Dyeing mechanism of disperse dye

The dyeing of hydrophobic fabric with disperse dyes may be considered as a process of dye transfer from
a liquire solvent ( water ) to a solid organic solvent(fibre).
Disperse dyes are added to water with a surface active agent to form an aqueous dispersion. The insolubility
of disperse dyes enablethem to leave the dye liquor as they are more substantive to the application of that
to the dye liquor increases the energy of dye molecules and accelerates the dyeing of textile fibres.
Heating the dye liquor swell the fibre to some extent and assists the dye to penetrate the fibre polymer
system. Thus the dye nolecule takes its place in the amorphous regions of the [Link] the fibre polymer
system, the dye molecules are held by hydrogen bonds and van der waals force.
The dyeing is considered to take place in the following simultaneous steps :-

1) Diffusion of dye in solid phase, into water by breaking up into individual molecules. This diffusion depends
on dispersibility and solubility of dyestuff and is aided by the presence of dispersing agent and increasing
temperature.
2) Adsorption of the dissolved dye from the solution onto the fibre surface. This dyestuff adsoeption by in the
dye bath and that in the fibre.
3) Diffusion of the adsorbed dye from the fibre surface into the interior of the fibre substance towards the
centre. In normal condition, the adsorption rate is always higher than the diffusion rate. Abd this is the
governing step of dyeing.

Properties of Disperse Dyes:

• Disperse dyes are nonionic dyes. So they are free from ionizing group.
• They are ready made dyes and are insoluble in water or have very low water
solubility.
• They are organic coloring substances which are suitable for dyeing
hydrophobic fibers.
• Disperse dyes are used for dyeing man made cellulose ester and synthetic
fibers specially acetate and polyester fibers and sometimes nylon and
acrylic fibers.
• Carrier or dispersing agents are required for dyeing with disperse dyes.
• Disperse dyes have fair to good light fastness with rating about 4-5.

Classification of Disperse Dyes:

According to Chemical Structure:

1. Nitro Dyes
2. Amino Ketone dyes
3. Anthraquinonoid dyes
4. Mono azo dyes
5. Di- azo dyes

Application Methods of Disperse Dyes:

1. Method N: Normal dyeing method. Dyeing temperature is 80-100°C.

2. Normal NC method: Method of dyeing at normal temperature with carriers.
Dyeing temperature 80-100°C.
3. Method HT: High temperature dyeing method. Dyeing temperature 105-
140°C.
4. Method T: Thermasol dyeing method. Dyeing temperature 180-220°C,
continuous method of dyeing.
5. Pad roll method: Semi continuous dyeing method.
6. Pad steam method: Continuous dyeing method.

CARRIER DYEING METHOD:

PROCEDURE:

1. At first, a paste of dye and dispersing agent is prepared and then water is
added to it.
2. Dye bath is kept at 60°C temperature and all the chemicals along with the
material are added to it. Then the bath is kept for 15 min without raising the
temperature.
3. pH of bath is controlled by acetic acid at 4-5.5.
4. Now temperature of dye bath is raised to 90°C and at that temperature the
bath is kept for 60 min.
5. Then temperature is lowered to 60°C and resist and reduction cleaning is
done if required. Reduction cleaning is done only to improve the wash
fastness.
6. Material is again rinsed well after reduction cleaning and then dried.
 Fig: Dyeing
curve

HIGH TEMPERATURE DYEING METHOD:

PROCEDURE:

1. At first a paste of dye and dispersing agent is prepared and water is added to
it.
2. PH is controlled by adding acetic acid.
3. This condition is kept for 15 minutes at temperature 60°C.
4. Then the dye bath temperature is raised to 130°C and this temperature is
maintained for 1 hour. Within this time, dye is diffused in dye bath, adsorbed
by the fiber and thus required shade is obtained.
5. The dye bath is cooled as early as possible after dyeing at 60°C.
6. The fabric is hot rinsed and reduction cleaning is done if required.
7. Then the fabric is finally rinsed and dried.
 Fig: Dyeing
curve

Thermosol Dyeing Method:

Dyeing of Polyester Fabric in Thermosol Dyeing Method

Thermosol method is continuous methods of dyeing with disperse dye. Here

dyeing is performed at high temperature like 180-220°C in a close vessel. Here
time of dyeing should be maintained very carefully to get required shade and to
retain required fabric strength.

Sequence:

Pading—-→Drying—-→Thermo fixing—-→After treatment

Procedure:

1. At first the fabric is padded with dye solution using above recipe in a three
bowl padding mangle.
2. Then the fabric is dried at 100°C temperature in dryer. For dyeing, infra red
drying method is an ideal method by which water is evaporated from fabric
in vapor form. This eliminates the migration of dye particles.
3. Then the fabric is passed through thermosol unit where thermo fixing is done
at about 205°C temp for 60-90 seconds depending on type of fiber, dye and
depth of shade. In thermosol process about 75-90% dye is fixed on fabric.
4. After thermo fixing the unfixed dyes are washed off along with thickener and
other chemicals by warm water.
5. Then soap wash or reduction cleaning is done if required. And finally the
fabric is washed.
What is Sulphur Dye?
Sulphur dyes are complex heterocyclic molecules or mixtures formed by melting
or boiling organic compounds containing amino or nitro groups with Na-
polysulphide and Sulphur. Sulphur dyes are so called as they all contain Sulphur
linkage within their molecules.

Fig: Sulphur dyes

Sulphur dyes are highly colored, water insoluble compounds and have to be
converted in to water soluble substantive forms (lucoforms) before application to
the textile materials. This conversion is carried out by a treatment with a reducing
agent like dilute aqueous Na2S. Since this lucoform of Sulphur dye is substantive
to cellulosic materials. They are absorbed on the fiber surface. Then they are
reconverted original water insoluble form of dye by oxidation. This oxidation is
carried out by “airing” (exposure to air) or by using an oxidizing agent like Na-
dichromate (Na2Cr2O7). Sulphur gives best result (Bright Tone) when they are used
to produce black, Black & brown shades but red shades cannot be obtained by
Sulphur dyes. The cotton textile materials dyeing with Sulphur dyes can be topped
with basic dyes for brightening the shades.
Characteristics of Sulphur Dyes:
The main properties and characteristics features of Sulphur dyes are mentioned
below:-

1. Sulphur dyes have Sulphur linkage within their molecules.

2. Sulphur dyes are highly colouerd water insoluble dyes. Some dyes are
partially soluble in water.
3. They have no direct affinity towards cellulosic fibres. To make them
substantive they are to be converted in to soluble lucoform by treating them
with reducing agents (Like dilute Na2S solution)
4. Sulphur dyes have good light fastness with rating about 4. This light fastness
may be improved by an after treatment with metallic salt.
5. These dyes have excellent wash fastness with rating about 3-4. This
good wash fastness is due to its larger molecular size & insolubility in
water.
6. They are not applicable to wool due to strong alkaline condition.
7. They are exclusively amorphous, few of them show crystallinity.

Classification of Sulphur Dyes:

Sulphur dyes may be classified in many ways. But according to their solubility
there are essentially 3 classes of Sulphur dyes as below:

1. Conventional or Water insoluble dyes

2. Leuco Sulphur dyes (Partially soluble) and
3. Solubilised Sulphur dyes.

These in turn are subdivided in to 6 sub classes, depending on the

method of application. Namely–

1. Method i
2. Method ii
3. Method iii
4. Method iv
5. Method v
6. Method vi

Features of Sulphur Dye

1. Amorphous Colloidal materials.

2. High molecular weight with various composition
3. Complex molecular structure –heterocyclic molecules containing Sulphur
linkage.
4. Decomposed by acids, with the liberation of H2S.
 5. Characterized by thiozine ring, containing Sulphur atom.

Chemical Structure:
Sulphur dye contain Sulphur atom in their molecule and is characterized by the
thiozine ring

A portion of Sulphur dye molecule is shown below:

The structure formula is incomplete because the complete composition and

structure of Sulphur dye is mot known.

Typical Recipe:
The Typical recipe of sulphur dyes for dyeing with cotton is as below:-

• Sulphur Dye : 10% (On the weight of the fabric)

• Na2S (Reducing Agent) : 1.5% (on the weight of the Dye)
• Salt : 8 gm/litre (NaCl)
• Soda Ash (NaCO3) : 7 gm/litre
• Temperature : 1000C
• Time : 90 minutes
• Material: Liquor : 1:20

Improving of Fastness Properties:

The light fastness of cotton dyeing with Sulphur dyes which is generally good
can be improved by after treatment with certain metallic salts. Thus a treatment
with CuSO4 & CH3COOH in presence of K2Cr2O7 or Na2Cr2O7 improves the light
fastness. When the dichromate is also present the washing fastness is slightly
improved. In actual practice the following after treatments are given: –

• CuSO4 Solution → 1-2% (on the weight of goods)

• CH3COOH (60%) → 1-2%
• Temperature → 700C
• Time → 20-30 Minutes

Or

• Na2Cr2O7 → 1-1.5 % (on the weight of goods)

• CuSO4 Solution → 0.5-1%
• CH3COOH (60%) → 1-2%
• Temperature → 700C
• Time → 20-30 Minutes

The latter one also improves the washing fastness of Sulphur dyed textile
materials.

Defects of Sulphur Dyeing:

They are mainly two defects which are common in Sulphur dyes which dyeing
with textile materials:-

1. Bronziness or Dullness of shades

2. Sulphur Black tendering

Causes for the Popularity of Producing Black Shades with Sulphur

Dyes:

1. Low cost
2. Fair to good light fastness
3. High Wash fastness
4. Easy to apply
5. Low energy required
6. Chemical resistance is moderate to good.
7. Wide range of shades especially on heavy, durable shades on apparel fabric.
Azoic dyes

The dyes containing insoluble azo group (-N=N-) are known as azoic dyes.

These dyes are not found in ready-made form. Azoic dyes are produced by a
reaction between two components. The components are:

1. Coupling Compound (Naphthol)

2. Di-azo –compound or diazo base or diazo salt.

The colored substance formed from this colorless compound is insoluble in water
and washing fastness of this shade is excellent.

Fig: Dyeing of cotton with azoic dye

Reaction:

Naphtholation:
Naphthols are insoluble in water and they are converted into water soluble
compound by treating with alkali.
This salt solution is used for the impregnation of fabric.

Diazotization:
A base containing amino group (-NH2) reacts with the NaNO2 (Sodium Nitrite)
to form a solution of diazonium chloride of that base in presence of excess HCl at
00-50C temperature.

Coupling/Developing:
The impregnated material is treated in a bath containing diazonium solution to
carry out to coupling and thus color is produced inside the fabric. The PH
maintaining is important.

Recipe of dyeing of cotton fabric with azoic dyes:

Naphtholation:

• Naphthol = 3%
• Glycerine = 1 g/L
• Caustic soda = 6 g/L
• Common salt = 15 g/L
• Time = 20-30 minute.
• Temperature = room.
• M: L = 1:30

Base solution (for diazotization):

• Base color = 3 %
• HCl = 3%
• NaNO2 = 2%
• Acetic acid = 2%
• Sodium acetate = 1%
• Temperature = 00-50C (with ice)
• Time = 20-30 minute.

Procedure:

• For making naphthol solution, at first naphthol, glycerine and caustic soda
are added in bath.
• Then common salt is put in the bath and mixed them well.
• Then fabric is immersed into this solution for few minutes.
• Then kept for 30 minute at room temperature.
• Then for diazotization at first base color, HCl and NaNO2 are added another
bath at 00-50C (with ice). Then sodium acetate and acetic acid is added to
maintain proper PH of the solution.
• Then the chemicals are mixed properly.
• After then the naphthalated fabric is immersed into that solution and color is
produced very suddenly.
• Finally the fabric is immersed for few minutes. And we got the final shade
of color.

After treatment:

• After dyeing operation is completed the dye material is put into a bath
containing cold wash.
• The material is treated with a 1g/L soap solution, which removes the unfixed
dye from fabric surface, and makes the surface clean.
• Then material is treated with a cold-water bath.
• Finally the material is dried in a drier.