Cold Brand Reactive Dyes-For Trial

Glimpse of reactive dyes

Stephen and Rattee, two textile chemists, were the first to show that certain dyes can chemically react with cotton fibre, forming covalent bonds and thus becoming part of fibre itself. Leveling archived in these dyes good and takes place very rapidly as compared to conventional dyes because of the small molecule size.

Combination of brightness, fastness and ease of application associated with reactive dyes enables this class of dyes to be the major class of dyes used today to colour cellulosics in Industries.

Properties of reactive dyes

The reactive dyes on account of sulphonic acid group in their molecule readily soluble in water.

Clarity and brightness of hue and easy penetration hence good leveling thanks to small molecule size of the dyes.

Textile material coloured with reactive dyes have to be thoroughly rinsed and soaped as the reactivity of the molecule towards hydroxyl group (from water), and dye reacted with water get deactivated and create poor rubbing fastness. Superficial dyes needs to be removed for better rubbing fastness. Formation of covalent bond between fibre and dye molecule takes place under alkaline condition. Hence a pH of around 9-10 with alkali(Na2CO3, NaOH, Na3PO4, NaHCO3, Na2SO3, Na2SO4 etc) maintained.

How dye reacts with fibre

Based on mechanism of bond formation reactive dyes can be classified in two categories: Tri-azinyl type ring system (nucleophillic substitution/etherification reaction).

Beta-Sulphatoethyl sulphone type( nucleophillic addition reaction/etherification reaction)

Industrial Range in each categories

1.Tri-aziny type dyes-- Procion dyes (From ICI), Drimarene (Clariant), Levafix (Bayer), Cibacron (Indo-swiss), Solidazol (Cassella), Sumifix supra (Sumitomo), Kayacelon (Nipon Kayaku).
2. Vinyl sulphone dyes Remazole dyes (Dystar), Levafix dyes (bayer) Primazin (BASF)

Based on reactive system these dyes can be classified under:

1. Mono functional dyes( eg. H brand/Hot brand reactive dyes) 2. Bi functional dyes ( eg M brand/cold brand reactive dyes). 3. Multi functional dyes( eg. HE dyes). Hot brand reactive dyes are characterized by presence of reactive groups at individual locations in the molecule (eg mono chlorotriazine, di cholorotriazine, vinyl sulphone dyes). Require high temperature for their fixation These dyes characterized by presence of two reactive groups at two different locations, may be same groups of different, out of reactive system range available. High exchaust dyes because of their larger size molecule and more recative dents leave very small amount of left over colour, or exchaust in large quantity- Mostly used recative dyes.

Reactive groups in dyes may be

MCT(monochlorotriazine) DCT (Dicholrotriazine) VS (Sulphatoethyl sulphone) TCP (trichloropyrimidine) DCO (Dichloroquinoxaline) MFT ( Monoflurotriazine) DFCP ( Difluorochloro pyrimidine) DCP (Dichloropyridazine) MSP ( Methylsulphonyl pyrimidine) Nicotinotriazinyl ( exclusively used in Japan)
Groups present in dyes in different composition and combination.

Chemistry of reactive dyes

In general reactive dyes for cellulosic material have certain chrematistics structure feature. S : solubilizing group S C B C : Chromophoric group X B : Binding group X : Reactive group

The dyeing process takes place at two different pH levels. Firstly the exhaustion of the dye take place at neutral pH and then the fixation is achived at alkaline pH. At neutral pH dye acts as a direct dye and mainly diffusion of the dye is takes place ( because of sustaintivity) pH of the dyebath maintained at 10.5-11.0 during fixation period, at this pH decomposition of the reactive site and generation of cellulose ion takes place.

Role of pH in reactive dyeing

High Cell-O ion Two factors decide the optimum pH for the dyeing purpose in reactive dyeing. 1. Creation of reactive environment by activation of reactive site and generation of fibre/cellulose ions. 11.5-12.0 High negative charge on fibre

10.5-11

Optimum range Less Cell-O ion for reaction

2. Creation of high negative charge/zeta potential with increases pH and hence less exhaustion of dye.

9.5-10.0

Less activation of dye reactive site

Theoretically 11 pH is best suited for high fixation and good results

Role of Salt in dyeing

Reactive dyes structure prior to activation is similar to a direct dyes and for their exhaustion we use salts like common salt and glauber salt, to reduce zeta potential. Cellulosic fibres acquire a negative charge when immersed in water, and their surface is anionic and reactive dyes too are anionic in nature. So we use salts to neutralize the charge and hence repulsion. Electrolytes like sodium chloride and glauber salts are used for this purpose. Sodium sulphate is milder in action so it is highly recommended for reactive dyes like Turquoise colour-in which levelness not achieved easily.

Unique feature of theses dyes is versatility of the application procedures and temperature, the dyeing can be done at temperature ranging from room temperature to steaming temperature.

Based on the dyeing temperature the dye can be classified as:

1. Cold brand reactive dyes.

2. Hot brand reactive dyes.

Hot brand reactive dyes

These dye have only one reactive site in their molecule to react, so the temperature require for fixation is high.

Dyes based on triazine bases molecular srtucture or vinyle sulphone based dyes come under this category.

Hot- brand Dyes (% shade) Parameter Starting temperature Dyeing before salt addition(min) salt(g/l) 15 50 20 60 <= 0.5% 0.5-2.0% 30 25 75 30 100 2.0-4.0% >=4%

Time of salt treatment(min)

Temperature of salt treatment(min) Alkali(g/l) Temperature of fixation

30

45
75-85

60

60

6 70-80

10

Washing

Moderate

Hot brand dyes Dyeing cycle

Salt Salt alkali alkali Fixation, 30-45min Exhaustion, 30 min

85OC
Drain Temp

Time

HE dyes dyeing cycle

HE dyes can be applied by three method- Iso thermal, migration and anti-migration method. Exhaustion temperature taken- 50-60OC and for fixation 80-85OC for better fixation rate and high exhaustion.

HE dyes process parameter

HE- Dyes (% shade)
Parameter Starting temperature Dyeing before salt addition(min) salt(g/l) Time of salt treatment(min) Temperature of salt treatment(min) Alkali(g/l) Temperature of fixation(min) 10 15 80-85 15 30 35 20 35 35 70-75 15 20 <= 0.5% 0.5-2.0% 30 30 50 60 30 80 60 2.0-4.0% >=4%

Washing

Through and repeated

Fastness properties
Efficient soaping and washing of dye produce very good fastness due to attachment of dye with cellulose through covalent bond. Fastness to light fastness is good

Fastness to hot acetic acid and NaOCl is poor, the same can be improved by mild ethylene diamine treatment(1 gpl).

Dyes sensitive to metal ions, especially to copper.

Disadvantages
Fastness to hot acetic acid and NaOCl is poor, the same can be improved by mild ethylene diamine treatment(1 gpl). Dyes sensitive to metal ions, especially to copper.

Dyeing recipe and process parameter

M- Brand (% shade) Parameter Starting temperature Dyeing before salt addition(min) salt(g/l) Time of salt treatment(min) Temperature of salt treatment(min) Alkali(g/l) Temperature of fixation(min) Washing 5 6 40-45 Through and repeated 15 20 30 20 30 30 40-45 8 10 <= 0.5% 0.5-2.0% 30 25 40 45 30 50 60 2.0-4.0% >=4%

Dyeing cycle cold brand reactive dyes

Predissolved dye at pH 6-7 Enter goods

Salt (1st half)

Salt (2nd half)

Alkali (1st half)

Alkali (2nd half)

Dyeing continued 20-30 minutes

10 min

At Room temperature

15 min
10 min 10 min 10 min

Drain Cold brand dyes show highest rate of absorption and diffusion at pH 10.5 11.5 and at Room temperature. Reaction rate constant - 1.8 X 104

Dyeing procedure with cold brand reactive dyes

Scoured/bleached yarn

Enter goods in blank bath Add pre dissolved dyes and dye for 15 min

Add pre dissolve salt in 2 portion to dye bath and dye for 10 minutes

Add pre dissolve soda ash in 2 portion to dye bath and dye for 10 minutes

Dyeing continues for 20-30 minutes Dye fixing and Drying Soap at boil and wash

Squeeze and Dry

Cold brand dyes gamet from Dystar

Sr. No. 1 2 3 4 5 6 7 8 9 10 11 12 13 Commercial NAME Reactive GOLDEN YELLOW MR Reactive YELLOW MGR Reactive YELLOW M4G Reactive YELLOW M8G Reactive YELLOW M3R Reactive YELLOW M4R Reactive ORANGE M2R Reactive ORANGE 35 Reactive RED M5B Reactive RED M8B Reactive PINK MB Reactive BLUE M2R Reactive BLUE M4GD C. I. Name Reactive YELLOW 44 Reactive YELLOW 7 Reactive YELLOW 22 Reactive YELLOW 86 ReactiveORANGE 86 ReactiveORANGE 14 ReactiveORANGE 44 ReactiveORANGE 35 Reactive RED 2 Reactive RED 11 Reactive RED 74 Reactive BLUE 81 Reactive BLUE 168

14
15 16 17 18 19

Reactive BLUE MR
Reactive NAVY BLUE M3R ReactiveTURQUOISE BLUE MG Reactive VIOLET M4R Reactive MAGENTA MB Reactive VIOLET M2R

Reactive BLUE 4
Reactive BLUE 9 Reactive BLUE 140 Reactive VIOLET 12 Reactive VIOLET 13 Reactive VIOLET 14

Comparison between HE dyes and cold brand reactive dyes

Cold brand reactive dyes Two reactive group present at same location. Dyeing time required is less than HE dyes. Salt concentration for exhaustion require is less. Highly exhaustive dyes Poly functional in nature, reactive site present at different location. Larger molecule size Dyeing time is more in HE dyes. Comparatively higher salt required for complete exhaustion. Higher dyeing temperature required for fixation. Less substantive towards cellulose, so lesser chances of unlevelness. 80-85% exhaustion can be achieved. Versatile for all depth shade. Hydrolysis observed but overall exhaustion is better because of large number of reactive sites.

Dyeing temperature require for fixation is lower.

The affinity of the dye towards fibre is very high so chances of unlevelness is more. The overall exhaustion is 65-70% of the initial dye bath concentration. Not suitable for darker shade. Dye hydrolysis chances are higher.

Concluding remarks
Cold brand dyes suitable for lighter shade on fabric and in yarn dyeing can be done without problem of unlevelness. Steam consumption is lower in case of cold brand dyes. Dyeing time is lesser. Dyeing chemical consumption is lower, so less load on effluent treatment plant (less ppm of COD and BOD) Dyes available in all range to be used. The exhaustion percentage is 75% (against 85% of HE dyes)