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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
+ 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.