Topics of Discussions

1. 2. 3. 4. 4 5. 6. 9. Review on "Sulphur Dyeing" History of Sulphur Dyes Synthesis of Sulphur Dyes Chemical P i i l Ch i l Principles of Sulphur Dyes fS l h D Structure of the Sulphur Dye market Sulphur Dyeing Process Benefits

History of Sulphur Dyes y p y
Significant Development
1873 Chance discovery Attempt to absorb an alkaline sulphuric liquor with sawdust cotton fabric that came into contact with the substance turned yellowish brown First sulphur dyes from defined chemical compounds produced by Vidal dyes when heated with sulphur or with sulphur and alkali G. Kalischer of Cassella developed Immedial Black V formed

1893 1897 1899 1909 1927

deep-bluish-black hue

Agfa introduced "Sulphur Black T" produced from inexpensive 2,4 dinitrophenol Sulphur Black 1 best-known sulphur dye L. L Haas and R Harz discovered Hydron Blue (Vat Blue 43 produced form carbazol R. 43, leucoindopheonol (VIII) Wolf von Heiman discovered Indocarbon (Sulphur Black 11)

Synthesis of Sulphur Dyes
Synthesis route for C. I. Sulphur Black 1 y p
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
Small sulphonated polymers Produced from organic intermediates with sulphur Cannot b split b k into the starting products be l back h d Halogen-free

Chemical reactions in Sulphur Dyeing Process
Reduction cleavage of disulfide bridges So ub e Soluble in aqueous alkaline solutions a a e so ut o s Affinity for textile fibre Oxidation of dyestuffs on fibre Insoluble in water Pigment cannot migrate out of fibre

Equation: R - S - S - R + 2e- ↔ R - S- + R - Sq Technical focus
90% of all continuous processes is one-bath pad-steam 80% of all exhaust processes are navy and black shades Denim application on Indigo ranges pp g g

Sulphur Black to be used for Denim
Product Name: C. I. Sulphur Black 1 Required Properties: Reduced sulphide quantity in dyestuffs Flexibility in use Either being reduced with sulphide or sulphide-free reducing agents (ecological issues) 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. Dextrose Monohydrate-Clariant recommends Glucose in combination with Caustic soda (Can be applied to other dyes but as instructed by the manufacturers & it might affect y g colour yield).

Glucose

Oxidizing agent-Selection depends on
Procedure used (continuous or exhaust dyeing) Fastness requirements Shade Dosing requirements Costs Environmental aspects

Recommended oxidation methods

1. Hydrogen peroxide (acidulated), pH 4,5, 70 °C 1 Hd id ( id l d) H 4 5 2. Hydron peroxide (alkaline), pH 10, 40 °C 3. Sodium bromate/metavanadate (acidulated), pH 4,5, 70 °C
Notes on oxidation methods
Oxidation with hydrogen peroxide in an alkaline medium is a simple method and produces clear shades but only d l h d b t l drawback i it reduces wet f t b k is d t fastnesses. Thi method i used when d i This th d is d h dyeing wound packages. Oxidation with hydrogen peroxide in an acid medium is a reliable method. The fastness and shades obtained are comparable with other common oxidation methods. 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 Dyeing : 100 % Cotton woven fabric : 30 g/l Hydron Blue R Stabilosol
Oxidation Hydrogen peroxide, pH 10, 40 °C Oxidation Sodium bromate, pH 4 - 4,5, 70 °C

Oxidation Hydrogen peroxide, pH 4 - 4,5, 70 °C

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

Exhaust Dyeing Common process
110 100 90 80 70 60 50 40 30

°C 45 45' 95 °C C 3 °C/min 10' 75 °C

5' 5' 5'

Rinse in overflow until liquor is clear

drain

10'

warm rinse drain cold rinse Oxidation min
0 20 40 60 80 100 120 140 160 180 200 220 240

Dye Reducing agent 20 Alkali Salt 10
0

10'

After-treatment in open-width washer (5 compartments) Boxes
1 2 3+4 5 Rinse at 20-40°C, water through put 4-6.0 l / kg fabric Oxidize with 4-5.0 g/l a suitable oxidizing agent, 70°C, pH 11.5–12.5 (replenishment solution of 40-50 g/l O idi i agent, feed 0.1 l/kg fabric) l ti f 40 50 /l Oxidizing t f d 0 1 l/k f b i ) 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 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?
To changes the Indigo shade To get more deep bluish black To have Special wash-down effects 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 Dyes l h
Economical dyes for muted and deep shades like dark brown, olive, navy and black 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

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