By: Imran

anwar 06-NTU-112

Imrananwar_112ntu@yahoo.com
NATIONAL TEXTILE UNIVERSITY
FAISALABAD

PAKISTAN

Date of Submission:15-01-2009
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 D−SO3−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.
Anthraquinon
Azo dyes:
e
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:
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.

Triphenylmethane

Application:
These dyes are applied in the following way,
1. The dye is dissolved in the water and it dissociates as follows,
D−SO3Na + H2O → D−SO3− + Na+
2. Wool−NH2 +H+ → Wool−NH3+
This H+ was liberated by the acid used for the acidic medium
3. Then the bond formation occurs as follows,
D−SO3− + Wool− NH3+ → Wool−NH3−SO3−D
In case of the silk and nylon wool is replaced by them in the equation
and the other reaction remains same.
The temperature of dyeing is 60 C ̊ and the migrating rate can be
increased by increasing the temperature up to 70 ̊C.
Exhausting Agent:
Na2SO4 is used as an exhausting agent.
This causes the repelling of D−SO3− group more towards the fibres
because of SO3- group present in it.
Retarding Agent:
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 not higher
than 85 ̊C.
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.
The reason for the mixing of the other monomer to it is that the
Glass Transition Temperature (Tg) of the acrylic fibres is 104 ̊C that requires
heating at high temperature. By this mixing the Glass Transition Temperature
falls to 80-85 ˚C.
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.
Ac−SO3− + D+ → Ac−SO3−−D+
 If we dye the fabric below 80-85 ˚C then the diffusion of the dye will be
difficult also it will not be uniform and the rate of dyeing is slow. But as
the temperature of the liquor is raised to 90 ˚C the 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

Methine 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.
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 60-70 ˚C so that the dye is
penetrated in this state in the 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 90-100 ˚C
 Dye for 30-35 minutes
 Then drain the dye liquor and wash the fabric with detergent at 60-70
˚C. This 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 50-60 ˚C.
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.
Temperature = 130 ˚C
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.