Course Code :TEX3021

Course Title : Wet Processing Technology-II

Assignment topic : Disperse Dye

Submitted To
Introduction:
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.

History of Disperse Dye:

In 1922, Green and Saunders made one type of coloured azo compound, in which a solubilizing
group (for example- methyl sulphate, -CH2-SO3H) is attached to amino group. In dye bath, they
are slowly hydrolyzed and produce azo compound and formaldehyde bi sulphate. This free azo
compound was capable of dyeing cellulose acetate fibres. This dye was named “ionamine”. But
this ion amine did not give satisfactory result in dyeing.
Later in 1924, Baddiley and Ellis produced sulphoricinoleic acid (SRA) for dyeing acetate fibres.
This SRA was used as dispersing agent. Later it was seen that SRA was capable of dyeing Nylon,
polyester, acrylic etc. In 1953 this dye was named as “Disperse Dye”.

Properties of disperse dye:

 Disperse dyes are non-ionic dyes. So they are free from ionizing group
 They are ready made dyes and are insoluble in water or have very low watr solubility.
Their solubility is at least 0.1gm/lit
  They are organic colouring substances which are suitable for dyeing hydrophobic
fibres from colloidal dispersion.
   Disperse dyes are used for dyeing man-made , ester-cellulose and synthetic fibres
specially acetic and polyester fibres and sometimes nylon and acrylic fibres.    Carrier
or dispersing agent are required for dyeing with disperse dyes.
 Disperse dyes have fair to good light fastness with rating about 4-5.
 The wash fastness of disperse dyes are moderate to good with rating about
 Disperse dyes have the ability to undergo sublimation that is they can be vaporized
without fastness or wash fastness for sublimation fastnes of disperse dyes the
following cause are responsible.
 Small molecular size of dye suff.
  No ionic group.
  No sulphonated group Sublimation property of disperse dyes are used in
transfer printing. But it is a disadvantageris matter. Because excessive hot
ironing or pressing of disperse dyes/printed material may result in color loss.
 Of all dyes stuffs disperse dyes are of the smallest molecular size.the size of dye
molecules are 2-3 nanometre.
 Generally dispwrse dyes are derivative of azo, anthraquinone, nitro and quinine group.

Classification of Disperse Dyes:

 
According to Chemical Structure:

According to chemical structure there are following types of disperse dyes:

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

Azo dyes:
Azo dyes are defined as compounds containing at least one azo group attached to sp2-
hybridized carbon atoms, such as benzene, naphthalene, thiazole and thiophene. Azo dyes are
by far the most important class and account for more than 50% of the total commercialized
disperse dyes in the world.

Anthraquinone disperse dyes :

Anthraquinone disperse dyes were among the early ‘acetate’ dyes and have made an important
contribution to the violet and blue shade range. They produce bright dyeings of excellent light
fastness and cause no dye stability problems during dyeing. ₍₄₎
Chemical Groups In Disperse Dyes:

The percentage of chemical groups present in disperse dyes are as below:

 Mono azo dyes ………………………….50%
 Anthraquinonoid dyes ……………….25%
 Diazo dyes …………………………………10%
 Methyne dyes ……………………………03%
 Styryl dyes …………………………………03%
 Acrylenebenzimidazol ……………….03%
 Quinonaphthalon dyes ………………03%
 Amino naphthyl amide……………….01%
 Napthoquinone imine ……………….01%
 Nitro disperse dyes ……………………01%
........................................................................
              Total  = 100%

Trade Names Of Disperse Dyes:

Name of dye Manufacturer Origin

Foron Sandoz Switzerland
Terasil Ciba-Geigy Switzerland
Dispersol ICI UK
Samaron Hoechst Germany
SRA British Celanese Ltd. UK
Setile ACNA Italy

Fastness properties of disperse dyes:

Fastness Acetate Triacetate Nylon Polyester Acrylic

Washing Moderate Good Poor –fair Good Very
good
Light Good Good Moderate-good Good Good
Crocking Good Good Good Moderate-good Moderate
Gasfume Fair Moderate Fair Moderate Good
fading
Disperse dyes can be divided into five series:
 E-type disperse dyes : they have good leveling properties, and are suitable for dip
dyeing process. Besides, some can be used for thermal transfer printing process.
 SE-type disperse dyes: they have general leveling properties and good color fastness to
sublimation, and can be used in  the dip dyeing and pad-dry-cure dyeing process of the
polyester fibers.
 S-type disperse dyes: they have high color fastness to sublimation, and are mainly used
in the pad-dry-cure dyeing process of the polyester blended fabric.
 P-type disperse dyes: they are used for the anti discharge printing of the polyester
fibers and cellulose fibers blended fabric.
 RD-type disperse dyes: they can be used for the rapid dyeing of the polyester fibers.
According to the different molecular structure of the disperse dyes , they can be
distribute into azo, anthraquinone, nitrodiphenylamine ,heterocyclic ring and other
types. Because of the absence of water-soluble gene, the  disperse dyes dissolved in
water is minimal.

Some Common and Generic Names and stracture for Disperse Dyes

Application Of Disperse Dye:

Disperse dye are mainly suitable for coloring hydrophobic fiber such as
1. cellulose ,   2.tri-acetate ,
 3. polyamide , 4. polyester ,
  5.polyamide , 6.polyacrylo nitrile etc.
They have become especially important, for polyester fibres as they are widely used as a blends
with cotton, wool, or any other man madefibres . Disperse dyes are also used to color plastic
jwellery, PVC rods and PVC/ PES film. 

Methods of application of disperse dyes:

 Dyeing of Polyester fabric with Disperse dyes:
 Method N- Normal temperature dyeing (80°C-100°C)
 Method NC- Normal temp dyeing with carriers (80-100°C) Or Carrier method.
 Method HT- High temperature dyeing (105°-140°C)
 Method T- Thermo sol method (180° -200°C)
 Method pad Batch- Semi continuous method.
 Pad steam method- Continuous method.

Factors Considered for Selection of a Method:
1. Availability of dyeing machine.
2. Required colour effect (dark/medium/light).
3. Required colour fastness.
4. Type of material to be dyed.
5. Cost of dye, chemicals and auxiliaries.
6. Overall economy of the system.
7. Dyeing temperature.

Mechanism of disperse dyeing:

The dyeing of hydrophobic fibres like polyester fibres with disperse dyes may be considered as
a process of dye transfer from a liquid (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 enable them to leave the dye liquor as they are more
substantive to the organic fibre than to the inorganic dye liquor. The application of heat to the
dye liquor increases the energy of dye molecules and accelerates the dyeing of textile fibres.
a) Dispersion of the disperse dye from the solid phase into water: When dispersing agent is
added to dye bath, it forms micelle and this micelle solubilize disperse dye molecules and
dissolve more dye from the solid particles.

b) Adsorption of the dissolved dye from the solution onto fibre surface: The dye adsorption by
the fibre is influenced by solubility of the dye in the dye bath. More the dissolved dyes in the
dye bath with aided by the dispersing agent, increase the dye adsorption onto the fibre surface.

c) Diffusion of the dye molecules from the fibre surface into the interior of the fibre substance
towards the centre: Heating of dye liquor swells the fibre to some extent and assists the dye to
penetrate the fibre polymer system. Thus the dye molecule takes place in the amorphous
region of the fibre polymer system. When the dye bath is cool down, then the dye molecules
are held (entrapped) by hydrogen bonds and van der waals’ force.

Carrier Dyeing Method:

The extreme crystalline nature of polyester fibre creates problem in obtaining dark shade by
conventional dyeing method even at high temperature. The  carrier are found to assist the
disperse dyes to enter the polyester polymer. The carriers swells the polyester fibre  &  increase
the inter polymer space & let the dye molecule to inter into the fibre easily.

Recipe:
Dye:
-For light shade<0.5%
-For medium shade 0.5-1.5%
-For deep shade >1.5%
 Carrier(Phenol) : 3 gm/lit
 Acetic Acid: 1 gm/lit
 Dispersing Agent: 2gm/lit
 Salt: 1-2 gm/lit
 PH: 4-4.5
 M:L: 1:10
 Time: 60 min
 Tempurature: 90°C

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.

Dyeing Curve:

Dyeing Curve

Advantage of Carrier method:

 Possibility of dyeing in simple dyeing equipment at atmospheric pressure at up to 100°C
for polyester fibre.
 Reduced dyeing cycle due to accelerate dyeing.
 Improved fatness properties due to increased Perpetration in the fibre.
 Moderate level dyeing in polyester dyeing.
 Increased rate of dyeing.
 Increased levelling and better coverage of barre.
 Some carriers reduce the staining of wool while dyeing polyester / wool blends.

High Temperature Dyeing Method:

In high temperature dyeing method either material or liquor should circulate. Otherwise dye
molecules will not penetrate inside the material. They will stay on surface only. This method is
also known as pressure dyeing which is used for highly crystalline synthetic fibres and their
blends.

Recipe:
 Lyogen DFT: 0.5 gm/lit
 Sandozen PES: 1.0 gm/lit
 Acetic Acid: 1 gm/lit
 PH: 5.5-6.0
 Temperature: 130°C
 Time: 1 hr

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 fibre 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.

Dyeing Curve:

Dyeing Curve

Advantages of high temperature dyeing method:

 Dyeing time are frequently shorter

 No need of carrier
 Maximum 98% dye fixation
 Loss of dye is less
 Light fastness and wet fastness is usually higher
 Better exhaustion and deeper dyeing can be produced.
 Faster diffusion of the dye in the fiber at elevated temperature.

Thermasol Dyeing Method:

Thermasol dyeing 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. The
sequence of operation is:
Pading - Drying - Thermofixing - After Treatment

Recipe:
 Dye: X gm/lit
 Dispursing Agent: 2 gm/lit
 Sodium Alginate Thickener: 5-10 gm/lit
 Citric Acid to get PH: 4-5

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 thermasol unit where thermo fixing is done at about
205°C temp for 60-90 seconds depending on type of fibre, dye and depth of shade. In
thermasol 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.

Advantages of thermosol process:

1. Dyeing time is very short
2. No need of carrier
3. Non toxic
4. There is no additional problem of removing carrier by using alkali.
5. Very bright shade is obtained.
 6. Excellent dye utilization (75-90%) is achieved.
COMPARISION AMONG 3 PROCESS

PARAMETER CARRIER HTHP THERMOSOL

Carrier is used for

Swelling Temperature Temperature
swelling

Temp 90 -95*C 130-160*C 180-220*C

Time 45 min 60 min 2-5 min

Effect on Not environment 

Friendly Friendly
environment friendly

Light fastness not Fastness property is

Fastness Good
good good to excellent

Molecular wt of dye Low Higher Medium

application Wool/PE CVC, TC TC, POLYESTER

Dyeing Of Polyester Fabric With Disperse Dyes (Carrier Method):

Principal
   The dyeing of hydrophobic fibres like polyester fibres with disperse dyes may be considered
as a process of dye transfer from liquid 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 enables them to leave the dye liquor as they are
more substantive to the organic fibre than to the inorganic dye liquor. The application of heat
to the dye liquor increases the energy of dye molecules and accelerates the dyeing of textile
fibres.
  Carriers Method

  Mechanism of Carrier Action :

            In carrier method of polyester dyeing, carrier is used. Carriers swell the fibre and
ultimately cause relaxation. They may operate by opening up the internal fibre structure and
allow the dye molecules to diffuse more rapidly. Its action may be described as below:

1. It creates dye film on fibre surface.

2. Carrier takes dye inside the fibre from dye carrier association.
3. It increases the solubility of dye in the dye bath and fibre swelling .
4. Carriers penetrate inside the fibre polymer chain and thereby reduce inter-chain
attraction. Thus polymer chains become movable and so dye molecules may enter the
polymer system of fibre.
5. It increases the absorbency power of fibre.
6. The absorbed carrier increases the rate of dye uptake by creating liquid co-fibre.
7. It lubricates the thermally agitated fibre molecules.
8. 2-10 gm/lit carrier is used depending on material and liquor ratio and depth of shade.
9. The automatic portion of carrier is postulated to have Van Der Waal’s force and
attraction for hydrophobic group of it attracts water.
10. With increasing molecular weight the carrier efficiency also increases up to a certain
limit.

Recipe:
Dye = 2% on the weight of fabric
Dispersing agent =  2 g/L
Carrier (Phenol) = 3 g/L
Acetic acid =  1 g/L
M: L =  1:30

weight :  2 gm polyester fabric.

Calculation:
Dyeing Curve:

Procedure :
According to dyeing curve at first auxiliaries and water are added in the dye bath. kept for 5
minute.

The material, dye is added respectively.

After 10 minutes salt is added.

Adding salt dye bath is heated to 400-500C  kept for 20-30 minutes.

This is the exhaustion period of dyeing.

Alkali is added in the dye bath.

Adding alkali the dye bath is heated for 40-60 minute at 50-60 0C.
 This is the fixation period.

After treatment :

1. The material is treated with a 1g/L soap solution, which removes the unfixed dye from
fabric surface, and makes the surface clean.
2. Material is treated with a hot water bath.
3. Material is treated with a cold-water bath.
4. Finally the material is dried in a drier.15

Dispersing agent:

Disperse dye produce dispersion in water. To uniform dyeing bath should be stable dispersion
& this is why a special chemical is used in dye bath named dispersing agent. They should be
effective under dyeing condition, stable to hard water, high temperature  & other dyeing
assistants.Disperse dye are smallest dye. They form aggregation when they are applied to the
bath. They produce a lamp & create a large size particle. This could not enter inside the polymer
so dye particle should be individualized to enter inside the fiber. So dispersing agent is added. It
separates the particle & produces dispersion in the dye bath.

Function of the dispersing agent:

The dispersing agent performs many function .such as……

1. It assists the process of particle size reduction of the dye.
2. It enables the dye to be formed in the powder form. When the powder is added to the
dye bath, it facilitates the reconversion of the powder into a dispersion that is required
for carrying out the dyeing.
3. It maintains the dispersion in a fine form in the dye bath throughout the dyeing process.
4. It increases the solubility of the disperse dye in eater.
5. Its effects on the rate of dyeing.
Chemicals used as dispersing agent:
 Soap powder
 TRO
   Alkylarylsulphonate
 Nopholene-B- sulphonate
 Formaldehyde
  Setamol BASF
 Edalon Sandoz

 Trade Names of Dispersing Agent

 Steamroll
 Edalon
 Hispogal
 Dispervat 60
 Dispersant WS
 Pidimol TD
 Nitamol NV- 50

Criteria of choosing the disperse dye for combine shade:

 The dyes should have or nearly same substantivity towards the fibers.
  The dye should have same hydrophobicity.
  Their characteristic should be same or nearly same.
  Should be same energy level
 Should have same dyeing method
  Same diffusion number

The effects of variations in disperse dyeing

 Crystal form of the disperse dyes

The possible different crystal forms of disperse dyes have beensuggested to influence the
saturation values achieved on polyester, due to differences in thevapour pressure and
solubility of the different forms of dye in both water and fibre(Biedermann, 1971, 1972).

 Dispersing agent
Disperse dyes are sparingly soluble in water and often crystalline with varying particle
size.These characteristics are inadequate for dispersing the dyes in water and cause
unleveldyeing. In order to achieve the required particle size and distribution (Heimanns, 1981),
thedisperse dye is milled, usually in the presence of a dispersing agent (Derbyshire et al, 1972).

 Particle size in dispersion of the dyes

The aqueous solubility of disperse dye particles in a dispersion increases with decreasingparticle
size (Kenneth & Skelly, 1973). Thus an increase in the severity of milling thataccompanies a
reduction in the particle size of the dye enhances the solubility andadsorption of disperse dye.

 pH of dyebath

In the commercial dyeing of polyester fibres with disperse dyes, dyeing is carriedout within the
pH range 5.5 to 6.5. Strongly alkaline or acidic conditions, such as higher thanpH 9 and lower
than pH 4, induce hydrolysis of the fibre as well as decomposition of azodisperse dyes (Nunn,
1979). In the case of high temperature dyeing, this degradation ofpolyester fibre and dye is
accelerated.

 Substantively of disperse dyes

The substantivity of disperse dyes towards polyester fibres is one of the most critical factorsin
determining dyeing behaviour and there have been many studies carried out to evaluatethe
substantivity of disperse dyes towards hydrophobic fibres, including polyester, in orderto select
suitable dyes. These attempts include the ‘Solubility Parameter Concept’(Ingamells, 1990) and
‘IOR (Inorganic/Organic) values’ (Kim et al, 2003).

 Temperature

The adsorption and diffusion of disperse dyes on polyester are greatly influenced by
temperature as an increase in temperature increases the mobility of the polymer chains in the
amorphous regions of the fibre. For the dye-hydrophobic fibre system, the affinity of the
disperse dye decreases with increase in dyeing temperature while the saturation value of the
dye in the fibre increases with increasing temperature (Bird et al, 1959; White, 1960). Heat
setting changes the morphology of the polyester fibres. When fabrics of polyester are heat set
in air under conditions of free shrinkage, the dye exhaustion first decreases and then increase
with increasing setting temperature.

 Fibre fineness

Much attention has been given recently to dyeing microfibres. In a broad sense, especially
inEurope, the term microfiber means fine fibers of less than 1.0 denier. However, in SouthKorea
and Japan, where fine-fibre technology is more advanced, fine fibres of 0.04–0.4denier class are
generally used in this filament area (Koh et al, 2006).18

Toxicity due to disperse dyes:

1. Allergies from dyes 2. Aquatic toxicity

3. Dyes removal techniques 4. Fenton process

5. Ozonation 6. Membrane separation

7. Chemical oxidation 8. Photochemical degradation

9. Coagulation/flocculation 10. Adsorption

11. Microbiological decomposition of synthetic dyes.

Reduction Clearing:

In the case of disperse dyeing on PES fibers,

 Particulate disperse dye molecules accumulate at the surface of the dyed substrate
because of the dye’s low aqueous solubility
 Dye auxiliaries may also be present at the surface of the dyed PES material

So, reduction clearing is carried out. The process requires,

1. An aqueous alkaline (NaOH) solution of Sodium hydrosulfite (Na2S2O4)

2. Non-ionic surfactant
3. 50ºC–80ºC temperature
4. Rinsing and neutralized using dilute CH3COOH

As disperse dyes have limited solubility in water, some particulate disperse dye may still be
blocked on the fibre surface after the completion of dyeing. The usual practical procedure for
removing this unwanted dye is called reduction cleaning. A typical reduction clearing recipe is
given below.
 Detergent 1g/l
 Caustic soda 2g/l
 Hydrose 2g/l
 Temp. 78°C
 Time 20 min
 Then cold rinse followed by hot wash and neutralized
Recent requirements in disperse dyeing technology:
Environmental issues have been gaining importance in all aspects of industrial production
(McCarthy, 1998), and various legislative requirements have emerged with increasing regularity
to reduce the impact of dyeing processes on the environment. In response, the industry has
been forced to become increasingly innovative in order to develop new products and practices
that are more environmentally friendly than existing ones (Lewis, 1999). Therefore, innovation
and developments in color chemistry and dyeing will allow the colorist to meet ever-increasing
environmental restrictions, produce novel effects, and reduce processing costs (Leadbetter &
Leaver, 1989). The demand for environmentally friendly dyes with high wet fastness on
polyester is increasing, and the so-called alkali-clearable disperse dyes suggest a promising new
direction (Fig. 8). These alkali-clearable disperse dyes obviate the need for sodium
hydrosulphite and significantly reduce the cost of effluent treatment (Koh & Greaves, 2001).
Recently, these types of dye have become technically important for the coloration of polyester
and its cellulosic blends. They perform well on international standard and commercial wash
fastness test (such as ISO C06 C2S) (Choi, 1999). To achieve acceptable levels of wet fastness
after post-heat treatment, the development of modern disperse dyes must be directed towards
satisfying a number of needs. Firstly, new dyes need to be tailored towards satisfying shorter,
more easily reproducible and more economical dyeing processes. Secondly, with the increasing
use of polyester and polyester blends in sports and leisurewear, there is a clear demand for
dyes of higher wet fastness. Indeed this requirement has become even more important with
the introduction of polyester microfibres, where higher depths of shade have to be dyed in
order to obtain the same visual yield as with conventional polyester fibre. Finally, the
development of new disperse dyes must take into account the effect that effluent from the
dyeing process will have on the environment, and aim to minimize such pollution. These
objectives are not mutually exclusive but interrelated; they must all be taken into account in
any dye development program (Leadbetter & Leaver, 1989).

Recent Advances in Disperse Dye Development and Applications:

The commercial development of new disperse dyes for 100% polyester and polyester/cellulose
blends is reviewed. The deficiencies of traditional anthraquinone disperse dyes for bright red
and bright blue shades are highlighted from the standpoint of today's requirements for higher
wetfastness and more economical processing. More acceptable alternative dyes are described
with emphasis on exhaust dyeing of 100% polyester microfibers and one-bath dyeing of
polyester/cellulose blends. Some aspects aimed at reducing environmental pollution, namely
alkali-clearable disperse dyes and choice of formulating agents, are discussed.
Conclutaion:
Disperse dye are the smallest dye of all dyes. They are insoluble in water. When they
are applied to the dye bath, they form dispersion. They are free from ionized group. So
they have low solubility in water& are suitable for dyeing hydrophobic fibres. The use of
dispersion dyes is fairly on a large scale, as fibres like polyester, nylon, polyester blends
and other synthetic textiles. Disperse dyes is mainly used for dyeing polyester yarn of
fabric. in the other hand, Reactive dyes are used for coloring cotton or cellulosic fiber.
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