Dyeing With Direct Dyes

Cheap Dyes Very easily dyed onto cellulosic fabrics Defination: Anionic dyes which have affinity for cellulosic fibre and are generally dyed from water in the presence of salt. Name is Direct Dye as dye can be directly applied on fibres/fabrics without any treatment.

IMPORTANT FACTORS
1. 2. 3. 4. DYES PROCESS AFTERTREATMENTS DYE-FIBRE INTERACTIONS

GROUPS THAT SHOW SUBSTANTIVITY

N=N Azo
NaO3S NH2

Gamma-acid

NaO3S

OH J-acid
CH=CH
Diphenyl

OH
Thiazole S HC CH HC

NH2

Stilbene

1 OR MORE GROUP CAN BE PRESENT

STRUCTURE OF DYES
1. CONGO RED
NH 2 N=N N=N NH 2

SO 3Na Congo Red

SO 3Na

This dye is no longer used as (a) at pH 3 or below it gives blue colour (b) It is made from benzidene amine which is carcinogenic

STRUCTURE OF DYES..contd
2. CHLORANTINE FAST GREEN BLL
Chlorantine Fast Green BLL NH O H2N SO3Na O NH NO3S NH N NH N COONa N =N OH

Blue dye and yellow dye are connected via triazine ring to get a green dye

STRUCTURE OF DYES..contd
3. C.I. Direct Yellow 12
C.I. Direct Yellow 12 H5C2O N=N CH=CH SO3Na SO3Na N=N OC2H5

This dye can be applied on cotton, wool and silk.

STRUCTURE OF DYES..contd
4. COPPER PHTHALOCYANINE
Copper Phthalocyanine N N N Cu N

NaO3S

N 2+ N SO3Na

N-

This is a general molecule which can be used as direct dye, acid dye or a reactive dye can be made based on them.

CHROMOPHORES IN DIRECT DYES

1. 2. 3. 4. 5. 6. Azo (90%) Stilbene Dioxane Quinoline Thiazole Anthraquinone

All direct dyes have a solubilising group Ex- SO3Na in Congo Red and so they form anionic molecule in water

DYEING PROCESS
The requirements are 1. DYE 2. AUXILLARY 3. pH 4. TEMPERATURE 5. MLR

METHODS FOR DYEING

1. BATCH PROCESS 2. SEMI-CONTINUOUS PROCESS 3. CONTINUOUS PROCESS Only batch process is used for direct dyes as the dyes have a high affinity for fibre.

Dye 1 has high affinity for fibre. Dye 2 has high affinity for water Partition coefficient = K= [D]f [D]s Higher the K, more is the dye taken up by the fibre, which is preferable for Batch Process.

 For continuous or semi-continuous process, dye should have very low affinity, because if the dye has high affinity it will be preferentially taken up which is called Tailing effect. At high temperature, dye has low affinity as dyeing is exothermic process. So for direct dyes high temperature should be used.

AUXILLARY
Salt is used as an auxillary in direct dyeing. Commercial dye 40-60%Dye + 40-60% Deluent Here the deluent is salt / electrolyte. So some dyeing occurs even if extra salt is not added.

EFFECT OF ELECTROLYTE

Zeta Potential Dye is negatively charged DSO3Na <=> DSO3- + Na+ So there is repulsion between dye and fibre. To overcome charge on surface or to suppress the dissociation reaction of dye, salt is used. Ex- NaCl, Na2SO4.10H2O (Glaubers salt)

pH
Normally neutral pH is used. In viscose rayon, if pH becomes alkaline, dye gets reduced and so lower shade is obtained. Optimum pH is 6-7

TEMPERATURE
For all direct dyes there is an optimum temperature Example- C.I.Direct yellow 12 .20oC C.I.Direct Red 81..60oC C.I.Direct Yellow 28100oC Many shades are obtained by mixing 2-3 dyes.

Dyeing of direct dye is carried out at 90-100oC for 1-2hrs

MATERIAL TO LIQUOR RATIO

MLR is a function of Machine the machine being used. Jigger Higher the MLR, lower is the dye Winch uptake. MLR
1:4

1:20

CLASSIFICATION OF DIRECT DYES

Class A : Self levelling (20%) Class B : Salt controllable (40%) Class C : Salt & Temperature

Class A- Self leveling direct dyes

Dyes in this group have good leveling characteristics and are capable of dyeing uniformly even when the electrolyte is added at the beginning of the dyeing operation. They may require relatively large amounts of slat to exhaust well.

Class B - Salt Controllable Dyes

These dyes have relatively poor leveling or migration characteristics. They can be batch dyed uniformly by controlled addition of electrolyte, usually after the dye bath has reached the dyeing temperature.

Class C - Salt and Temperature Controllable Dyes

These dyes show relatively poor leveling or migration and their substantivity increases very rapidly with increasing temperature. Their rate of dyeing is controlled by controlling the rate of rise of the dyebath temperature as well as controlling the salt addition. Some of these dyes require very little salt to show good exhaustion in light shades.

TESTS TO FIND CLASS OF DYE

1. Levelling or migration test (i) 2.5g hank of cotton, 1%shade, 20%NaCl, M:L::1:30, boil, 30mins (ii) Dyed hank + Undyed hank(2.5g), 10%NaCl, M:L::1:30, boil, 30mins The 2 hanks are compared, If almost equal shade Class A If large difference Class B or Class C

2. Salt test 3 dye baths are dyed with 1% shade Quantity of salt varied- 0.6%, 0.8%, 1% MLR:1:30, 100oC, 30mins Hanks squeezed and removed. Salt conc increased to 20% in all baths and 2nd set of hanks inserted. If Set 1 lighter or equal to Set 2 Class B If Set 1 darker than Set 2 Class C

AFTER TREATMENTS
Direct dyes have W.F. of 2-3 L.F. of 3-4 generally Hence, after treatment is required. Dye molecule size is low low wash fastness. If molecule size is increased, the fastness will improve.

AFTER TREATMENTScontd.
1. Diazotisation and Development
Amino group of dye can be diazotised and coupled. NaNO2 + HCl HNO2 + NaCl
+ D-NH2 + HNO2 + HCl --> D-N D-N _ NCl + OH _ NCl + 2H2O D N=N OH + HCl

Developer (beta napthol)

Additional azo group change in shade

AFTER TREATMENTScontd.
Developers used are-Napthol, m-phenylene diamine phenol, resorcinol. Dyes that are used in such way are called D&D dyed (Dyed & Developed dyes)

AFTER TREATMENTScontd.
If Dyes does not have NH2 group, coupling is done with diazonium salt.
NH2
O2N + _ _ N-Cl N

p-Nitro aniline C.I. Azoic Diazo Component 37 NO2

Diazotised p-nitro aniline

AFTER TREATMENTScontd.
2. Treatment with Metal Salts CuSO4 or K2Cr2O7 or mixture of both. Improves the L.F. & to a extent W.F.also. Trade names of dyes- Cuprofix, Cuprophenyl, Cuprantine

AFTER TREATMENTScontd.
Dyes that have the following structure can be treated with Cu.
Treatment with metal salts OH N=N OH O _ Cu _ O N=N

OH groups at o,o position to azo ring or derivatives of

OH N=N COOH

OH COOH

Treatment is 0.25-2% CuSO4 + 1% CH3COOH, 20-30min at 60oC

AFTER TREATMENTScontd.
3. Formaldehyde Treatment Given to those dyes which have amino group situated at p-position to azo group.
Formaldehyde treatment NH2 NH 2 HN 2 D + HCHO + D NH2 HN 2 D NH 2 CH D NH2 NH2

2-3% HCHO(30%)+ 1% CH3COOH(30%), 30min, 30oC

AFTER TREATMENTScontd.
4. Cationic Fixing Agent Different kindsa) Quarternary ammonium compounds b) Amino triazine condensates c) Pyridinium derived bases All have a quarternary Nitrogen Nowadays, Condensation product of dicyandiamide, formaldehyde and ammonium chloride are most commonly used.

AFTER TREATMENTScontd.
+ N O S 3 Dye

Bond is weak, so can withstand only few washes. Sometimes reduces L.F.