able acrylic, but have no affinity towards cellulosics. To dye
cellulosics with basic dyes the material must be treated with suitable
mordanting agents.
 (a) Congo Red (b) Benzopurpurine 4B (BP4B)

 Advantages of Basic Dyes

 High Tinctorial strength
 Moderate substantivity
 Relatively economical
 Wide shade range
 Includes some of the most brilliant synthetic dyes
 Shows good brightness

 Limitations of Basic Dyes

 Poor shade stability
 High acid content
 Coloured backwaters
 Very poor lightfastness
 Preferential dyeing

 Modified Basic Dyes

These dyes, generally based on the chemistry of basic dyes, have
longer molecular structures than traditional basic dyes, and thus
have significantly improved properties. Though still cationic in
nature, modified basic dyes exhibit improved fibre coverage and
substantivity on many furnishes,making them ideal for dyeing
applications. Lightfastness is also improved considerably over
traditional basic dye.
Key advantages over conventional basic dyes:-
 Excellent substantivity
 Better Lightfastness
 Covers all fibres
 Clear backwaters

3) Direct Dyes : Direct Dye is a class of dyestuffs that are applied directly
to the substrate in a neutral or alkaline bath. They produce full shades
on cotton and linen without mordanting and can also be applied to
rayon, silk, and wool. Direct dyes give bright shades but exhibit
poor washfastness. Various aftertreatments are used to improve the
washfastness of direct dyes, and such dyes are referred to as
“aftertreated direct colors”. Direct Dyes are molecules that adhere to the
fabric molecules without help from other chemicals. Direct dyes are
defined as anionic dyes with substantivity for cellulosic fibres, normally
applied from an aqueous dyebath containing an electrolyte, either
sodium chloride (NaCl) or sodium sulfate (Na2SO4). The dyeing process
with direct dyes is very simple, Direct dyeing is normally carried out in a
neutral or slight alkaline dyebath, at or near boiling point , but a
separate aftertreatment such as cationic dye fixing , to enhance wet
fastness has been necessary for most direct dyeing .

Direct dyes are used on cotton, paper,leather, wool, silk and nylon. They
are also used as pH indicators and as biological stains.

 Properties
Chemically they are salts of complex sulfonic acids. 
Structure:- More than 75% of all direct dyes are unmetallised azo
structures, great majority of them are disazo or polyazo types.
Ionic Nature:- Their ionic nature is anionic. 
Solubility:- They are soluble in water .

Affinity:- They have an affinity for a wide variety of fibers such as

cotton ,viscose, silk jute ,linen etc.. They do not make any permanent
chemical bond with the cellulosic fibers but are attached to it via very
 week hydrogen bonding as well as vander waals forces. Their flat shape
and their length enable them to lie along-side cellulose fibers and
maximize the Van-der-Waals, dipole and hydrogen bonds.

 Types of Direct Dyes

The SDC classification of direct dyes is follows
I. Class A – dyes that are self-levelling, i.e. dyes of good migration or
leveling properties.
II. Class B – 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.
III. Class C – 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.
  Application Of Direct Dye
Direct dyes are usually applied with the addition of electrolyte at or
near the boil in the machines capable of running at atmospheric
pressure .But in HTHP dyeing machines it is carried out at
temperatures above the boil in case of pure as well as blended yarns. 
An addition of alkali, usually sodium carbonate, may be made with
acid-sensitive direct dyes and with hard water as well as to enhance the
dye solubilisation. When cellulose is immersed in a solution of a direct
dye it absorbs dye from the solution until equilibrium is attained, and
at this stage most of the dye is taken up by the fibre. The rate of
absorption and equilibrium exhaustion vary from dye to dye. The
substantivity of the dye for cellulose is the proportion of the dye
absorbed by the fibre compared with that remaining in the dyebath.

4) Disperse Dyes : A class of slightly water-soluble dyes originally

introduced for dyeing acetate and usually applied from fine aqueous
suspensions. Disperse dyes are widely used for dyeing most of the
manufactured fibers.
Dyes are colored, unsaturated organic chemical compounds capable of
giving colour to a substrate (a textile), i.e. colouring or dyeing it.
The term “disperse dye” have been applied to the organic colouring
substances which are free from ionizing groups, are of low water
solubility and are suitable for dyeing hydrophobic fibres. The dye has
derived its name for its insoluble aqueous properties and the need to
apply it from an aqueous dispersion. Of all the dyes, they are of the
smallest molecular size. Disperse dyes have substantivity for one or
more hydrophobic fibres e.g. cellulose acetate, nylon, polyester, acrylic
and other synthetic fibers. The negative charge on the surface of
hydrophobic fibres like polyester can not be reduced by any means, so
non-ionic dyes like disperse dyes are used which are not influenced by
that surface charge.
 Properties
i. Disperse dyes are nonionic dyes. So they are free from ionizing
group.
ii. They are ready made dyes and are insoluble in water or have very
low water solubility.
iii. They are organic colouring substances which are suitable for dyeing
hydrophobic fibres.
iv. Disperse dyes are used for dyeing man made cellulose ester and
synthetic fibres specially acetate and polyester fibres and sometimes
nylon and acrylic fibres.
v. Carrier or dispersing agents are required for dyeing with disperse
dyes.
vi. Disperse dyes have fair to good light fastness with rating about 4-5.
vii. The wash fastness of these dyes is moderate to good with rating
about 3-4.
viii. Of all dyestuffs disperse dyes are of smallest molecular size.
ix. Generally disperse dyes are derivatives of azo, anthroquinone, nitro
and quinine groups.
x. They do not undergo any chemical change during dyeing.
xi. In presence of nitrous oxide, textile materials dyed with certain blue
and violet disperse dyes with an anthraquinone structure will fade.
This is called gas fading of disperse dyes which is a defect of this
dye. 
5) Mordant dyes : A dyestuff that requires the use of a mordant. There
are very few synthetic dyestuffs currently in use that require a separate
mordant, except for some dyes for wool, where mordant dyes are still
quite popular. Since chromium is almost exclusively used as the
mordant on wool, chrome dye has become essentially synonymous with
mordant dye. Many natural dyes (plant extracts, etc.) require a mordant.
The mordant used can significantly influence the hue produced with a
particular dyestuff. These are special acid dyes in which certain metal
atom can be introduced during dyeing. These are water soluble dyes and
affinity for silk, wool and polyamides. Mordant dyes requires a mordant
in their application and these dyes upon cobination with the mordant
deposit on the fiber in the form of insoluble color. Most commonly dyes
have hydroxyl or carboxyl groups and are negatively charged (anionic) in
nature.
 Properties
1. These dyes are economical dyes and are generally used to produce
dark shades such as dark greens , dark blues and blacks.
2. These dyes have good leveling and color fastness properties.
3. The interaction between fiber and dye is established through very
 strong ionic bonds , which are formed between the anionic groups of
the colorant and ammonium cations on the fiber. Chromium or the
metal ion acts as bridge between the dye and fiber , which gives rise to
a very strong linkage , resulting into excellent fastness properties.

However there are disadvantages of the chrome dyes also such as

longer dyeing cycles, difficulties in shading , risk of chemical damage
to the fiber and the potential release of chromium in the waste water.
 Applications
 Chrome-Mordant Process
In chrome mordant process, the fiber is first treated with potassium
dichromate in the neutral bath or in the presence of either sulfuric or
formic or oxalic acid. When sufficient amount of chromium is taken
up by fiber , it is taken out , squeezed and entered in the dye bath
containing acid mordant dye. The dye form an insoluble complex with
chrome present on the fiber .
 After Chrome Method
In this method the substrate is first treated with the dye , the dye is
exhausted by the addition of an acid , and after complete exhaustion
the material is taken out squeezed and then run in a solution
containing potassium dichromate and an acid. Metal dye complex is
formed on the fiber , which is insoluble.
 Meta Chrome Process
This is a single bath process , in which the material is treated with in a
bath containing acid mordant dye , potassium dichromate and
ammonium sulphate.
The dye along with potassium dichromate and ammonium sulphate
got absorbed by the fiber and evenly distributed but no complex is
formed because the pH is not suitable for the chemical reaction to
take place.
In the second step of the meta chrome process, when the dye bath is
heated , ammonium sulphate is converts into ammonia and sulphuric
 acid , which makes the bath strongly acidic and potassium dichromate
in the presence of strong acid now react with the dye molecule
forming an insoluble complex on the fiber.
A dyeing cycle for dyeing of wool with chrome dyes is shown below:-

Here, 
A=Gluber salt+Acetic acid+Leveling agent
B= Dye
C= Potassium Dichromate
D=Acid

6) Vat Dyes : Vat dyes are insoluble and cannot be used directly on textile
materials and requires vatting. Vat dye mainly used for cellulose fiber
dyeing but in protein fiber dyeing pH should be controlled. Dyeing
process is difficult from other dye. Among all the dyes, vat dye has the
best fastness properties though rubbing fastness is not good.
VI. Dyeing Techniques
1. Direct Dyeing: Direct, or substantive, dyes are applied to the fabric
from a hot aqueous solution of the dye. Under these conditions, the dye
is more soluble and the wettability of natural fibres is increased,
improving the transport of dye molecules into the fabric. In many cases,
the fabric is pretreated with metallic salts or mordants to improve the
fastness and to vary the colour produced by a given dye (see
above Natural dyes: Mordants).

2. Disperse Dyeing : Penetration of the fabric by the dye is more

difficult with the hydrophobic synthetic fibres of acetate rayon, PET, and
acrylics, so an alternate dyeing technique is needed. These synthetic
fabrics are dyed by immersion in an aqueous dispersion of insoluble
dyes, whereby the dye transfers into the fibre and forms a solid solution.
These disperse dyes were originally developed for acetate rayon but
became the fastest growing dye class in the 1970s because of the rapid
increase in world production of PET, which can be dyed only with small
disperse dyes. Transfer into the fibre from a boiling dye bath is aided by
carriers (e.g., benzyl alcohol or biphenyl). The transfer mechanism is
unclear, but it appears that the fibres loosen slightly to permit dye entry
and, on cooling, revert to the original tightly packed structure. Dyeing at
higher temperatures (120–130 °C [248–266 °F]) under pressure avoids
the need for carriers. With the Thermosol process, a pad-dry heat
technique developed by the DuPont Company, temperatures of 180–220
°C (356–428 °F) are employed with contact times on the order of a
minute.

3. Vat Dyeing : Conversion of a soluble species to an insoluble dye after

transfer to the fibre is the basis of vat dyeing, one of the ancient
methods. Indigo is insoluble but is readily reduced to a soluble,
colourless form, leucoindigo. After treatment in a leucoindigo bath, the
fabric becomes coloured upon exposure to air; atmospheric oxygen
regenerates indigo by oxidation. In contrast to leucoindigo, indigo has
no affinity for cotton. Water-insoluble aggregates of indigo molecules
larger than the fibre pores are firmly trapped within the fabric. This
process was traditionally done outdoors in large vessels or vats and,
hence, was named vat dyeing, and the term is still used for this
procedure.
4. Azo Dyeing Techiniques : The discovery of the azo dyes led to the
development of other dyeing techniques. Azo dyes are formed from
an azoic diazo component and a coupling component. The
first compound, an aniline, gives a diazonium salt upon treatment
with nitrous acid; this salt reacts with the coupling component to form a
dye, many of which are used as direct and disperse colorants. These dyes
can be generated directly on the fabric. The process in which the fabric is
first treated with a solution of the coupling component and then placed
in a solution of the diazonium salt to form the dye on the fabric was
patented in 1880. Alternatively, the fabric can be treated with a solution
of the diazo component before diazotization, followed by immersion in a
solution of the coupling component; this process was patented in 1887.
These are ingrain dyeing methods. Because many azo dyes are
substituted anilines, they can be transformed to ingrain dyes for
improved fastness after application as direct or, in some cases, disperse
dyes to cotton and acetate rayon, respectively.

5. Reactive Dyes : Reactive dyeing directly links the colorant to the fibre
by formation of a covalent bond. For years, the idea of achieving high wet
fastness for dyed cotton by this method was recognized, but early
attempts employed conditions so drastic that partial degradation of the
fibres occurred. Studies at a Swiss dyeing company called Ciba in the
1920s gave promising results with wool using colorants having
monochlorotriazine groups. (Triazines are heterocyclic rings containing
three carbons and three nitrogens within the ring.) However, there was
little incentive for further development because the available dyes were
satisfactory. These new dyes, however, were sold as direct dyes for many
years without recognition of their potential utility as dyes for cotton.

In 1953 British chemists Ian Rattee and William Stephen at ICI in

London found that dyes with dichlorotriazinyl groups dyed cotton under
mild alkaline conditions with no fibre degradation. Thus, a major
breakthrough for the dye industry was made in 1956 when ICI
introduced their Procion MX dyes—reactive dyes anchored to the fibre by
covalent bonds—100 years after the discovery of the first commercial
synthetic dye by Perkin. The generation and subsequent bonding of these
three new dyes (a yellow, a red, and a blue) with fibres has a common
basis, namely, the reactivity of chlorine on a triazine ring. It is readily
displaced by the oxygen and nitrogen of ―OH and ―NH 2 groups.
Reaction of a dye bearing an amino group with cyanuryl chloride links
the two through nitrogen to form the reactive dye. A second chlorine is
displaced (in the dyeing step) by reaction with a hydroxyl group of cotton
or an amino group in wool. A key feature of cyanuryl chloride is the
relative reactivity of the chlorines: only one chlorine reacts at 0–5 °C
(32–41 °F), the second reacts at 35–50 °C (95–122 °F), and the third
reacts at 80–85 °C (176–185 °F). These differences were exploited in the
development of series of related reactive dyes.

The introduction of the Procion MX dyes triggered vigorous activity at

other companies. At the German company Hoechst Aktiengesellschaft, a
different approach had been under study, and in 1958 they introduced
their Remazol dyes. These dyes are the sulfate esters of
hydroxyethylsulfonyl dyes, which, on treatment with mild base, generate
the vinylsulfone group. This group, in turn, reacts with cellulose to form
a unique dye-fibre bond.

In the Procion T series, marketed by ICI in 1979, particularly for dyeing

cotton in polyester and cotton blends by the Thermosol process (see
above Disperse dyeing), the reactive dye is bonded through a
phosphonate ester. The introduction of reactive dyeing not only provided
a technique to overcome inadequacies of the traditional methods for
dyeing cotton but also vastly increased the array of colours and dye types
that could be used for cotton, since almost any chromogen can be
converted to a reactive dye.