Sulphur Dyes

Sulphur Dyes
Sulfur dyes are the most commonly used dyes manufactured for cotton. They are
inexpensive, generally have good wash-fastness, and are easy to apply. Sulfur
dyes are predominantly black, brown, and dark blue. Red sulfur dyes are
unknown, although a pink or lighter scarlet color is available.
The sulphur dyes are named so because of the presence of sulphur atoms in their
molecules. Like direct dyes, sulphur dyes are also quite cheap for dyeing
cellulosic textiles with limited color fastness properties.
Sulfur linkages are the integral part of chromophore in sulfur dyes. They are
organic compounds consisting of sulfide (–S–), disulfide (–S–S–) and polysulfide
(–Sn–) links in heterocyclic rings. They feature thiazoles, thiazone, thianthrene,
and phenothiazonethioanthrone subunits. Being nonionic, sulfur dyes are
insoluble in water.
Properties of Sulphur Dyes

1. Sulphur dyes have Sulphur linkage within their molecules.
2. Sulphur dyes are water insoluble dyes.
3. To increase the substantivity of this dye they are to be converted in to
soluble leuco form by treating them with reducing agent.
4. Sulphur dyes have moderate to good light fastness with rating about 4.
This light fastness may be improved by an after treatment with metallic
salt.
5. These dyes have fair to good 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.
Classification of Sulphur Dyes

Sulphur dyes are classified based on chemical structure and application.
 Chemical classification includes two types, sulphur dyes and sulphurised
vat dyes.
i) Sulphur dyes include only sulphur linkages and are reduced with Na2S
at boil.
ii) Sulphurised vat dyes retain both sulphur linkage as well as carbonyl
group as chromophore and are reduced with Na2S2O4 and NaOH
combination at specific temperature but cannot be reduced with Na2S.
Mechanism of Sulphur Dyes

 The Sulphur dyes contain Sulphur linkage within their molecules.
 They are insoluble in water but can be made soluble in water by treating
them with reducing agents.
 This also makes them substantive towards cellulosic fibres.
 Na2S acts as reducing agent that breaks the Sulphur linkage and break down
the longer molecules in to simple components which can penetrate the
material (fiber/fabric) surface easily.
 This thios containing the –SH groups are readily oxidized by the action of
atmospheric O2 or any other oxidizing agents (eg. Na2Cr2O7).
 This reconverts the water soluble leuco form of Sulphur dye into previous
water insoluble form which has a very good wash fastness property.
 Sulphur dyes are negatively ionized. Addition of salt improves efficiency of
dyeing by increasing physical force.
 Oxidizing is occurred as like ----
Reducing Step of Sulphur Dyes

Reducing step is the most important in the application of sulphur dyes. Unless the
dyes are converted into the completely soluble form, the full color value cannot be
achieved. The solubility of reduced sulphur dyes varies appreciably from dye to
dyes. The reducing agents used for sulphur dyes are:
1) Na-Sulphide (Na2S)
2) Na-Hydro Sulphide (NaSH)
3) Thioglycolic Acid (HS-CH2-COOH)
 But, Na Sulphide is the most widely used reducing agent for dissolving
sulphur dyes. These may be replaced by Na-Hydrosulphide in some cases.
 Again, over reducing of the dye may take place, leading to a product having
lower affinity for cellulosic fibres.
 Hence lower color yields are obtained along with wastage of dyestuff.
 In some cases lower wash fastness results if Na-Hydrosulphide is used.
 It also decreases the life time of the vessel.
Dyeing Steps of Sulphur Dyes

 Once reduction and solubilisation is over, wet cotton is dyed at 90–95°C for
30–60 min after which salt is added and dyeing is continued for further 1.5–
2 h; the bath is drained out and dyed cellulose is washed thoroughly.
 Due to the presence of large amounts of dye required to produce deep shades
and its moderate affinity for cellulose, dyeing time before and after salt
addition should be kept on the higher side to promote exhaustion of bath.
 Reduction as well as dyeing of cotton is preferably carried out in jigger or
winch.
 At least four turns are imparted in dye bath after which salt is added and
further eight turns are imparted at boil.
 The bath is dropped, dyed cotton is cold washed for 2 turns, oxidized for 2–4
turns followed by soaping, washing and padding with CH3COONa.
Oxidation Step of Sulphur Dyes

After dyeing the reduced water soluble form of the dyes have to be converted in to
the original water insoluble form by oxidation.
The commonly used oxidizing agents are-
1) Potassium dichromate (K2Cr2O7)
2) Na-Perborate (Na2H4B2O8)
3) Na-per carbonate (NaHCO3)
4) Na-peroxide (Na2O2)
The method of oxidizing agent selection plays an important role in the

development of correct shades & their optimum fastness properties. Using of
different oxidizing agents may give the following results-
1) Use of perborate or per carbonate in presence of acetic acid gives brighter shade.
2) Treating dyed material with dichromate without rinsing reduces color losses and
causes dull shade.
Defects of Sulphur Dyeing
Stripping of Sulphur dyes

 Unevenly dyed shades on cellulosic materials with sulphur dyes may be
corrected by a treatment with a warm solution of Na2S in the presence of
polyvinyl pyrolodine.
 If this method is found to be ineffective then the uneven dyed material may
be treated with a solution of a NaOCl or bleaching powder (2-3 gm/litre of
available chlorine).
 In some cases bleaching with KMnO4 solution may be effectively carried
out. In other cases the dyed material may be treated with warm NaOCl
solution in the presence of NaOH.
 The uneven dyeing of material causes due to the following reasons:
i) The oxidation of dye during dyeing when the material comes in contact with
air.
ii) Presence of gummy material on the fabric.
iii) Defective Dye.

Sulphur Dyes

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Sulphur Dyes

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Sulphur Dyes

Properties of Sulphur Dyes

Classification of Sulphur Dyes

Mechanism of Sulphur Dyes

Reducing Step of Sulphur Dyes

Dyeing Steps of Sulphur Dyes

Oxidation Step of Sulphur Dyes

The method of oxidizing agent selection plays an important role in the

Stripping of Sulphur dyes

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