Sulfur Dyes

Lecture # 5
Textile Dyes and Dyeing
Dr. Rehan Abbasi
Contents
+ Introduction
+ Chemical structure
+ Classification
+ General properties
Introduction
+ Sulphur dyes are non-ionic, possess sulphur linkage, are water
insoluble and produce shades that are reasonably cheap and wash
and light fast.
+ Dyes are applied in reduced and solubilized anionic state possessing
affinity for cellulosic substrates.
+ After dyeing, oxidation is carried out to restore parent non-ionic dye
structure;
+ Sulphur dye-cellulose attachment is established through physical
forces with dye aggregation occurring in situ
Why sulphur dyes called sulphur dye?
+ In 1873 Sulphur dyes was discovered and its name was ‘Cacho
de Laval’, after few years they saw this dyes carried organic
vegetable matter which is sodium sulphide and sulphur. That’s
means it contains di-sulphide (s-s) linkage in their chemical
structure.
+ The dyeing process is carried out in an alkaline condition.
Dye-S-S-Dye
Chromophore Disulphide linkage Chromophore
Chemical Structure
Properties of Sulfur dyes
+ They contain sulphur linkages within their molecules
+ Sulphur dyes are insoluble in water
+ They are soluble in a solution of sodium sulphide (Na2S)
+ The sodium sulphide (Na2S) acts as a reducing agent, severing
the sulphur linkage and breaking down the molecules into simpler
compounds, which are soluble in water
+ The wash fastness is good, and the light fastness is satisfactory
+ But poor fastness to chlorine
Properties of Sulfur dyes (Cont.)
+ Anionic dye.
+ Water insoluble dye.
+ Sulfur dye is used to dye cotton, cellulose, regenerated cellulose.
+ Two stage dyeing.
+ Only few dark shade are available. (Navy, black, coffee).
+ Wash fastness excellent.
+ Rubbing fastness average.
+ Light fastness very good. If wash the fabric with metallic salt (copper sulfate ), its light fastness will be
excellent.
+ Very cheep dye.
+ Sulfur is unhygienic for nature and human body.
+ Sea water fastness is poor (because of Cl- anion).
Classification of Sulphur Dye
+ Sulphur dyes

+ Leuco sulphur dyes

+ Solubilised sulphur dyes

Mechanism of Sulphur Dyeing
+ The insoluble dye is converted to smaller soluble
componentscalled thiols by reducing agent
Dye.S – S.Dye + 2H Dye.SH + HS.Dye
(Insoluble (Reducing agent) (Thiols)
sulphur dye) Smaller components of dye
soluble in water

The thiols containing the SH group are readily oxidised in the fibre to the
original insoluble sulphur dye, giving a colour with a very good washing
fastness

Dye.SH + HS.Dye + O Dye.S – S.Dye + H2 O

Leuco form
+ Leuco is the colorless form of dye, creates as a result of its insoluble
form interacting with alkaline liquor. This color retunes upon oxidation.
+ This conversion is carried out by dilute aqueous solution of sodium
sulfide. This leuco compound has affinity towards cellulose fiber &
they sensitive to atmospheric oxygen.
+ This reduction form of sulfur dye absorbed by the fiber substance and
dyeing occurred.
+ After dyeing it finally again reconverted into insoluble form of dye by
chemical oxidizing with Na/K dichromate.
Dyeing of Cellulose with Sulphur Dye
Dyestuff is pasted Boiling water is then Dyebath is prepared
with soda ash and added to the paste with the dye paste
sodium sulphide until the dye + Sodium Chloride /
dissolves Glauber salt (Added
gradually at 1000C)

The fabric is then The extra liquor is The fabric is

oxidized with a squeezed off impregnated in the
solution of sodium immediately dye bath and dyeing
perborate at 40-500C is carried out at boil
for 20 minutes for 60 minutes

After oxidation, soaping is carried out at boil for 20 –

30 minutes followed by hot water and cold water
washing
Dyeing of cotton with Sulphur dyes
Recipe:
+ Dye = 8 – 12%
+ Reducing agent (Na2S) = 8 g/l
+ Alkali (Na2CO3) =10 g/l, NaOH=5g/l
+ Salt ( NaCl) =10g/l (increase affinity)
+ Wetting agent =1g/l
+ Sequestering agent =1g/l
+ Leveling agent =1g/l
+ Temp =80◦C
+ Time =40min
Dyeing of cotton with Sulphur dyes (Cont.)
+Oxidation and neutralization done simultaneously because they contain same PH
and temperature.
+CH3COOH =1g/l
+Na2Cr2O7 =1g/l
+Temp =50◦C
+Time =10min
Soaping:-
+Detergent =1g/l
+Temp =70◦C
+Time =5-10 min
After Treatment
The washing and light fastness can be improved by using one of
the following after-treatment
+ Treatment with metallic salt e.g. dicromate and copper sulphate
either alone or in combination
+ Topping with basic dye
Cotton goods dyed with sulphur colour can be topped with basic
dyes to get enhance brilliance shade and improved washing
fastness properties as well
Stripping of Sulphur dyes
+ Stripping is the process by which to remove the excess dye for
uneven dyeing or shade matching. In sulfur dyeing stripping is
done with the help of NaOCl.
NaOCl = 2-3 g/l
Temp = 70◦C
Time = 10 – 20 min
Uses of Sulphur dyes
+ The sulphur blacks are especially adapted for the dyeing of fast
blacks on hosiery, as also are the brown colors, as the dyestuff
stands the repeated washings and the effect of the acid
perspiration to which the color of hosiery is subjected.
+ Sulphur dyes are on of the most used for producing bright and
brown shade on cellulosic fiber products. Mainly used for cotton,
hemp, viscose fabric dyeing, and can also be used to top and
viscose fiber protoplasmic coloring. Sometimes also used in leather
and paper dyeing. Sulphur dyes is used both in dyeing and printing.
Faults of sulfur dyeing
+ Tendering.
+ Bronziness.

+ Tendering: Tendering is a strength loss fault of sulfur dyeing/ sulfur dyed

fabric. Cellulose fabric may degrade upon long storage. It is causes due
to formation of sulfuric acid. This fault is called tendering.
S + H2O +2O2 H2SO4
+ If we wash fabric with 2-3 g/l of buffer solution (CH3COONa), then this
problem will be eliminated.
Faults of sulfur dyeing
Bronziness: Bronziness is a fault of sulfur dyeing, where sulfur
black or navy color fabric may change to bronze or reddish shade.
Causes:
+ Excessive delay between lifting of the fabric from dye bath to
washing off.
+ Use excess amount of salt.
+ Use excess amount of dye.
+ Insufficient amount of reducing agent.
Advantages
+ The main advantage of using sulphur dye lies in their low cost, even when
producing deep shades on cotton with good wash and light fastness,
compared against other classes of cotton dye.
+ Consumption of costlier indigo in dyeing denim can be reduced by topping
or bottoming with sulphur dye. In topping, denim dyed with indigo to a lighter
shade is re-dyed with sulphur dye to develop the desired shade.
+ The bottoming process is just the opposite: denim dyed with sulphur dye is
then re-dyed with indigo, with the sulphur dye remaining at the bottom of the
indigo layer. The top or bottom can be accomplished by applying sulphur
dye in the pre-wash, final indigo bath, or in the after-treatment section.
Limitation
+ Inadequate tinctorial ability limits production of light shades.
+ Limited hue range – true red, orange and yellow cannot be produced.
+ Shades lack brightness (though this can be manageably .
+ Improved by topping with basic dyes.
+ Bronzing and Tendering
+ Not applicable on swimming costumes for fear of discolorization.
+ Not applicable on protein fibres due to the high alkalinity of the bath.
Thank You