Dye Classes

Dyestuffs
Coloured objects acquire their true colours because they absorb a definite portion
(complementary colour) of white light (visible portion of sunlight) and unaffecting the rest.
Some chemical groups such as azo (-N=N-), Keto (>C=O) etc. which are responsible for the
absorption of a portion of light are called chromophores and a compound containing a
chromophore is called a chromogen. When a chromogen contains other groups called
auxochromes like amino (-NH2) group the coloured compound acquires an additional
property of getting bound to textile fibres. In other words, coloured compounds containing
auxochromes become dyes.

A simple method of applying dyes to cotton fibres involves the dissolution of the dye in
water, entering the fibre material in the dye solution and slowly heating the system when the
dye dissolved in water is gradually transferred to the fibre because of the higher affinity of
the dye for the fibre than for the water. Since in this case dyeing is done directly on cotton,
dyes belonging to this class are called direct cotton dyes or direct dyes. The solubility of the
dye in water, so very useful in dyeing it on cotton, has a disadvantage after dyeing. When
the dyed cotton cloth is entered into hot water, some of the dye present on cotton comes out
and dissolves in the water, i.e., a part of the dye gets stripped or bleeds into the water. This
stripping action is accelerated if soap is present in the hot or boiling water, when we say that
the dye has poor washing fastness. Thus during washing of differently coloured as well as
white clothes in one bucket using hot soap solution the dyes form coloured garments bleed
into the soap solution and stain other garments. Therefore, such clothes which were dyed
with direct dyes should not be washed together with other clothes.

If water-insoluble dyes are applied on cotton, the dye will not bleed into the washing
solution and clothes dyes with different dyes from such class of dyes can be washed
together. However, before dyeing these insoluble dyes they have to be temporarily converted
into a water-soluble form and after dyeing, should be converted into their original insoluble
form. Indigo was dyed by this method in ancient India (and hence its name) in wooden vats
(tubs). Synthetic dyes, which are dyed like Indigo, are called vat dyes. Another class of dyes
called sulphur dyes (since they contain sulphur) are, like vat dyes, insoluble in water and
have to be temporarily converted into water-insoluble (leuco) forms before dyeing and
reconverted into water-insoluble forms after dyeing. The washing fastness of both these
classes of dyes is excellent.

Another method of applying water-insoluble dyes (and hence producing wash-fast dyeings)
is to form a coloured pigment in the fibre material itself. In this case Naphthols and bases
are used to form the pigment. Naphthols are insoluble in water and have to be dissolved in
caustic soda solution, by heating if necessary. When cotton is entered into this solution, it
absorbs and retains the soluble form of the naphthol. The second component (base) is then
diazotized and the naphtholated cotton is dipped into the diazotized base solution at
appropriate pH when a coloured pigment is formed in the fibre substance. This is called and
ingrain dye or an azoic pigment.
There are other water-soluble dyes, which are dyed on wool and silk in the presence of acids
like sulphuric, hydrochloric, acetic and formic acids, and hence these are called acid dyes. In
contrast to acid dyes, there are basic dyes which also dye wool and silk directly. They have
no affinity for cotton, but can be dyed on cotton with the help of a mordant (which has
affinity for both the fibre and the dye). Thus cotton is first treated with a solution of the
mordant and then with a solution of the basic dye.

When acetate rayon was introduced at the end of World War I, this fibre could not be dyed
with the then existing dyes and for this purpose, special dyes, which are generally not
soluble in water, were developed. These are dispersed in water with the help of a dispersing
agent and during dyeing the acetate fibre takes up the dye. These dyes are called acetate
dyes or disperse acetate dyes. When polyamide and polyester fibres were later developed
these dyes were found to dye the new fibres. Further research was needed to develop better
dyes for colouring these fibres, especially the polyester fibres. These are now known as
disperse dyes.

There are other classes of dyes which like ingrain dyes, are formed in the fibre by the dyer
or the printer. These are also not marketed in the final form, but as intermediate compounds
(dye-formers). Thus aniline can be applied in its soluble salt form on cotton fabric and
progressively oxidized to a wash-fast black pigment called Aniline Black. Since the final
black shade is produced by oxidation, these dyes are called oxidation colours. Some metal
oxides are coloured and it is possible to deposit them in the fibre to produce wash-fast
dyeings. This can be done by applying a water soluble salt of the metal, followed by treating
with sodium hydroxide solution and exposing it to the air, when an oxide of the metal is
formed in the fibre. Iron buff, manganese brown, chrome yellow, chrome orange, etc. are
produced in this manner. These are called mineral colours. A mixture of chromium oxide and
ferric oxide produced in cotton fabrics in proper portions is known as mineral khaki and is
dyed extensively on cloth intended for producing military uniforms.

The dyeing of textile fibres with the above-mentioned dyes involves one or more of the
following principles:
1. physical adsorption of water-soluble dyes by the fibre from a solution of the dye in
water and attachment of the dye in the fibre substance by certain physical forces like
hydrogen bonding, electrostatic attraction etc.
2. mechanical trapping of the insoluble dye in the fibre and
3. dissolution of the dye in the fibre

It was in 1956 that a fourth principle of dyeing was introduced, when a water-soluble dye
could actually combine chemically with the fibre (cotton) in the presence of soda ash and
become a part of the fibre itself, thereby ensuring excellent washing fatness. These dyes are
called reactive dyes, since they chemically react with the fibre substance forming a covalent
bond between the dye and the fibre.

Some vat dyes, azoic pigments and other pigments (phthalocyanine pigments) containing
copper, cobalt, nickel etc in them are manufactured and supplied in an insoluble form to the
printer, who uses them as such (without solubilising them). Such coloured substances are
called pigments and are extensively used in pigment printing. The difference between a dye
and a pigment is not a clear-cut one. Thus a vat dye is a dye when applied on cotton after
converting into its soluble form, to be reconverted into the original insoluble form, once it
enters the fibre structure; but the same coloured compound is a pigment when used in
printing, without converting into the water soluble form.

Thus it may be said that dyes are supplied by dyestuff manufacturers either as ready-made
dyes, which may be applied as such if they are water soluble or after temporarily
solubilising them, to be insolubilised subsequently, or as one or more intermediate
compounds from which the dyer or printer has to form the dye/pigment during dyeing or
printing. The dyes may be classified as follows:

Vat dyes
These are the most important dyes (and most expensive also) for dyeing and printing on
cotton and other cellulosic fibres. As a class, their fastness properties to washing, light,
perspiration, chlorine, rubbing etc. are excellent; in fact they have excellent all round
fastness.

Vat dyes are insoluble in water and have to be dissolved in water by using sodium hydroxide
and sodium hydrosulphite, usually at 50o C for 15 – 20 minutes. This process is known as
vatting.

o ONa

( Vat dye Na2S2 O4 (Sodium salt of

in solution ) NaOH leuco vat dye )
soluble
o ONa

In their soluble forms they behave like direct dyes and hence can be dyed on cotton. They
remain in the soluble form only in the presence of excess of sodium hydrosulphite and
sodium hydroxide and therefore during the entire dyeing period both these chemical should
be present in the dyebath in sufficient quantities to keep the dye in the soluble form. The
soluble form as well as sodium hydrosulphite react with oxygen of the air and if all the
hydrosulphite reacts with oxygen, the soluble dye reacts with oxygen and starts getting
converted into its original insoluble form. When this happens no further dyeing is possible.
After dyeing from a bath containing sodium hydroxide and hydrosulphite and after the dye
bath is nearly completely exhausted, the dyed material is removed, squeezed and exposed to
air when the leuco vat dye (soluble form) is converted back into the insoluble form. In some
cases where this reconversion by oxygen of the air takes long time, other oxidizing agents
like sodium perborate, hydrogen peroxide, potassium dichromate etc. may be used to hasten
the reconversion (oxidation). At the end of this treatment, the dyed material is washed,
soaped at the boil with a solution of a detergent and soda ash for 10 to 15 mins, washed and
dried.

Unlike direct dyes, which are dyed at the boil, vat dyes are dyed at lower temperatures.
Depending on the temperature of dyeing, they are divided into four classes: cold dyeing dyes
(Ik class, which are dyed at 200 C – 300C; warm dyeing dyes (Iw class), which are dyed at the
300 C to 400C) ; and special dyeing dyes (IN special class ), which are dyed according to
individual process . The dyeing time is usually 45 to 60 min.

In the case of cold dyeing and warm dyeing dyes (I k and Iw ) the exhaustion of the dye bath is
usually low and hence they need exhausting agents like common salt or Glauber’s salt to be
added to the dyebath after the dyeing has proceeded at the appropriate temperature for some
time. On the other hand, the rate of dyeing of normal dyeing (IN) dyes is so fast even at 500C
that they not only do not need any exhausting agents, but also their dyeing has to be retarded
(slowed down) by the addition of certain retarding agents (also called leveling agents) such
as Dispersol VL ,Tinegal CV , Albatex PO, Remol OK, Evasol N , Levogal CVN etc.

Solubilised vat dyes

Before the application of vat dyes they have to be solubilized (vatted) by the dyer (treating
with a hot solution of sodium hydrosulphite in the presence of sodium hydroxide). There is
another method of solubilizing the vat dyes, but this is done by the dyestuff manufacturer
and supplied to the dyer or printer in a powder form, which is soluble in water. These are
called solubilized vat dyes and are chemically sodium salts of sulphuric esters of leuco vat
dyes.

o OH OSO3H OSO3Na
Sodium
salt of
sulphuric
ester of leuco
vat dye
o OH OSO3H OSO3Na
Leuco vat Sulphuric ester
dye of leuco vat dye

When they are dissolved in water they do not generally produce the same colour as their
parent vat dyes. Like direct dyes they ionise in water.

_
OSO3Na OSO 3

(H 2O) +
+ 2 Na

_
OSO3Na OSO 3

They have affinity for cotton and other cellulosic fibres and they can be exhausted by the
addition of common salt to the dyebath. They are usually applied to cotton materials at
room temperature. After applying them onto cotton, the regeneration into the original vat
dye is done in a second bath containing sodium nitrite and Sulphuric acid at 500C to 600 C.

OSO3Na o
(O)
(H+)

OSO3Na o
Solublised vat dye Vat dye
The solution of sodium nitrite and Sulphuric acid provides acidic, oxidizing conditions,
which are needed for the regeneration of the original vat dye.

The power form of the solubilized vat dye is stable to storage, if properly stored away from
sunlight and air (moisture, oxygen and carbon dioxide). Their solutions are also stable if
properly stored. If they come into contact with acidic fumes and oxygen, the parent vat dyes
from which they were made are formed, which then do not go into solution during their
application and hence a part of the dye is wasted.

Reactive dyes

These dyes are soluble in water. Their application to cotton materials involves two distinct
steps – (1) dyeing with the dye in the presence of common salt to effect as much exhaustion
as possible and (2) chemically reacting the dye with the fibre (fixation) in the presence of an
alkali, like soda ash, caustic soda, sodium silicate, etc. In the first stage of dyeing, it
resembles direct dyes in that its exhaustion (to a lower extent) can be brought about by
adding common salt or Glauber’s salt. However, the dye also reacts with water (only after
the addition of alkali) and when this takes place, the dye gets deactivated (hydrolysed) and
then it cannot react with the cotton fibre. In the dyeing and fixing of reactive dyes, 5 to 30
% of the dye used for dyeing is deactivated and hence this is a waste. The activated dye has
some affinity for cotton and hence is absorbed and retained by cotton. Because of the lower
affinity of the deactivated dye (compared to direct dyes on cotton) , the washing fastness of
this form of the dye present on cotton is very poor and hence it gets washed out
progressively during the washing of the garments made from such fabrics. Therefore as a
part of the dyeing process, the fabrics are boiled with a soap solution after the fixation step,
when most of the deactivated dye is removed from the dyed fabric. The other form of the
dye present in the fibre in a chemically reacted form is not removed during the soaping step,
since it is firmly bound to the fibre by a covalent bond.

Dyes based on the dicholoro – triazine are very reactive and they can react with the fabric
even in the cold (300C) and hence they are called cold dyeing reactive dyes. Monochloro –
triazine dyes are less reactive and need higher temperature for bringing about the reaction
with the fibre. Vinyl sulphone , trichloro – pyrimidine , dichloro – quinoxalinyl etc. are
some of the other reactive systems present in reactive dyes.

All these dyes need alkali for fixing on textile fibres. Reactive dyes are developed for wool
and silk, nylon and also exclusively for printing, which are characterized by high fixation
rate and lack of substantivity for the fibre. Some of them are based on multiple reactive
systems:

Cl

N N
N
NaO3S D NH NH Cl
N
N N

NHR
In this case two triazine rings are linked through a bridging group. Both the rings have
reactive chlorine atoms and one of them, a dyestuff portion also. This dye has a non-
coplanar structure as a result of this; the dye does not have any affinity for cellulosic fibres.
Even if one chlorine atom reacts with water (and gets deactivated), the other chlorine atom
can react with cellulose. Thus there is a greater probability of the dye reacting with the fibre
than a triazinyl reactive dye containing only one triazine ring and one or two chlorine atoms.
In other system of reactive dyes introduced for printing purpose, the chlorine atom of the
dicholoro – triazine ring is replaced by methoxy group :

Cl Cl

N N N N
NaO3S D NH Cl NaO3S D NH OCH3
N N
(Di-chloro dye) (Reactive dye for printing)

Azoic Colours
These are not ready–made dyes but the dyer or the printer has to form them in the fibre.
These are supplied as naphthols and bases. The naphthols are marketed under the different
trade names like Naphthol , Brenthol , Irganaphthol , etc. The second Component is
marketed as fast Colour Base , such as Brentamine Fast Colour Bases , etc.

A naphthol may produce different colours with different bases. Some of the colours
produced with some combination of naphthols and some bases are shown in Table 4.

The application of azoic colours involves two steps –naphtholation (dyeing with naphthol)
and development (coupling of diazotised base with naphthol).

Naphthols are insoluble in water but are solubilized in the presence of sodium hydroxide
when the sodium naphtholate is formed , usually at high temperatures :

OH
NaOH ONa
CO NH
CO NH
( Naphthol AS )
( Naphtholate )

These soluble forms have affinity for cotton fibres. Like direct dyes they can be exhausted
by the addition of common salt or Glauber’s salt. However, their affinity is generally low.
Naphtholation is done at room temperature in few minutes. In the meantime the base is
diazotised (treated with concentrated hydrochloric acid and sodium nitrate at low
temperature, i.e. 00 to 50C for 15 to 20 min) and the naphtholated material is entered into the
diazotised base solution.
 NH2 N2Cl
(HCl)
(NaNO2)
Cl CH3 Cl CH3

(Fast Red TR Base) (Diozotised Base)

ONa N Cl

+
2

CONH Cl CH 3

CH

N=N Cl

( Azoic pigment )
OC ONa

NH

When the naphtholated cotton is removed from the naphtholated bath and squeezed, some
solution also accompanies the cotton and when this is entered into the solution of the
diazotised base, the naphthol taken up by the cotton reacts with the diazotised base and
forms the colour pigment, which is firmly held in the fibre. However, the naphthol dissolved
in the solution accompanying the cotton also forms the coloured pigment, which is not
firmly fixed in the cotton, but is loosely deposited on the fibre surface. Since this is not
fixed, it rubs out later from the dyed material. Therefore after dyeing, the material is treated
with a boiling soap solution, when most of the loosely held pigment is removed from the
fibre surface and held in suspension in the soap solution. It is not possible to remove all the
loosely held pigments from the fibre surface. Therefore the rubbing fastness of azoic
dyeings is not very good.

The diazotised base solution is not stable. If it is kept even at room temperature (30 0C) for
some time it gets decomposed and then it does not react with naphthol. Secondly during
diazotization, suffocating fumes (nitrogen dioxide) are liberated (from hydrochloric acid and
sodium nitrite). In order to avoid this step (in the textile mils) the dyestuff manufacturers
diazotise the bases, stabilise them and supply them in a powder form as Fast Colour Salts.
These have to be simply dissolved in water at room temperature before use (this solution
should never be heated, otherwise they get decomposed) and they do not require the addition
of hydrochloric acid and sodium nitrite.

When a solution of sodium naphtholate is added to a solution of a diazotised base or a Fast

Colour Salt, the coloured pigment is formed immediately, which gets precipitated.
However, when the diazotised base is converted by the action of caustic soda into anti –
diazotate or by reaction with a water – soluble amino compound into a diazoamino
compound, the resulting compound loses the coupling power and hence can be mixed with
sodium naphtholate without the danger of the premature formation of the pigment. Such
mixtures (in the powder form) of naphtholates and deactivated diazonium salts are marketed
as Rapid Fast (antidiazotates) and rapidogen (diazoamino compounds) colours. When these
come into contact with an acid , the active diazo salt is reformed , which then reacts with
the naphtholate present to form the azoic pigment. Rapidogen colours need stronger acids
for activation , while Rapid Fast Colours need very mild acidity (even the atmospheric
carbon dioxide , i.e. carbonic acid) to activate them. These are especially useful in textile
printing.

Direct dyes

These are water soluble dyes, having affinity for cellulosic fibres. These are sodium salts of
aromatic sulphonic acids and when dissolved in water, ionise into dye anion and sodium
cation.

(H2O)
R – SO3Na RSO3 - + Na+

Some of the dyes need a little amount of soda ash to completely dissolve them in water. The
free sulphonic acid form of the dye is less soluble than the corresponding sodium salt and to
convert any residual free sulphonic acid form that may be present in the commercial sample,
into the sodium salt, sodium carbonate should be added:

2R – SO3H + Na2CO3 2R – SO3Na + H2O + CO2

During dyeing, the dyestuff molecules are taken up by the fibre from
the dyebath and retained in it. When the dyeing is carried out in hot solution, the rate of
dyeing increases. If common salt or Glauber’s salt (Sodium Sulphate) is added to the
dyebath during dyeing, more dye is taken up by the fibre i.e. the dyebath is exhausted to a
great extent than , in the absence of the salt. Hence these salts are exhausting agents for
direct dyes while dyeing on cotton.

As a class, direct dyes have poor washing fastness and poor light fastness. However, these
fastness properties can be improved by certain after – treatments. Thus when cotton yarn or
cloth dyed with a direct dye is treated with a solution of potassium dichromate and acetic
acid for 15 to 20 min. the washing fastness of the dyeing is improved. Similarly an after –
treatment with copper sulphate and acetic acid improves light fastness. Cationic dye-fixing
agents dissolve in water to ionise into cations and anions :

R’4NX R’4N+ + X –

When a cotton material dyed with a direct dye is treated with the above solution , the dye
anion present on the fibre combines with the cation of the dye – fixing agent and forms an
insoluble or less soluble complex, thereby improving the washing fastness of the after –
treated dyeing.
R – SO3Na RSO3 - + Na+

R’4NX R’4N+ + X –

RSO3 - + R’ 4 N+ RSO3 . R’4N

Dyeing takes place slowly at low temperatures and in the absence of salts (electrolytes). If
the dyeing is started at elevated temperatures (950 to 1000C) in the presence of salt, the dye
rushes on to the fibre material and uneven (non – uniform) dyeing results. In order to avoid
this, the dyeing is started in the absence of salt and at room temperature. The dyebath is
slowly heated and then the salt is added. The temperature of the dyebath is raised still
further to 100 0C and the dyeing continued at the boil till the exhaustion of the dyebath is as
complete as possible. At the end of the dyeing, the material is rinsed in cold water. If it is
soaped at the boil, much of the dye bleeds out into the soap bath and therefore this after
treatment is not given to direct dyeing.

Acid Dyes

These dyes are easily applied on wool, silk and nylon fibres. They are generally dyed in the
presence of acids like Sulphuric, acetic or formic acid. They produce a wide range of
brilliant shades, but the fastness properties of individual dyes vary considerably.

Acid dyes, like direct dyes, are also soluble in water and produce coloured anions and
sodium cations:
H2O
R – SO3Na RSO3 - + Na+

However, these do not dye cotton and other cellulosic fibres (they have no affinity for these
fibres).

In the case of dyeing with these dyes on protein fibres in the presence of an acid, the amino
group of the fibre acquires a positive charge by protonation :

HOOC – W NH2 + HCL HOOC – W – NH3+Cl-

(Wool)
Thus the acid produces cationic sites in the fibre. These sites attract and retain the dye anion
HOOC – W – NH3+ . Cl- + R – SO3 – Na+

HOOC – W – NH3O3S – R + NaCl

The higher the concentration of the acid in the dyebath, more cationic sites are produced in
the fibre and more dye is taken up, i.e. acids act as exhausting agents while dyeing acid dye
on wool. It is seen from the reversible reaction that sodium chloride is formed as a result of
the dyeing reaction (forward reaction). Thus if the salt concentration is increased in the dye
bath, the rate of the backward reaction (stripping) is increased. In fact, salt acts as a
retarding agent in the dyeing of acid dyes on wool. In order to get uniform dyeing results,
the dyeing is started in the presence of salt and a small amount of an acid in the cold,
followed by raising the temperature gradually. In order to exhaust the dyebath, more of acid
is added to the dyebath and the dyeing continued.

Acid mordant dyes

These water – soluble dyes are also for dyeing wool and silk and are special acid dyes in
which a certain metal atom (chromium atom) can be introduced during dyeing. When a
solution of an acid mordant dye in water is mixed with a solution of potassium dichromate
in the presence or absence of Sulphuric acid, chromium from dichromate forms a complex
with the dye. This complex is insoluble in water and hence is precipitated. This precipitate
is used in dyeing mordant dyes on wool. There are different methods of producing this
complex (dye-chromium complex) in wool. For example, in one method, called chrome
mordant method, wool is first treated with a solution of potassium dichromate in the
presence or absence of Sulphuric, formic or oxalic acid. When sufficient amount of
chromium is taken up by wool, it is removed from the solution, squeezed and entered into
the dye solution. The dye is taken up by the wool from the dyebath and this dye forms the
insoluble complex in the fibre thereby producing excellent washing fastness.

In another method called the after-chrome method, the wool is first dyed with the dye as if it
is an acid dye. At the end of dyeing, the dyebath is exhausted by adding an acid. The dyed
material is removed, squeezed and entered into a solution of potassium dichromate and an
acid. In this case also the metal-dye complex is formed in the fibre. These two processes are
lengthy ones since chroming and dyeing (or dyeing and chroming) have to be carried out
separately in two solutions. There is a simpler process, called metachrome process, also
called chromate process. This is based on two principles;
1. when the dye is mixed with a solution of potassium chromate, no insoluble complex
is formed, and
2. when ammonium sulphate solution is boiled, it decomposes into ammonia and
Sulphuric acid and under the boiling conditions the ammonia gas is drawn out of the
solution, leaving behind the Sulphuric acid which is produced. Thus when wool is
entered into a dyebath containing the dye, potassium chromate and ammonium
sulphate at room temperature, the metal-dye complex is not formed in the dyebath.
The dyeing of wool with the dye starts taking place. The dyebath is then gradually
heated to boil. Under boiling conditions acidity is developed (in the meantime most
of the dye has been taken up by the fibre) and potassium chromate is converted into
dichromate, which than forms the complex in the fibre.

Metal – complex dyes

In the case of mordant dyes the metal-dye (chromium dye) complex is formed by the dyer
himself during dyeing. There are other dyes which are supplied by the dyestuff
manufacturers and these dyes already contain the metal (usually chromium) in their
structure, so that the dyer need not use any metal salt during the application. These are called
metal-complex dyes. Two types (1: 1 metal-complex and 1:2 metal-complex) of such dyes
are available depending on whether one or two molecules of the dye are complexed with one
atom of the metal.

1:1 Metal-complex dyes (Neolan, Palatine fast) need a large amount of Sulphuric acid in the
dyebath for proper dyeing and 1:2 metal complex dyes are usually dyed in the neutral
medium. Irgalan, cibalan, etc. dyes belong to 1:2 metal complex dye class. These are suited
for application on polyamide and wool, especially when blended with cellulosic fibres, since
they are dyed from a neutral dyebath in which the cellulosic component is not damaged.
This is not the case with 1:1 metal-complex dyes, which need strong acids in the dyebath.
These acidic conditions damage the cellulosic component of the blend during dyeing.
Therefore 1:1 metal-complex dyes are not used on wool and nylon when cellulosic fibres are
blended with them. In both the cases the dyeing is done at the boil.

Basic dyes
The most brilliant dyes among all synthetic dyes are found in this class of dyes. However,
they have poor light fastness (they fade in sunlight quickly). They are soluble in water and
produce coloured cations and chloride or other anions.
(H2O)
R4NCl R4N+ + Cl-
Addition of glacial acetic acid helps to dissolve the basic dye quickly in water.

Basic dyes have direct affinity for wool and silk which have carboxyl groups in them.

HOOC- W- NH2 H+ + -OOC-W-NH2

R4NCl R4N+ + Cl-

 -OOC-W-NH2 + R4N+ R4N + OOC-W-NH2

The carboxyl groups ionise and produce negative sites which attract and retain the dye
cation, thereby producing washfast dyeing.

They do not have affinity for cellulosic fibres. For dyeing them on cotton materials, the fibre
is first treated with a mordant like tannic acid followed by fixing with tartar emetic solution
in water and finally dyed in a solution of basic dye. Tannic acid has affinity for cotton and
also for the dye. In this case, tannic acid is fixed on cotton and then takes up the basic dye.

Auramine, Malachite Green, Methylene Blue, Rhodamine, Safranine, Magenta etc. are some
of the basic dyes.

Cationic dyeable acrylic fibres contain acidic groups introduced during their manufacture.
Special cationic dyes are available for dyeing these fibres. These are available under
different trade names such as Astrazon ( Bayer), acronol (ICI), Basavryl (BASF) etc. As a
rule, basic dyes have better light fastness on acrylic fibres than on cotton or silk.

Disperse dyes

Generally these dyes are insoluble in water. However, they are soluble in hot water to some
extent, the solubility increasing with temperature and due to this solubility the dyeing of
synthetic fibres, especially polyester fibres, is facilitated at elevated temperature.

These dyes are mechanically ground to very small particle size and with the help of a
dispersing agent (already incorporated in the dyestuff powder or liquid dispersion as
marketed) they can be dispersed in the dyebath. When a man-made fibre (polyester, nylon,
cellulose acetate etc.) is entered into the dyebath and the temperature is raised, the solubility
of the dye in water is increased and the dissolved dye is taken up by the fibre, in which it is
retained. Since the dissolved dye is removed from the dye bath by the fibre, some more of
the dispersed dye goes into solution, to be eventually picked up by the fibre. This sequence
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 like soap. Dyeing of
polyester and polyamide is a difficult process, since these fibres have a very compact
structure and the dye molecules find it difficult to penetrate into the fibre. The dyeing
process itself is modified in this case. For example, the property of softening of these fibres
at elevated temperatures (1300C to 2000C) is used in dyeing disperse dyes on polyester
fibres. At these temperatures, the fibres soften and the dye molecules penetrate well inside
the fibre and when the dyed fibre is cooled the dye is trapped inside the fibre. In another
method, called carrier dyeing the dyeing is carried out in a boiling dispersion (100 0C) of the
dye in water in the presence of a carrier like phenyl phenols, diphenyl, chlorobenzenes, butyl
benzoate, salicylic acid etc. During dyeing, the polyester fibre absorbs 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 its structure collapses, thereby trapping the dye in the fibre
structures.
A good disperse dye should have good fastness to light, gas fumes and sublimation. The
washing fastness is generally good.

Oxidation Colours

Aniline black is most important dye in this class. This is not a ready-made dye but has to be
formed in the fibre by the dyer or printer. Aniline is an oily liquid (called aniline oil),
immiscible with water. When concentrated hydrochloric acid is added to it, it forms a salt
(aniline hydrochloride or anilinium chloride) which is soluble in water.

NH2 NH3Cl
+ HCl

(Aniline ) ( Aniline hydrochloride )

Sodium chlorate and potassium ferrocyanide may be added to a solution of aniline

hydrochloride. Cotton cloth padded with solution, dried and exposed to an atmosphere of
steam, when aniline gets progressively oxidised to a compound having a bottle green colour.
This is further treated with a solution of potassium dichromate in the presence of Sulphuric
acid when a jet black (Aniline Black) shade is produced. This black is fast to washing, light,
chlorine etc. The development of black colour involves subjecting aniline to acidic,
oxidizing conditions and hence this lends itself, like solublised vat dyes, to resist style of
printing either for white or coloured effects.