Cotton Dyeing

Content
1. Structure of cotton fiber
- Influence of structure on dyeing
- Effect of Mercerization

2. Dyes used for cotton fiber

-

Direct dye
Vat dye
Sulfur dye
Reactive dye
Comparison of properties of dyes

Structure of cotton fiber

A: inaccessible region :
1) Cotton fiber consists of an assembly of fibrils
2) Cotton is accessible to water and dye molecule only
at fibrillar surface by way of pores and channels

elementary fibrils are so close to one another

B, C: accessible region:
relatively disordered

Influence of cotton type on color

Table. Color difference ( E) after dyeing with CI Direct Green 27

1) The most obvious macrostructural feature to affect the dyeing is its specific surface area, which is inversely
related to its fineness. The finer the fiber, the greater is the rate of dyeing
2) Pale flecks in dyed cotton fabric are caused by immature(or thin-walled) fiber,
since immature cotton fibers lack of a fully developed secondary wall where dye molecules can enter

Effect of Mercerization
Table. Effect of Mercerization on dye absorption
Absorption(mg/g)
CI Direct Red 2

CI Direct
Yellow 12

Unmercerized

Mercerized

25

10

Mercerized and
dried

16

Fig. Cross-section of Mercerized cotton

Table. Change in pore distribution by Mercerization
Diameter of pore
(nm)

<1

1~3

Total pore volume

of cotton (cm3/g)

0.13

22

20

53

100

Total pore vol. of

Mercerized cotton

0.32

0.26

0.16

0.02

0.76

42

0.12

34

3.0~
10

>10

0.32

0.03

21

Table. Effect of tension on dye absorption

Sum

Absorption(mg/g)
CI Direct Red 2

CI Direct Blue 1

Unmercerized

15

1.5

Mercerized
with tension

29

2.4

Mercerized
without tension

35

2.7

0.60

100

Properties of direct dyes

1. Anioic dyes with substantivity for cellulose fibers
2. Substantivity is defined as the attraction between a fiber and a dye
3. Structural factors affecting substantivity
1) Linearity
The more linear is the dye molecule,
the higher is substantivity

2) Planarity
The more planar,
the higher is the substantivity
NaO3S

NH2

OCH3
N N

OH
N N
OH
NaO3S

HO

vs

N
OH N

NH2

N N

N N

NH2 H3CO

SO3Na

NaO3S

vs

H2N

OCH3

SO3Na

N N

N N
NaO3S

SO3Na

SO3Na

NaO3S

SO3Na

NH2

N N
H3CO

3) Number of OH, NH2 group

Substantivity increases as the dye molecule has more number of OH and NH 2 groups
which form hydrogen bonding
4) Number of SO3Na group
Substantivity decreases as the dye molecule has more number of SO 3Na group
which provides water solubility

H2N

Application properties of direct dyes

1.Aggregation of dyes
1) Dyes often exist in aqueous solution as aggregates of several molecules
2) Aggregation is promoted by a high ratio of molecular mass to sulphonate group(SO3Na)
3) An addition of sodium carbonate is advantageous to break aggregates
2. Rate of dye absorption
1) The rate of uptake by cellulose vary extremely widely
2) A decisive factor is tendency to aggregate, since this greatly retards mobility into fiber
3. Salt sensitivity
1) Direct dyes vary appreciably as regards the effect of neutral salt
2) The lower the ratio of molecular mass to number of sulphonate group, the less absorption
take place without neutral salt
4. Temperature sensitivity
1) Effect of an increase in temperature is to increase the dyeing rate, but to decrease the
equilibrium exhaustion
2) Consequently, for a fixed dyeing time there is an optimum temperature
It is important to know the application properties in selection for mixture reciepes, in
order to achieve optimum results and to prevent uneven dyeings

Typical dyeing process of direct dyes

1. Self levelling dye :
dyes have good migration
or levelling properties

2. Salt controllable dye :

3. Temp. controllable dye :

addition of salt gives level

dyeing

The exhaustion is controlled by the

addition of salt and temperature

Boil x 45~60min

Boil x 45~60min

30~40min
40
40

Boil x 45~60min

1: dye

1: dye

1: dye

2: neutral salt

2: neutral salt

2: neutral salt

2.5~10 %owf

portionwise addition of
salt during heating

portionwise addition of
salt at boil
3: heating slowly

Aftertreatment
1. Copper salt treatment
1) Dyes containing two hydroxy groups in position ortho to the azo group
2) 0.25~2% CuSO4, 1% CH3COOH, 60 x 20~30min
3) Marked improvement in light and washing fastness
OH

HO
OH

H2NO2S

OH

N N
NaO3S

N N
N
H

SO2NH2

SO3Na

2. Fixing agent treatment

1) Cationic surfactant
- Interaction with sulphonate groups in direct dye, conferring improved washing fastness
- Complex usually dissociates in hot detergent solutions above 60
2) Polymeric material
- long chain polyamine
- dicyandiamide-formaldehyde adducts
- Forming a lake stable in hot detergent solution
- Copper salts are added to compensate the decreased light fastness

Properties of vat dye

1. Vat dyes contain two or more keto groups.
they are water-insoluble and exhibit excellent washing and light fastness on cotton
2. Chemical structure
O

N
H

H
N

NH O
O

HN

O
O

Indigo

Derivative of AQ (Indanthrone)

3. Forming Leuco dye by reduction(vatting)

O

OH

O-Na+

OH

O-Na+

Na2S2O4
NaOH
O
Vat dye
water insoluble
no substantivity to cotton

Enolic acid leuco dye

practically insoluble
little substantivity

Leuco dye
water soluble
high substantivity

Dyeing receipe of vat dye

1.

Indigo vat dye

stock solution : indigo 5g + NaOH (30Be) 17g + warm water 35g + hydrosulphite 5g
liquor ratio : 1:20, dyeing temp. : 20~25 C, dyeing time : 15min

2. Anthraquinone vat dye

Conditions

NaOH
(30Be)
(cc/l)

Hydro
sulfite
(g/l)

Neutral
salt
(g/l)

Reduction
Temp.
(C)

Dyeing
Temp.
(C)/
Time(min)

Dye
IN

Pale-med.
Heavy

25-32
32-40

4-6
6-8

60

60/
30-60

IW

Pale-med.
Heavy

13-17
17-22

4-5
5-7

10-15
15-25

45-50

45-50/
20-45

IN + IW

Pale-med.
Heavy

19-25
25-31

4-5.5
5.5-7.5

5-10
10-20

45-50

45-50/
20-45

IK dyes : have a low substantivity and are dyed at RT with a little NaOH and a high salt concentration
IW dyes : have a high substantivity and dyed at 50 C with more NaOH and less salt
IN dyes : have a much higher substantivity and dyes at 50 C with still more NaOH

Typical dyeing process for vat dyes

absorption (stage 1) levelling (stage 2) oxidation stage soaping stage
95~100x 10min

45~60x 30min
50~60

12

34

1: fabric, 2: vat dye, 3: NaOH, 4: levelling agent, 5: hydro

6: salt, 7: oxidizing agent, 8: soaping agent

Absorption and levelling of vat dyes

Fig. Absorption behavior of a leuco dye

Fig. Change in dye conc. In fiber cross-section

Stage 1 : It is characteristic of vat dyes that they exhaust rapidly, even at relatively low temperature
Most of the dye (80-90%) exhausts within about 10 min
The dye is absorbed initially in the outer of the fiber, causing ring dyeing
The rate of dyeing is related to surface area of fiber, dye concentration, liquor ratio, etc.
Stage 2 : The second stage is governed by the diffusion of the dye into the interior core of the fiber
The rate of diffusion is dependent on dyeing temperature

Properties of sulfur dye

1. Surfur dyes contain sulfide linkage (-S-S- or S-S-S-) in the molecule.
They are water insoluble, and their chemical structure are usually not definite.
2. Chemical structure
N

N
H2N

NH2
S S

S S
x

CI Surfur Yellow 4

3. Forming leuco sulfur dye

Na2S
Dye S-Na+

Dye S S Dye
Sulfur dye
water insoluble
no sbustantivity to cotton

4. Fastness
1) high washing fastness
2) low rubbing fastness

O2

-S+Na Dye

Leuco sulfur dye

water soluble
substantivity to cotton

Dyeing receipe and process of sulfur dyes

1. Dyeing receipe
Pale

Heavy

Dye (%owf)

10~20

Na2S (%owf)

10~20

Na2CO3 (%owf)

10~20

Na2SO4(%owf)

10

20~30

Liquor ratio

1:20

2. Dyeing process
1) Dissolving dye
- the same amount of Na2S and Na2CO3
as that of sulfur dye
- soft water without Ca and Mg ion
2) Dyeing
- large amount of Na2SO4 is needed

add Monopol oil for levelling

start at 50
heating rate : 1 /min
temp. and time : boil x 40~50min

3) Washing
- cold water
- over flow, 30min
4) Oxidation
- H2O2(35%) 2cc/l
acetic acid 2cc/l
- 50 x 20min
5) Soaping
- Na2CO3 3g/l
soaping agent 1g/l
- 90 x 10min
6) Aftertreatment
- CuSO4 or K2Cr2O7 with acetic
to improve color fastness

Properties of reactive dye

1. Dyes containing reactive group which can form the covalent bond with cotton fiber
2. Classification
1) Vinylsulfone type
OH
NaO3SOH2CH2CO2S

NH2

N N

N N

NaO3S

SO3Na
Cl

Cl

2) MCT type
SO3Na

N
OH HN

N
N

SO2CH2CH2OSO3Na

H
N

H
N

N
N

N N

NH

OH

NaO3S
N N

NaO3S

SO3Na

NaO3S

SO3Na

Cl

3) Supra type

N
SO3Na

OH HN

N
N

H
N

N N
NaO3S
SO3Na

SO3Na

SO2CH2CH2OSO3Na

Comparison of exhaustion curves

Cl
N

MCT

100

Relative Strength(%)

Dye

60
40

Supra

Vinyl sulfone

20
0

20

Neutral Salt
Dye
Dye

SO2CH2CH2OSO3Na

Low substantivity

60

40

80

Dyeing Time(min)

Alkali

Akali

High substantivity

80

Dye

SO2

CH

High substantivity

CH2

Comparison of application properties of reactive dyes

Substa
ntivity

Dyeing
temp.
()

Fixation
(%)

VS

low

50~60

Supra

medium

MCT

high

Property

Dyes

Wash
ability

Stabilit
y to
alkali

Stabilit
y to
acid

60~70

good

bad

60~70

80~90

good

80

70~80

bad

Dyeing method

Batch

Conti
nuous

CPB

good

good

good

good

good

good

good

good

good

good

medium

good

good

bad

1) Factors affecting dyeing properties of reactive dyes :

type and number of reactive group, chemical structure of chromogen, bridging group
2) Factors affecting substantivity in reactive dyeing
chemical structure of reactive dye, concentration of dye, liquor ratio, amount of neutral salt,
dyeing temperature, rate of heating, pH, etc.

Example of dyeing process of reactive dyes

1. MCT type

Salt
Salt

Dye

Alkali

Alkali

80 x 45~60 min

Salt

Soaping

25

2. Supra type
60
Salt

Dye

Alkali

45~60 min

Alkali
Soaping

25
Alkali(1/3)

3. VS type
Salt

Alkali(1/3)
25

Alkali(1/3)

60
Dye

Dye

60 min
Soaping

Comparison of properties of dyes for cotton

1) General properties
Dyes

merit

demerit

Simple and short process

Low cost

Dull color
Low washing fastness

Vat dyes

High washing fastness

High light fastness

Difficult dyeing process

High price

Reactive dyes

Bright color
High washing fastness

Relatively low fixation

High chemical consumption

Direct dyes

2) Fastness
Dyes
Color fastness

Direct dye
pale

heavy

Reactive dye
pale

heavy

Vat dye
pale

heavy

Test method

Washing (staining)

2-3

1-2

4-5

4-5

4-5

KS K 0430

Washing (fading)

1-2

1-3

3-4

4-5

Round-o-meter

Rubbing (wet)

2-3

1-2

3-4

3-4

3-4

KS K 0650

Rubbing (dry)

2-3

3-4

Crock meter

Perspiration

1-2

3-4

3-4

4-5

ISO 105-E04

Chlorine

2-3

3-4

KS K 0725

Light

Carbon arc

Light + perspiration

1-2

3-4

0701+ Carbon arc