Topics of Discussions

1. Review on "Sulphur Dyeing"

2. History of Sulphur Dyes
3. Synthesis of Sulphur Dyes
4
4. Ch i l Principles
Chemical P i i l off Sulphur
S l h Dyes
D
5. Structure of the Sulphur Dye market
6. Sulphur Dyeing Process
9. Benefits
Historyy of Sulphur
p Dyes
y
Significant Development
‰ 1873 Chance discovery
Attempt to absorb an alkaline sulphuric liquor with sawdust Æ cotton fabric that
came into contact with the substance turned yellowish brown
‰ 1893 First sulphur dyes from defined chemical compounds produced by Vidal Æ formed
dyes when heated with sulphur or with sulphur and alkali
‰ 1897 G. Kalischer of Cassella developed Immedial Black V Æ deep-bluish-black hue
‰ 1899 Agfa introduced "Sulphur Black T" produced from inexpensive 2,4 dinitrophenol Æ
Sulphur Black 1 Æ best-known sulphur dye
‰ 1909 LL. Haas and R
R. Harz discovered Hydron Blue (Vat Blue 43
43, produced form carbazol
leucoindopheonol (VIII)
‰ 1927 Wolf von Heiman discovered Indocarbon (Sulphur Black 11)

Synthesis of Sulphur Dyes

Synthesis
y route for C. I. Sulphur
p Black 1

Saponification

2,4 Dinitrochlorobenzene 2,4 Dinitrophenolate

Sodium salt
Sulfuration

2,4 Dinitrophenolate
Sodium salt
Synthesis of Sulphur Dyes
Proposed structure for C. I. Sulphur Black 1

F. Gordon and P. Gregory, Organic Chemistry in Colour (1983)

Chemical Principles of Sulphur Dyes

¾ Small sulphonated polymers
¾ Produced from organic intermediates with sulphur
¾ Cannot be
b split
l b back
k into the
h starting products
d
¾ Halogen-free

Chemical reactions in Sulphur Dyeing Process

Reduction cleavage of disulfide bridges
‰ So
Soluble
ub e in aqueous alkaline
a a e solutions
so ut o s
‰ Affinity for textile fibre
Oxidation of dyestuffs on fibre
‰ Insoluble in water
‰ Pigment cannot migrate out of fibre
Equation:
q R - S - S - R + 2e- ↔ R - S- + R - S-
Technical focus
‰ 90% of all continuous processes is one-bath pad-steam
‰ 80% of all exhaust processes are navy and black shades
‰ Denim application
pp on Indigo
g ranges
g

Sulphur Black to be used for Denim

‰ Product Name: C. I. Sulphur Black 1

‰ Required Properties:
¾ Reduced sulphide quantity in dyestuffs
¾ Flexibility in use
¾ Either being reduced with sulphide or sulphide-free reducing agents (ecological issues)
¾ High Concentration (In case of Liquid Sulphur)
Sulphur Dyeing Process
Dyeing mechanism
‰ Reduction
Convert the dye into soluble leuco form by adding reducing agent and alkali.
‰ Oxidation
Convert dyestuffs in fibre back into insoluble pigment form by adding oxidizing agent.

Reducing agent-Selection depends on

‰ Sulphur dye range
‰ Economic efficiency
‰ Environmental aspects
‰ Dyeing process
Ecological reducing agents
‰ Hydrosulfite/Glucose This so called binary system forms sulfuric acid in dye bath
which acts as an optimum reduction system for sulphur
dyeing. The redox potential of this binary system is lower
than that hydrosulphite alone. Therefore, there is no risk of
over reduction and thus destruction of sulphur dyes.
‰ Glucose Dextrose Monohydrate-Clariant recommends Glucose in
combination with Caustic soda (Can be applied to other dyes
but as instructed byy the manufacturers & it might
g affect
colour yield).
Oxidizing agent-Selection depends on
¾ Procedure used (continuous or exhaust dyeing)
¾ Fastness requirements
¾ Shade
¾ Dosing requirements
¾ Costs
¾ Environmental aspects
Recommended oxidation methods
1. Hydrogen
1 H d peroxide
id (acidulated),
( id l d) pH H 4,5,
4 5 70 °C
2. Hydron peroxide (alkaline), pH 10, 40 °C
3. Sodium bromate/metavanadate (acidulated), pH 4,5, 70 °C
Notes on oxidation methods
¾ Oxidation with hydrogen peroxide in an alkaline medium is a simple method and produces
clear
l shades
h d but
b t only
l d
drawback
b k iis it reduces
d wett ffastnesses.
t Thi
This method
th d iis used
d when
h d dyeing
i
wound packages.
¾ Oxidation with hydrogen peroxide in an acid medium is a reliable method. The fastness and
shades obtained are comparable with other common oxidation methods.
¾ Oxidation with sodium bromate contributes to slightly formation of AOX in waste water. It takes
place rapidly and is a reliable method.
Black dyeings oxidized in an acid medium requires a final buffer with soda ash and/or sodium acetate
to prevent any tensile strength loss.
Shade Comparison-Depending on the Oxidation Method
One-Bath Pad-Steam Process, pick-up 70%, 1 min steaming at 102 °C
Fabric : 100 % Cotton woven fabric
Dyeing : 30 g/l Hydron Blue R Stabilosol
Oxidation Oxidation Oxidation
Hydrogen peroxide, pH 4 - 4,5, 70 °C Hydrogen peroxide, pH 10, 40 °C Sodium bromate, pH 4 - 4,5, 70 °C

Wetting Agents
Only anionic wetting agents can be used for dyeings with sulphur dyes
Î Check the wetting agent by the "Hydron Blue Test“ prior to use.
Nonionic wetting agents can lead to precipitation of the dye
Î Result will be unevenness,
unevenness less yield,
yield poor rubbing fastness
fastness.

Exhaust Dyeing
Common process
110
°C
100 45' 95 °C
45 C
3 °C/min
90

80
10' 75 °C
70

60
Rinse in drain
overflow until 10'
50
liquor is clear
5' 5' 5'
40

30 warm rinse
Dye drain
Reducing agent 10'
20 cold rinse
Alkali
10 Salt Oxidation
0 min
0 20 40 60 80 100 120 140 160 180 200 220 240
After-treatment in open-width washer (5 compartments)
Boxes
¾ 1 Rinse at 20-40°C, water through put 4-6.0 l / kg fabric

¾ 2 Oxidize with 4-5.0 g/l a suitable oxidizing agent, 70°C, pH 11.5–12.5 (replenishment
solution
l ti off 40-50
40 50 g/l
/l O
Oxidizing
idi i agent,t feed
f d 0.1
0 1 l/kg
l/k fabric)
f bi )

¾ 3+4 Soap with 1-2.0 g/l detergent, pH 9-10, 2 ml/l acetic acid 80%, 95-100°C (must be kept
constant), replenishment 10-20 g/l detergent, feed 0.1 l/kg, counter-flow principle

¾ 5 Rinse at 40°, add acetic acid to set pH 5-6 (check with pH meter). Up to 80°C is possible,
if cylinder dryer follows.

Remarks: keep in all compartments selected temperature, pH and water-flow constant

To cover typical indigo blue shade

Why to apply a sulphur top?

¾ To changes the Indigo shade
¾ To get more deep bluish black
¾ To have Special wash-down effects
¾ To eliminates contamination of indigo dye bath with sulphur dye
Other Dyeing Processes
Dyeing of Cellulose/Polyamide blended fabric with Sulphur Black
‰ One-bath one-step black dyeing
‰ Short dyeing time
Dyeing of Polyamide micro-fibre
‰ High light and wash fastness
‰ Deep Black
Dyeing of cationic ally pre-treated Cotton
‰ wash-out look
Benefits
Benefits for using Sulphur
l h Dyes
‰ Economical dyes for muted and deep shades like dark brown, olive, navy and black
Î this is the shade range that predominates in sulphur dyes
‰ Favourable cost structure at process
‰ For Black very high perspiration and wet light fastness
‰ Especially suitable for deep shades with excellent appearance of the goods
‰ Good consumer fastness properties
‰ Various possibilities for ecological dyeing processes