Port City International University.

Assignment
Study on Vat dye, Sulphur dye, and Azoic dyeing process.

Course title
Colour Chemistry.

Course code
CHEM-221

Submitted to
Mr. Md. Iusuf Khan (Senior Lecturer)
Textile Department.

Submitted by
Robel Mahmud (BTE-01806348)
Saranika Barua (BTE-01906409)
Borhan Uddin Tanjil (BTE-01906410) BTE-19 (Evening)
Bipasha Rani Das (BTE-01906413)
Rayhana Tajrin (BTE-01906418)

Submission Date
10-12-2020
Study on Vat dye, Sulphur dye, and Azoic dyeing process.

Contents
Introduction: ............................................................................................................................................. 5
1 Vat dye: ................................................................................................................................................... 6
1.1 History of Vat dye: .......................................................................................................................... 6
1.2 Properties of vat dyes: .................................................................................................................... 7
1.3 Classification of vat dyes: ............................................................................................................... 7
1.4 Trade name of vat dyes: ................................................................................................................. 8
1.5 Mechanism of dyeing with vat dyes: ............................................................................................. 9
1.5.1 Aqueous dispersion: ................................................................................................................. 9
1.5.2 Vatting: ..................................................................................................................................... 9
1.5.3 Dye absorption: ........................................................................................................................ 9
1.5.4 Re-oxidation of vat dye:........................................................................................................... 9
1.5.5 Soaping of vat dye: ................................................................................................................. 10
1.6 Vat Dyeing auxiliaries: ................................................................................................................. 10
1.6.1 Reducing agent:...................................................................................................................... 10
1.6.2 Caustic soda:........................................................................................................................... 11
1.6.3 Wetting agent: ........................................................................................................................ 11
1.6.4 Sequestering agent: ................................................................................................................ 11
1.6.5 Dispersing agents: .................................................................................................................. 11
1.6.6 Neutral salts:........................................................................................................................... 11
1.7 Common Method of application of vat dye: ............................................................................... 11
1.8 Faults found in vat dyeing: .......................................................................................................... 12
1.9 Stripping of vat dyes and correction of faulty dyeing: .............................................................. 12
2 Sulphur dye: ......................................................................................................................................... 13
2.1 History of Sulphur dye: ................................................................................................................ 14
2.2 Properties of Sulfur Dyes: ............................................................................................................ 14
2.3 Types of Sulfur Dyes:.................................................................................................................... 15
2.4 Trade Names of Sulphur dye: ...................................................................................................... 15
2.5 Mechanism of The Sulfur Dyeing:............................................................................................... 15
2.5.1 Dissolving The Dyestuff:........................................................................................................ 15
2.5.2 Reducing The Dyes to Form a Leuco Compound: .............................................................. 16
2.5.3 Dyeing with The Reduced Dyes: ........................................................................................... 16
 2.5.4 Washing Off the Un Exhausted Dyestuff: ........................................................................... 16
2.5.5 Oxidation Back to The Parent Dye: ..................................................................................... 16
2.5.6 After Treatment: .................................................................................................................... 17
2.5.7 Dye Fixing Treatment: .......................................................................................................... 17
2.5.8 Softening: ................................................................................................................................ 17
2.5.9 Final Treatment: .................................................................................................................... 17
2.5.10 Use of Standing Bath: .......................................................................................................... 17
2.6 Sulphur Dyeing auxiliaries: ......................................................................................................... 18
2.6.1 Reducing Agent: ..................................................................................................................... 18
2.6.2 Oxidizing agents:.................................................................................................................... 18
2.6.3 Sequestering agents: .............................................................................................................. 18
2.7 Common Problem of Sulphur dyes: ............................................................................................ 18
2.7.1 Poor wash and rubbing fastness: .......................................................................................... 18
2.7.2 Bronziness:.............................................................................................................................. 19
2.7.3 Tendering: .............................................................................................................................. 19
2.7.4 Poor color value: .................................................................................................................... 20
2.8 Stripping of Sulphur Dyes: .......................................................................................................... 20
3 Azoic Dye: ............................................................................................................................................. 21
3.1 History of Azoic Dye: .................................................................................................................... 21
3.2 Properties of Azoic Dyes: ............................................................................................................. 22
3.3 Application Methods: ................................................................................................................... 22
3.3.1 Dissolving of Naphthols: ........................................................................................................ 22
3.3.2 Naphtholation:........................................................................................................................ 23
3.3.3 Diazotisation: .......................................................................................................................... 24
3.3.4 Development or Coupling: .................................................................................................... 26
3.4 After-treatments: .......................................................................................................................... 27
3.5 Problem in dyeing with azoic color: ............................................................................................ 27
3.6 Stripping of Azoic Colorants: ...................................................................................................... 28
Conclusion: .............................................................................................................................................. 28

Table 1 Trade name of vat dyes. .............................................................................................................. 8

Table 2 Trade Names of Sulphur dye. .................................................................................................. 15
Table 3 Required quantities of chemical for dissolving 1 part of napthol. ........................................ 23
Table 4 Chemical required in parts for 1 unit of fast bases for diazotization. .................................. 25
Table 5 Coupling ratios of various naphthols and fast bases. ............................................................ 26
Figure 1 Thioindigo & Indigo .................................................................................................................. 7
Figure 2 anthraquinone ............................................................................................................................ 8
Figure 3 Soluble Sodium salt of Leuco vat dye. ..................................................................................... 9
Figure 4 Re-oxidation of vat dye............................................................................................................ 10
Figure 5 .................................................................................................................................................... 10
Figure 6 .................................................................................................................................................... 11
Figure 7 Partial chemical structure of proposed for Sulfur Black 1. ................................................. 13
Introduction:
Dyed flax fibers have been found in the Republic of Georgia in a prehistoric cave dated to 36,000 BP.
Archaeological evidence shows that, particularly in India and Phoenicia, dyeing has been widely carried
out for over 5,000 years. Early dyes were obtained from animal, vegetable or mineral sources, with no to
very little processing. By far the greatest source of dyes has been from the plant kingdom, notably roots,
berries, bark, leaves and wood, only few of which are used on a commercial scale.

The first synthetic dye, mauve, was discovered serendipitously by William Henry Perkin in 1856. The
discovery of mauve also led to developments within immunology and chemotherapy. In 1891 Paul
Ehrlich discovered that certain cells or organisms took up certain dyes selectively. He then reasoned that
a sufficiently large dose could be injected to kill pathogenic microorganisms, if the dye did not affect
other cells. Erlich went on to use a compound to target syphilis, the first time a chemical was used in
order to selectively kill bacteria in the body, he also used methylene blue to target
the plasmodium responsible for malaria.

However, A dye is a colored substance that chemically bonds to the substrate to which it is being applied.
This distinguishes dyes from pigments which do not chemically bind to the material they color. The dye
is generally applied in an aqueous solution, and may require a mordant to improve the fastness of the dye
on the fiber.

Both dyes and pigments are colored, because they absorb only some wavelengths of visible light. Dyes
are usually soluble in water whereas pigments are insoluble. Some dyes can be rendered insoluble with
the addition of salt to produce a lake pigment.

Let it go away, here we mainly discussed about Vat dyes, Sulphur dyes, and Azoic dyes. So let’s take a
look about this dyes.
1 Vat dye:
The vat dyes are found amongst the oldest natural coloring matters used for textiles. The word ‘Vat’
means Vessel. The dye takes their generic name from vatting. The vat dyes are naturally obtained
coloring matter from the ancient time and kept into wooden vat and make solubilized in vat by process
of fermentation – so it is called Vat dye.

The vat dyes are all insoluble in water and cannot be used for directly dyeing without modification.
When treated with reducing agents they are converted into Ieuco compounds, all of which are soluble
in water in the presence of alkalis. ‘These leuco compounds are substantive towards cellulose and
reoxidize to the insoluble colored pigment within the fiber when exposed to air. The leuco compounds
are often colorless or of quite a different color from the product of oxidation. During dyeing process,
it is this soluble form of the dye that is applied on cotton, followed be reconversion of the soluble form
into the original insoluble form. As a result, the insoluble dye is trapped in the fiber substance and
cannot come out during or other wet treatments, thereby ensuring excellent fastness to washing and
wet treatments. Most of the vat dyes are extremely fast to light

1.1 History of Vat dye:

Indigo has been known in India since the earliest periods of which historical records exist. Until the
beginning of the Present Century Indigo was obtained the most important was exclusively from plants
of which Indigofera tinctoria, originally cultivated in India.

According to the writings of Julius Caesar the Ancient Britons used Woad to stain their bodies and
faces and Tyrian Purple was exported from Tyre to the Mediterranean countries nearly 4000 years ago,
Tyrian Purple is extracted from a shell fish and is therefore of animal origin, but Woad and Indigo exist
in plants, combined with glucose in the form of glucosides.

The successful large scale production of Indigo from naphthalene dates from about 1900 and, since
then, the synthesis of vat dyes has been an extremely active field of research and many new members
have been added to this class.

The knowledge related to Indigo and its properties spread gradually to Egypt and other countries of the
Middle East and hence of Greece, Rome and Europe.
1.2 Properties of vat dyes:
 Vat dye is water insoluble and can’t be directly applied to textile material but they have to be
converted into their water soluble form.
 Mainly use for cellulose fiber dyeing but in protein fiber dyeing pH should be controlled.
 The particle size of vat dye should be as small as possible. The top quality dyes available
generally have an average particle size of well below 1um.
 Commercial vat dyes are marketed in different forms such as past, supra paste, Double paste,
Powder etc.
 Rubbing fastness not good.
 Various shade is found.
 Dyeing process is difficult.
 Washing fastness of vat dye is very good.

1.3 Classification of vat dyes:

On the basis of Chemical structure, there are mainly two types of vat dyes.

1. Indigoid vat dyes which are usually derivatives of indigotin (-NH- Chromophore
group), or thioindigo (-S-) Chromophore group.

Figure 1 Thioindigo & Indigo

 2. Anthraquinoid vat dyes derived from anthraquinone (one or more Quinone groups are
Chromophore group).

Figure 2 anthraquinone

1.4 Trade name of vat dyes:

Trade name of vat dye vary from country to country. Here some trade name given below with their
company and country name.

Table 1 Trade name of vat dyes.

Trade Name Company Country

Artex vat Rainbow Texdyes Corp. India
Benxanthrene Chemiwquip Ltd. India
Calconoid AAmerican Cyanamid Co. USA
Cibanone Ciba-geigy A.G. Switzerland
Caledon I.C.I. U.K.
Durindone I.C.I. U.K.
Indanthrene Farbenfabriken Bayer A.G. Germany
Metavat Universal Dyestuff Indus India
Mikanthrene Mitsui Chemical Industry Japan
Paradone L.B. Holiday & Co. UK
Sandothrene Sandoz Ltd Switzerland
Supranthrene Associated dyestuff ind. India
Solanthrene Francolor France
1.5 Mechanism of dyeing with vat dyes:
The application of vat des to cellulosic materials occurs in following stages:

1.5.1 Aqueous dispersion: The insoluble vat dyes, in this stage, is dispersed in water.

1.5.2 Vatting: In this stage, insoluble vat dye is reduced to produce weak acidic leuco form. Sodium
hydro sulphite used as a reducing agent. Again salt formation by neutralizing their hydroxide to give a
water soluble product. Sodium hydroxide is used as a solubilizing agent.
The reaction of vatting is given bellow.
Na2S2O4 + 2H2O  2NaHSO3 + 2[H]

Figure 3 Soluble Sodium salt of Leuco vat dye.

1.5.3 Dye absorption: The vatted dye- molecules are substantive to the cellulose material. To
achieve adequate exhaustion, an electrolyte is added to the dye liquor and temperature may be increased
from 20° to 60°C. In this stage, the textile material must be immersed in dye liquor to prevent oxidation
of leuco compound.

1.5.4 Re-oxidation of vat dye: In this stage, the soluble form of leuco vat dye absorbed by the
fiber is converted to its original color and insoluble form. This oxidation is brought about by
atmospheric oxygen or by chemical oxidation (involving the use of a chemical like Na per borate, K
dichromate).
 Reaction as follows:

Figure 4 Re-oxidation of vat dye

In order to keep the dye always in the soluble form, the equilibrium should be shifted to the left, which
can be ensured by adding more sodium hydroxide.

1.5.5 Soaping of vat dye: During the previous stage, some insoluble vat dye may be deposited on
the surface of the textile material. This has to be removed to prevent poor rub-fastness as well as shade
changing. By soaping off, this surface dye can be removed.

1.6 Vat Dyeing auxiliaries:

1.6.1 Reducing agent: The most important reducing agent is Sodium dithionite, generally referred
to as Hydrosulphite or Hydrose.

Function-
In this stage, insoluble vat dye is reduced to produce weak acidic leuco form.
Na2S2O4 + 2H2O  2NaHSO3 + 2[H]

Figure 5
1.6.2 Caustic soda: Caustic soda: Sodium hydroxide is used as a solubilizing agent. Salt formation by
neutralizing their hydroxide to give a water soluble product.

Figure 6

1.6.3 Wetting agent: To emulsify the waxes in the grey cotton and to ensure a satisfactory
penetration of the dye liquor into the substrate.

1.6.4 Sequestering agent:

 Chelation the alkaline-earth ions contained in the grey cotton and the process water.
 Preventing the precipitation of pectin and of the almost insoluble alkaline-earth salts of leuco dyes.

1.6.5 Dispersing agents:

 Prevents the aggregation of undissolved particles.
 Particularly important in the oxidizing and washing-off process.

1.6.6 Neutral salts: Sodium sulphate or chloride can increase the substantivity of the leuco dye for the
fiber

1.7 Common Method of application of vat dye:

1. Conventional or reduced vat color method.
2. Pigmentation or Pigment Padding System.
a. Pad-Steam method. b. Pad -Jig method.
3. Vat acid process.
1.8 Faults found in vat dyeing:
 Dark Selvedge: If over oxidation occurs during vat dyeing in Jigger M/C, dark selvedge creates.
This fault can be removed by the arrangement of pouring Caustic-Hydrose solution in both
selvedges during dyeing.
 Light spots: This fault founds if faults in pretreatment of fabric i.e. bleaching, mercerizing,
desizing.
 Deep spots: Deep spots happen due to uneven oxidation and reducing which can be removed by
stripping method.
 Uneven color: Faulty weaving, uneven tension of warp and weft ad faulty mercerizing creates
uneven color.

1.9 Stripping of vat dyes and correction of faulty dyeing:

Faulty dyeing can be corrected by levelling, stripping or over dyeing. Levelling can be carried out on
winch or jig at 80-90°C, or even above boil in package-dyeing machines.

It is not easy to remove the color from vat-dyed materials. By using reducing agents only, stripping is not
possible as the leuco compound formed is quickly reabsorbed. The stripping from the dyed goods either
partially or to a pale ground shade suitable for redyeing, may be carried out by using a levelling agent
such as Dispersol VL or Matexil DN-VL, 2 – 5 gm/l or polyvinylpyrrolidone (Albigen A, BASF) in blank
reducing bath containing caustic soda and hydrosulphite. The latter chemical has a particularly strong
action; several successive baths containing this agent at a concentration of 1-2 g/l are preferred over single
bath treatment with stronger solution, because in the latter case redeposition of precipitated dye on the
goods may occur.

Complete stripping is possible using Lissolamine V (ICI) in the caustic soda-hydrosulphite bath. The
stripping may be done by treating the dyed material with 3 – 5% Lissolamine V, 4 – 5% caustic soda
flakes and 6% sodium hydrosulphite (all o.w.m.) at a M: L ratio of 1:5 at 95-90°C for 30-45 minutes. This
is followed by cold rinsing, mild bleaching, rinsing and soaping, at boil. Lissolamine V may be added to
the bleaching bath to hasten bleaching.
2 Sulphur dye:
The characteristic feature of this is that they all contain Sulphur linkages within their molecules. They are
usually insoluble in water, but dissolve in a solution of sodium sulphide to which sodium carbonate may
or may not be added. The sodium sulphide acts as a reducing agent, severing the Sulphur linkage and
breaking down the molecules into simple components which are soluble in water and substantive towards
cellulose.
Dye.S – S.Dye + 2H  Dye.SH + HS.Dye

The thiols, containing the SH groups, are readily oxidized in the fiber to the original insoluble Sulphur
dye, giving a colour with very good wet-fastness.

Dye.SH + HS.Dye + O  Dye.S – S.Dye + H2O

The exact chemical structure of sulfur dyes is not known, but these dyes contain sulfur as an integral of
the chromophore as well as in the polysulphide side chains. These are produced by theorization or
sulphurisation of organic intermediates containing nitro and amino groups.
Sulphur Black is an outstanding member of Sulphur dyes family.

Figure 7 Partial chemical structure of proposed for

Sulfur Black 1.
2.1 History of Sulphur dye:
The first sulphur dye was made in 1873 by heating sawdust with Sulphur and caustic soda. This substance
was adsorbed from an alkaline liquor by cotton and subsequent oxidation with potassium dichromate
produced a brown shade of quite good wet-fastness.

This particular color, however, never achieved commercial success and the real pioneer of sulphur dyes
was Vidal, who, in 1893, produced the Vidal Blacks by fusing paraphenyl-enediamine, or para-
aminophenol, with sodium sulphide and sulphur. It has necessary to oxidize the Vidal Blacks on the fiber
with potassium dichromate to develop the black.

In 1897 Kalischer prepared Immedial Black FF by heating 2: 4-dinitro-4-hydroxy diphenylamine with

sodium polysulphide and it met with great success because it was not necessary to oxidize it with
dichromate. These discoveries were followed by the addition of man new members to the class of the
Sulphur dyes prepared by the action of Sulphur and alkalis, under the influence of heat, upon a variety of
phenols, amines, nitro compounds, and quinoneimines.

2.2 Properties of Sulfur Dyes:

 Economical dyeing with excellent tinctorial value and good build up properties.
 Good overall colorfastness properties such as wash fastness, light fastness, perspiration fastness
etc. Moderate fastness to crocking and poor fastness to chlorines bleaching agents such as
bleaching powder and sodium hypochlorite.
 Limited shade range to produce only dull shades and there is no true red dye in the range.
 These dyes can be applied by exhaust, semi continuous or continuous dyeing methods on garment,
yarn, knits, fabric as well as loose stock etc.
 Available in powder, granules and liquid forms.
 Sulphur black 1 is the major black dye used world vide for dyeing of cellulosic’s.
 The conventional dyeing process is not environment friendly due to pollution problems of sodium
sulphide as well as sod/pot. Dichromate.
 When dyed by using nonpolluting reducing and oxidizing agents the process is environment
friendly.
2.3 Types of Sulfur Dyes:
There are three classes of sulfur dyes, which are available commercially,

1. Conventional water insoluble dyes which have no substantivity to cellulosic.

2. Solubilized sulfur dyes, which are water soluble and non-substantive to cellulosic.
3. Pre-reduced sulfur dyes, in the stabilized leuco compound form, which are substantive to
cellulosics.

2.4 Trade Names of Sulphur dye:

Trade name of Sulphur dye vary from country to country. Here some trade name given below with their
company and country name.
Table 2 Trade Names of Sulphur dye.

Trade Names Name of Manufacturer Country of origin

Calcogen Dyes Dept. American Cyanamid Co. USA
Pyrogene Ciba Switzerland
Thional Sandoz Switzerland
Solfo ACNA Italy
Sulfogene Du pont USA
Thional Imperial UK
Mitsui Sulpher Mitsui Chemicals Ind. Co. Ltd Japan

2.5 Mechanism of The Sulfur Dyeing:

The application of the sulfur dyes involves several steps, which are described as given below,

2.5.1 Dissolving The Dyestuff: The dye Is taken in an SS vessel (size of the vessel should be selected
as per the quantity and solubility of the dyes) and pasted well with a good alkali stable wetting agent and
small quantity of soft water. Arequired quantity ofsoda ash may be added to neutralize any acid formed
in the dyestuff during strong. (If the acid is not neutralized, it will react with the sodium sulphide, resulting
into formation of H2S gas, which will result into incomplete and Poor reduction of the dyes). It is very
important that the dye dissolution must be complete otherwise particles of the undissolved dyes may
deposit on the surface of the substrate resulting into patchy dyeing and poor rubbing / washing fastness.
2.5.2 Reducing The Dyes to Form a Leuco Compound: Chiefly sodium sulphide is used as a
reducing agent for the sulfur dyeing. The quantity of the reducing agent depends upon the shade depth
and M: L of the bath. For complete reduction the required quantity of the sodium sulphide is dissolved in
a separate container and solution is allowed to settle for 10-15 min. Before decanting the clear solution
into the dye dissolving vessel. Further boiling water is to be added to make up the required volume, then
heated to boil for 10-15 minutes either by live steam or indirect heating, for complete reduction of the
dyestutf.

2.5.3 Dyeing with The Reduced Dyes: It is advantageous that the goods are scoured well before
dyeing, to have a satisfactory absorbency for better penetration. The dye bath is kept ready with small
quantity of the alkali stable and aompatible wetting agent, a dye bath stabilizer, sodium sulphide and
caustic soda or soda ash to maintain the alkalinity of the dye bath. The dye solution is then added through
a filter cloth slowly over 15-25 min- utes and then run for another 15 minutes at 40-50 oC, then
temperature is raised to 60oC and electrolyte is added in at least 3 portions. The quantity of salt added is
depends upon the type of shade, depth and dyestuffs, however a maximum quantity does not exceed more
than 15 gpl. The temperature is then raised to above 80oC or even boil depending upon the dyes and kept
for sufficient time to get the desired shade.
After getting the correct shade the bath is either dropped by draining the contents or by collecting it in the
storage tanks for reuse after replenishing with fresh dyestuffs.

2.5.4 Washing Off the Un Exhausted Dyestuff: With an objective of achieving the highest possible color
fastness results such as, washing, rubbing, light and perspiration, the material is washed and rinsed several
time with fresh water to remove maximum possible loose residual dye as well as sodium sulphide from
the material. At the end of the washing process the water should be clear, with no further leaching out
color. After washing the material is given a hot wash at 700C.

2.5.5 Oxidation Back to The Parent Dye: The oxidation is done to reconvert the leuco compound
back to insoluble parent dye. There are number of methods available for oxidizing the leuco compound
which are used either independent or in combination, such as-
a. Oxidation by exposing the dyed material to atmospheric oxygen.
b. Oxidation by the dissolved oxygen in the fresh water.
c. Chemical oxidation, by employing different oxidizing chemicals, such as-
 i. Acetic Acid.
ii. Sodium perborate in cold at neutral pH.
iii. Hydrogen peroxide and acetic acid.
iv. Potassium or sodium bicarbonates and acetic acid.

2.5.6 After Treatment: After oxidation and hot wash, the material is neutralized with soda ash to
adjust the pH and then soaping treatment is done with a neutral soap and soda ash at boil. Followed by a
hot wash at 850C.

2.5.7 Dye Fixing Treatment: Optifix is a cationic dye fixing agent, which is applied in alkaline
conditions (at a pH of 10-11), and is a suitable dye fixer for Sulphur dyed material to improve the color
fastness.

2.5.8 Softening: A suitable (compatible) softener can be applied to the dyed material as per the intended
end use and dyestuff applied.

2.5.9 Final Treatment: To avoid the tendering of the dyed material final wash is given to maintain a
slight alkaline pH by a weak base or acid neutralizing agent at the end without further washing. Following
treatments are recommended,
a. Soda ash wash 2-3 gpl.
b. Sodium Acetate 2-3 gpl.
c. Tetrasodium pyrophosphate 5.0 gpl.
d. Lime and tannic acid treatment.

2.5.10 Use of Standing Bath: Since a large quantity of the dye always present in the unexhausted
form in the spent liquor, this remaining dye can be reused, after replenishing with fresh dye. This system
is particularly suitable when producing repeated lots of the same shade with a single dye, such as black.
The dye liquor at the end of dyeing cycle is collected in the tanks, to replenish the bath a separately made
dye solution is added and calculated quantities of sodium sulphide, soda ash as well as salt are added. The
final volume is made up to the required level and reused. Usually a 50 -70% dye is replenished in case of
blacks. The spent bath use is not recommended in case of mixture shades, due to difference in the
exhaustion and fixation of individual dyes.
2.6 Sulphur Dyeing auxiliaries:
Basically three types of auxiliaries required in Sulphur dyeing process. This are mentioned below.
2.6.1 Reducing Agent: The two most important reducing agents for Sulphur dyes are Sodium
sulphide (Na2S) And Sodium Hydro sulphide (NaHS). The Sulphur dyes contain Sulphur linkage within
their molecules. They are Insoluble in Water but can be reduced to become soluble in water by treating
with reducing agents and shows substantantivity towards cellulose. Sodium sulphide acts as reducing
agent that breaks the Sulphur linkage break down the molecules into simpler components can easily
penetrate the fabric surface.

2.6.2 Oxidizing agents: After dyeing, the reduced, water soluble form of the dye has to converted
into the original water-insoluble form by oxidation using a wide range oxidizing agents. Dichromate
Acetic acid, Hydrogen per-oxide, ammonium persulphate used as oxidizing agents. The thiols containing
the – SH groups are readily oxidized in the fiber to the original insoluble Sulphur dyes by oxidizing agent
and gives a color with very good wet fastness properly.

2.6.3 Sequestering agents: Sequestering agents based on sodium hexametaphosphate the sodium salt
of ethylene diaminetertra acetic Acid (EDTA) are widely used in dyeing with Sulphur dyes where the
water quality is low. Wetting agents- majority of Sulphur dyes are unaffected by most wetting agents.
These are usually Non-ionic surfactants and should be avoided, both in pre-scouring and in the dye bath
itself.

2.7 Common Problem of Sulphur dyes:

Common problem of Sulphur dyes is mentioned below.
2.7.1 Poor wash and rubbing fastness: Poor washing and rubbing fastness is generally caused by
improper color dissolution, color precipitation, poor solubility of the dyes, poor and insufficient washing
after dyeing of unexhausted dyes and poor or insufficient soaping treatment.
To get overall good fastness properties –
a. The dye dissolution must be complete and it should be filtered before adding to the dye bath,
because insoluble dye particles, if present, will stick at the outer surface of the substrate causing
unleveled dyeing and poor wash and rub fastness.
 b. The color should be dissolved in sufficient quantity of water, by keeping in mind the maximum
solubility of the dye.
c. The water and the salt should be free from calcium and magnesium, which, if present will make
insoluble inert salts, which precipitates especially in the closed dyeing machines, in the form of
sludge.
d. The washing after dyeing and soaping treatment must be efficient to clear all the unused dye as
well as chemicals, before going to the next operation such as oxidation and neutralization
respectively.

2.7.2 Bronziness: There are various reasons for bronziness in the sulphur dyed material such as, in
sufficient quantity of sodium sulphide or reducing agent, resulting into quick oxidation of surface dyeing.
The presence of excess dyestuff on the material caused by high concentration of of dye or electrolyte,
delay between dropping of bath and washing, oxidation step. Following are the corrective actions for
correcting and avoiding the bronziness problem.
a. Proper dissolution of the dyestuff.
b. Thorough washing and treatment with reducing agent before oxidation.
c. Use of surfactants, sequestering agents, dispersing agents, dye bath stabilizers, and antioxidants in
reducing bath.
d. Using sufficient and calculated quantity of reducing agents.
e. Using appropriate quantity of electrolyte e.g. less than 15 gpl.
f. After treatment with 2-3 gpl TR oil+ 1-2 cc/ltr of ammonia in luke warm bath, to overcome the
problem.
g. Treatment with soap solution at boiling temperature.
h. Using a blank bath of sodium sulphide.

2.7.3 Tendering: Tendering means the loss of strength or degradation of cellulosic materials upon
storage. The tendering is caused by the acid formation from the free sulphur present in the dyed material
by the action of moisture and air. The acid produced reacts with cellulose and degrade it, resulting in loss
of strength. The tendering can be minimized by giving after treatments with acid neutralizing agents or by
weak alkaline washing at the end of dyeing process.
2.7.4 Poor color value: Poor color value is caused by insufficient amount of reducing agent, presence
of calcium salts in water and salt, over reduction of dyestuff, over oxidation etc.

2.8 Stripping of Sulphur Dyes:

Partial stripping of Sulphur dyes can be done by treating in a blank bath of reducing agent (6 g/l sodium
sulphide) at a temperature as high as possible. A blank bath containing 4.5 – 9 g/l sodium hydrosulphite,
2 – 3 g/1 sequestering agent at 90 – 95°C will strip off 10 – 20% of dye, while addition of a stripping
agent such as polyvinyl pyrolidine will remove a further 10 – 20%. It is advisable to redye from fresh
bath.
3 Azoic Dye:
Dyes having an azo group (-N = N-) structure in the molecular structure are collectively referred to as
azoic dyes. Azoic dyes are the most widely used types of synthetic dyes, accounting for more than 50%
of synthetic dyes. Common azoic dyes include acid, direct, active, cationic dyes and so on. They are
widely used in the dyeing and printing of a variety of natural and synthetic fibers. They are also applied
in the coloring of paints, plastics, rubber, and the like. Azoic dyes have the advantages of wide
chromatographic range and strong color fastness, so they are widely used for the dyeing in textile industry.

In the production of azoic dyes, diazotization and coupling reactions are two main processes and basic
reactions, and the reaction process is affected by various reaction conditions. A small amount of azoic dye
is also synthesized by oxidative condensation rather than by 2 coupling reaction of a diazonium salt.
Diazotization and coupling are two important reactions that are commonly used for dyeing and printing.

3.1 History of Azoic Dye:

In 1834, Mitseherlich prepared azobenzene by adding potassium hydroxide and nitrobenzene in an ethanol
solution. However, the production and application of azoic dyes was after 1858. After the first commercial
azoic dye BismarkBrown was prepared in 1863, azoic dyes began industrial production.

In 1884, the synthesis of Congo red can be called a milestone in the history of the development of azoic
dyes. With Congo red as a dye, the printing process can be greatly simplified without the addition of a
catalyst. Moreover, different colors can be obtained by adjusting the structures of azoic dyes.

According to statistics, in 1998, azoic dyes accounted for 60% to 70% of dye market of the world. At
present, in addition to dyeing textile materials, azoic dyes can also be used for dyeing chemical fibers,
paper, leather, food, cosmetics and other industrial products.

The azoic dye also has photochromic characteristics, so that it can be used as a recording medium for an
erasable rewritable optical disk after the polymer film is doped with ‘an azoic dye. In addition, azoic dyes
can use in modern high-tech fields such as liquid crystal display, dye laser, and fluorescent labeling of
DNA molecules in life sciences.
3.2 Properties of Azoic Dyes:
 Azoic dyes are directly insoluble.
 Excellent light fastness.
 Heat resistance moderate.
 Good wash fastness.
 Poor rubbing fastness.
 They contain water insoluble Azo group (-N=N-).
 They are fund of solid and powder form.
 Toxic and hazardous.
 Salt increases Substantivity.

3.3 Application Methods:

The four steps of application of azoic colours are:
1 Dissolution of naphthols.
2. Naphtholation.
3. Conversion of bases into diazo compounds.
4. Development or coupling.
The dyeing follows after treatment like repeated cold wash, hot wash, acid treatment for neutralization
and thorough soaping.

3.3.1 Dissolving of Naphthols: Naphthols are insoluble in water. They are treated with caustic soda
to make them soluble in water when they are converted into sodium salt or naphthola.
There are two methods of dissolving naphthols, namely:
1. Hot dissolving method.
2. Cold dissolving method.
In hot dissolving method, the naphthol is pasted with a wetting agent (T.R. Oil) and a small quantity of
hot water is added to make a smooth paste. The required quantity of sodium hydroxide is added and boiled
until the milky dispersion is converted into a clear solution. The remaining quantity of cold water is added
to make the solution of desired concentration. In the case of Naphthol AS - SW, AS - SG and AS SR, the
powder is pasted with the wetting agent and required quantity of caustic soda solution (620Tw or 366 g /l)
is added. The paste is heated in a water bath or kept overnight, then remaining water is added.
Formaldehyde, if required, may be added after cooling down to room temperature.
In cold dissolving method, the naphthol is pasted with industrial alcohol or methylated spirit. Required
caustic soda solution (620Tw) is added with stirring. The quantities required are much less than those
required in hot method. The required quantities in hot and cold method are shown below in the table.

Table 3 Required quantities of chemical for dissolving 1 part of napthol.

Napthol Caustic soda solid Alcohol or spirit 40% Formaldehyde

AS-LB 0.2 (0.2) 1.25 0.5(0.5)
AS-SG 0.33 (0.1) 1.0 ×
AS-SR 0.33 (0.1) 1.0 ×
AS 0.5 (0.2) 1.0 1.0 (0.5)
AS-E 0.5 (0.17) 1.0 0.75 (0.5)
AS-BS 0.5 (0.17) 1.5 1.0 (0.5)
AS-OL 0.5 (0.17) 1.0 0.5 (0.5)
AS-EL 0.5 (0.17) 1.0 0.5 (0.5)
AS-BT 0.5 (0.2) 1.0 ×
AS-D 0.5 (0.17) 1.0 1.0 (0.5)
AS-PH 0.5 (0.17) 1.0 1.0 (0.5)
AS-TR 0.7 (0.17) 1.5 1.0 (1.5)
AS-BO 0.9 (0.2) 1.75 1.0 (0.5)
AS-G 1.0 (0.23) 1.0 ×
AS-SW 1.3 (0.17) 1.25 1.0 (0.5)
Notes: The quantity of wetting agent is just that required for pasting, usually equal quantity of napthol.
The bracketed quantities are for cold dissolving method.
Alcohol or sprit is required only for cold dissolving method.
For alcohol/sprit and formaldehyde, the quantities are by volume against weight of napthol.

3.3.2 Naphtholation: The second stage of application of azoic colors is the treatment of textile
substrates with naphthol solutions. As the naphthols have low affinity for cellulosic textile substrates, the
best method of their application is by padding method. Hence, the depth of azoic dyeing is normally
expressed in terms of grams per litre naphthol as in case of padding recipes. The quantity of fast base
required is not necessary to be mentioned as it is dictated by the coupling ratio, i.e. the quantity of fast
base required for unit weight of naphthol, which is constant for a naphthol-base combination.
However, depending on the availability of equipment, different dyeing methods are used, such as open
beck, tub-dip, circulating liquor, jigger, padding methods, etc. These involve different material to liquor
ratio and concentration of azoic components.
The total quantity of caustic soda present in naphtholation bath determines the stability of the solution,
resistance to air exposure and the quantity of alkali binding agent required in the developing bath.
Minimum quantities of caustic soda required in naphtholation bath are 1.6 and 33g/1 (25 and 5g/l for both
Naphthol AS-SGand AS-SR) for light and deep hades respectively. For Naphthol AS-G, maximum
concentration for deep Shade is 25 g/1and minimum for light shade is 1 g/1.
As the naphthol solution is colourless or of slightly yellowish tone, it is not possible to make a visual
assessment of the amount of the coupling component being absorbed at the end of impregnation. Hence,
careful preparation and control of impregnating liquor is necessary to ensure consistent final shade.

3.3.3 Diazotisation: Two general methods are used for diazotisation of fast bases, namely:
1. Direct method.
2. Indirect method.

Most of the bases are diazotised by the direct method. The method is suitable for bases; whose
hydrochlorides are easily soluble in water. The base is pasted with concentrated hydrochloric acid and
little cold water. Hot or cold water is then added with stirring. The solution is then cooled to 100C with
ice and the sodium nitrate solution (1:1) is added with vigorous stirring, maintaining the temperature in
the range of 100-120C (50C for Garnet GBC). Coupling will net occur if the pH is too low. Hence, after
keeping the solution for 20 minutes, the excess hydrochloric acid is neutralised with sodium acetate
crystals. The alkali binding agent, such as aluminium sulphate or acetic acid, is then added. Alum produces
sulphuric acid when dissolved in water,
Al2(SO4)3 + 6H2O 2Al(OH)3 + 3H2SO4
and it is this acid that binds sodium hydroxide:
H2SO4 + 2NaOH → Na2SO4 + 2H2O
The solution is then filtered and made up to the required volume depending on the concentration of the
fast base required. With Red RC and Red KB, aluminium sulphate is preferred to acetic acid.
The indirect method of diazotisation is used for the bases, hydrochlorides of which are not easily soluble
in water. The fast base is pasted with a little water and sodium nitrate solution (1:1) is then added. More
hot or cold water is added with stirring The mixture is added to a solution of hydrochloric acid 320Tw
with continuous stirring, maintaining the temperature in the range of 10-15°C using ice. After keeping the
solution for about 20 minutes the excess hydrochloric acid is neutralised with sodium acetate and the
alkaline binding agent such as acetic acid or alum/aluminium sulphate, is added. The solution is filtered
and made up to the required volume. The quantities of various chemicals required for diazotization of fast
bases by direct and indirect methods are shown in below the table.

Table 4 Chemical required in parts for 1 unit of fast bases for diazotization.

Fast Bases 1 2 3 4 5 pH
Yellow GC 5+ 1.2 0.5 1.0 0.75 4-5
Orange GC 5+ 1.2 0.5 1.0 0.75 4-5
Scarlet GGS 4 2.0 0.36 2.5 × 4-5
Scarlet RC 20 1.0 0.4 0.75 0.5 4-5
Red KB 10+ 1.0 0.4 0.75 0.6 5.5-6.5
Red RC 10+ 1.0 0.5 0.75* 0.3 5.5-6.5
Garnet GBC 15 1.2 0.32 1.25 × 4-5
Orange GR* 2.0 2.25 0.55 1.2 0.7 4-5
Red B* 1.5+ 1.75 0.5 0.85 0.75 4-5
Bordeaux GP* 2.0+ 1.75 0.5 0.85 0.75 4-5
Marked bases are diazotised by indirect method.

Details of chemicals:
1. Cold water, + hot.
2. Hydrochloric acid, 320Tw.
3. Sodium nitrite.
4. Sodium acetate (* Extra 5g/l required in developing bath)
5. Acetic acid (50%) as alkali binding agent, alternately aluminium sulphate, equal to the weight of
base except for Scarlet RC and Red KB.
pH = Optimum pH for developing bath.
Fast colour salts are freely soluble in water. Before development, these are to be dissolved in water, first
by pasting with little water and then by adding five times water maintaining the temperature at 30°C. The
solution is kept for 5-10 minutes and filtered through a fine cloth.

3.3.4 Development or Coupling: The naphtholated material is treated with the diazonium solution
in the development bath for 20-30 minutes when the final shade appears on the material. The development
may be carried out in long liquor open beck or jigger or in short liquor as in tub or padding mangle.
An addition of 25 g/l common salt is made in all development baths except for Fast Black K. 10 g/I
common salt is added in case of Garnet GBC Case or colour salt. Common salt is omitted when
development is done by padding or in highly concentrated solutions.
In many cases, the coupling is quite slow, which is unfortunate, because it allows more time for the
naphthol to migrate. To make the reaction as rapid as possible, the concentration of the diazotised base
should at no time fall below 0.5 g/1. The addition of an assistant, such as a sulphated fatty alcohol or an
ethylene oxide condensate (eg. Remol AS), tends to improve the speed of the reaction and also to keep
the pigments formed in the solution as suspension. These are particularly important in the case of package
dyeing machine as the deposition of such pigment may disturb the flow of liquor. The actual quantity of
diazotised base required in the development depends on the quantity of naphthol in the naphtholating bath
and the coupling ratio. The coupling ratio is the quantity of fast base required for 1 part of naphthol. The
coupling ratios of various naphthols and fast bases are shown below in the table.

Table 5 Coupling ratios of various naphthols and fast bases.

Fast Bases AS ASG AS-BS AS-SW AS-TR AS-LB AS-SG

Yellow GC 0.95 1.05 0.8 0.8 0.8 0.37 0.31
Orange GC 0.95 1.05 0.8 0.8 0.8 0.37 0.31
Scarlet RC 1.2 1.25 1.05 1.05 1.05 0.03 0.47
Red KB 1.05 1.15 0.90 0.90 0.90 0.42 0.42
Red RC 1.10 1.20 0.95 0.95 0.95 0.44 0.42
Garnet GBC 1.47 1.57 1.25 1.25 1.25 0.58 0.53
Orange GR 0.75 0.75 0.60 0.60 0.60 0.27 0.25
Red B 0.90 0.95 0.75 0.73 0.75 0.35 0.30
Bordeaux GP 0.90 0.95 0.75 0.75 0.75 0.35 0.30
For example, when naphtholation is done with 5 g/1 Naphthol AS, the concentration of Yellow GC base
in the development bath should be 5x0.95 = 4.75 g/l where 0.95 is the coupling ratio.
3.4 After-treatments: After developing, the material is washed repeatedly in cold water, then in hot
water and rinsed in acidified water (3 ml/1hydrochloric acid, 320Tw). It is then washed again with cold
water and carried forward for soaping. Soaping removes loosely fixed azoic pigments from the surface of
the material, thereby increasing fastness to rubbing, light and chlorine. It also develops the true shade of
azoic combinations. Soaping is carried out at boil with 3 g/l soap or detergent and 2 g/l soda ash for a
period of not less than 15 minutes, giving adequate agitation or squeezing to dislodge the adhering
particles. It is then washed well and dried.
The combinations of Yellow GC with Naphthol AS and AS-SW and Orange GC with Naphthol AS are to
be soaped at 65°C. The reddish streaks of Naphthol AS-G combinations with fast bases, namely Yellow
GC, Orange GC, Scarlet GGS, Red KB, and Red RC, caused by faulty dyeing, can be removed by boiling
with soap along with 0.5g/l sodium hydrosulphite and 0.5 ml/l caustic soda, 62°Tw. With some other
combinations, it may lower chlorine fastness.

3.5 Problem in dyeing with azoic color:

1) Uneven shade: The reason for uneven shade are-
 Faulty liquor movement.
 Faulty fabric movement during naphtholation.
 Improper naphtholation.
 Improper hydroextraction.

2) Naphthol Migration: The naphthol in fabric goes to base solution of the bath and reacts with base there
other than in the fabric. This is called naphthol migration. This occurs due to-
 Improper selection of naphthol.
 More moisture in fabric.

3) Slow coupling reaction: The reasons for slow coupling reaction are-
 Improper selection of base to mix with naphthol.
 Wrong range of pH in bath, i.e. more acidity.

4) Blinding effect: In case of rayon dyeing a blinding effect may occur, due to-
 Presence of alkali during naphtholation.
 Improper value of pH.
 Presence of alkali in coupling bath.
This blinding effect may be presented by using alkali binding agent (e.g. alum).

5) Pigment on fibre surface: The reason for this are:

 Unfixed dye on fibre surface
 Improper washing after dyeing

This can be prevented by-

 Using binding agent for alkali.
 Curing process.

3.6 Stripping of Azoic Colorants:

Azoic dycing can be stripped with powerful reducing agents, although dyes based on highly substantive
naphthols are difficult to deal with. Certain yellow azoic dyeing is resistant to reducing agents and can,
therefore, be only partially stripped.
The stripping is carried out with sodium dithionite in the presence of a cation-active substance such as
Matexil SC-A50 (cetyl trimethyl ammonium bromide). The material is treated at boil for 30-45 minutes
in a liquor made up with 2% Matexil SC-A50 and 4% caustic soda. The temperature is then dropped to
just below the boil and 5-6% sodium dithionite is added. After a further 30-45 minutes, the liquor is run
off and stripping is completed by bleaching with sodium hypochlorite. Benzimidazoles are also claimed
to increase the stripping action of alkaline hydrosulphite baths. Polyvinylpyrrolidone, under various
proprietary names, e.g. Albigen A (BASF), is also a useful addition to the stripping bath. Combinations
from substantive naphthols may be difficult to strip completely. In general, the last traces of naphthol are
very difficult to remove.

Conclusion:
Dyes that are used by the textile industry are now mostly synthetic. They are mostly derived from two
sources namely, coal tar and petroleum-based intermediates. These dyes are marketed as powders,
granules, pastes or liquid dispersions. The concentrations of active ingredients typically range from 20 to
80 percent. The textile dye segment is characterized by new dyes. These new dyes are regularly developed
for meeting the demands of new technology, new kinds of fabrics, detergents, advances in dyeing
machineries, along with overcoming the serious environmental concerns posed by some existing dyes.
However, Vat dyes are widely used for colouring cellulosic fibre, especially cotton fibre along with
viscose rayon, leather, and other fibres. Indigo dye is the most used vat dye as it becomes the base for
dyeing denim fabrics.

The sulfur dyes are widely used in piece dyeing of traditionally woven cotton goods such as drill and
corduroy fabrics. The cellulosic portion of polyester-cotton, and polyester–viscose blend is dyed with
sulfur dyes.

On the other hand, Azoic dyes are used for producing bright shades of colour such as orange, red, scarlet,
navy blue, and black color.
Whatever, certain azo dyes can break down under reductive conditions to release any of a group of defined
aromatic amines. Consumer goods that contain listed aromatic amines originating from azo dyes were
prohibited from manufacture and sale in EU countries after the German ban in 1997. Many azo pigments
are non‐toxic, although some, such as dinitroaniline orange, ortho nitro aniline orange, or pigment orange
1, 2, and 5 are mutagenic. Likewise, several case studies have linked azo pigments with basal cell
carcinoma.

Without this, there are also many other dyes used in the textile sector, such as Acid dyes, Basic dyes,
Reactive dyes, Direct dyes, Disperse dye, Mordant dyes, etc.