Dyeing of Cellulosic Fabrics With Reactive Dyes

1
Dyeing Department Technical Weeks - 03.07. 02 Susanne Ehret

O
O
O
O H
O H
C H
2
O H
C H
2
O H
O
H O
O H
O
O
O
O H
O H
C H
2
O H
2
Market share of dyestuffs for cellulosic fibers worldwide
Reactive
48%
Direct
19%
Vat
16%
Sulphur
15%
Others
2%
3
Reactive dyes are the most important
dyeclass for cellulosic fibers
Dyeing auxiliaries
R e a c t i v e
4 8 %
D i r e c t
1 9 %
V a t
1 6 %
Su l p h u r
1 5 %
Ot h e r s
2 %
To obtain a levelled dyeing the

Demands on dyeing auxiliaries for dyeing with
reactive dyes by the exhaust method
are demonstrated and furthermore
the most important dyeing parameters are
explained
4
The fabric should not contain any disturbing
residual substances
Demands on pretreated cellulosic fabric
pH neutral - slightly acid
no heavy metal and low alkaline earth metal
content
good absorbency
low content of residual surface active agents

no residual peroxide !
5
Residual products from preparing process
in the reactive dyebath
Safety can be achieved
by using an agent for
peroxide destruction
before the dyeing process
0.1 g/l residual peroxide

0.1 g/l residual hydrosulfite

2.0 g/l MEROPAN BRE

0.5 g/l CHT - CATALASE BF
Original
dyeing
6
Products for peroxide destruction
Inorganic salts

MEROPAN BRE

_economic process:
saving of water, energy
and time

Enzymes / bio-catalysts

CHT-CATALASE BF
CHT-CATALASE FTS 40

_dyeing in the same bath
_low water consumption
_economic process
_ecological process
no waste water pollution!

7
Application requirements of MEROPAN BRE
check
pH - and
H
2
O
2

MEROPAN
BRE
If necessary
rinse, refill
reactive
dyeing
process
dye bath destruction of residual peroxide
bleach
95 C / 203 F,
30 min
cool down to
80 - 90 C/
176 - 194 F

bleach bath
> pH 10
Advantage: - one bath-two step bleach possible,
- residues of MEROPAN BRE do not disturb the reactive dyeing process
15 min
8
Enzymatic destruction of peroxide
Enzymes are bio-catalysts:
Catalysts are chemical substances which accelerate reactions
without being used up.
Enzymes are formed in the living organism. This natural production is
also used in a synthesis way, the enzymes are produced with fungi or
bacteria cultures on large scale.
Advantage: completely biodegradable!
Because of their cellular structure
the enzymes have a clear defined surface.
An enzyme has on the surface an
active centre with an equal complementary centre.
the enzymes work like a key-lock princip

+
+
enzyme substrate
enzyme-substrate-complexe
enzyme splitting product splitting
9
Efficiency of catalases
Catalases are enzymes which accelerate the decomposing reaction
from hydrogen peroxide to inactive oxygen and water.

The catalase accelerates the reaction but is not used up and will
be continuously efficient.
The catalase does not have any influence on the dyestuff, therefore it can
be dyed directly without intermediate rinsing process.
H O
O
2

H
2
O
+
CHT-
CATALASE
BF
+
H
2
O
H
O
H O
H
O
10
CHT catalase product range
CHT-CATALASE BF CHT-CATALASE FTS 40
thermostable product low temperature/low-price

20 - 60 C / 68-140F 20 - 40 C / 68-104 F
pH range: 4 - 9 6 - 9
time: ~ 10 min ~ 10 min
0.3 - 0.6 g/l 0.3 - 0.6 g/l

at 20C / 68F
1 part CHT-CATALASE BF = 1 part CHT-CATALASE FTS 40
at 40C / 104F
1 part CHT-CATALASE BF = 1.5 parts CHT-CATALASE FTS 40
11
CHT-CATALASE BF and CHT-CATALASE FTS 40
range of use in comparison
C F
40 104
50 122
60 140
70 158
80 176
90 194
pH-value
1 2 8 9 10 11 12 3 4 5 6 7
FTS 40
BF
30 86
20 68
10 50
CHT-CATALASE FTS 40 is cheaper,
but less thermostable
12
For optimum efficiency
following conditions are required:

Application requirements:

H
2
O
2
bleach
Rinse
Fresh bath (check pH)
Add catalase
Treat 10 - 15 min at required temperature
Remaining peroxide control, e.g. with Merck
test stripes
Dyeing in the same bath
13
Detection and semiquantitative determination of peroxides
in aqueous solutions with test strips
Analytical test strips from Merck
contain peroxidase.
Peroxidase transfers oxygen from the peroxide to an organic redox
indicator, which is then converted to a blue-coloured oxidation
product.
Instructions for use:

Immerse the reaction zone in the solution for 1 sec.
Shake off excess liquid from the strip.
Compare with the colour scale (0.5-25 mg/l H
2
O
2
)after
15 sec.

The appearance of any blue coloration within 3 min
can be interpreted as a positiv reaction.
14
Determination of residual peroxide on bleached fabric
A drop of TiCl
4
reagent is put on the bleached fabric.
The colour is compared with a scale.
without H
2
O
2
with H
2
O
2

15
Application amount of peroxide killers
MEROPAN BRE

1 part H
2
O
2
35% = 2 parts MEROPAN BRE
1 kg H
2
O
2
35% 2 kg MEROPAN BRE

CHT-CATALASE BF
1 part H
2
O
2
35% = 0.167 part CHT-CATALASE BF
1 kg H
2
O
2
35% 0.167 kg CHT-CATALASE BF 0.93
16
Demands on lubricants for
cellulosic fibers
With lubricant
reduces creases on piece
dyeing
prevents cracks and
abrasion marks
reduced textile-to-textile
friction
CHT solution:
BIAVIN - lubricants
17
Demands on lubricants for
cellulosic fibers
The BIAVIN lubricants allow smoothly
running dyeing processes on the
following conditions:

_ heavily loaded jet and overflow dyeing
machines, for delicate, light, but bulky
fabrics
_ for harsh fibers with the tendency to
form cracks
_ for pile fabrics sensitive to abrasion
18
CHT - range cellulosic lubricants
application amount
0.1 - 0. 3 g/l
reduces friction of fabric
exhaust onto the fabric with salt
washed off by rinsing
Cell, PES, PA, WO, silk
emulsified fat compound
concentrated product
anionic
BIAVIN 109
application amount
1.0 - 2.0 g/l
viscosity is slightly increased
excellent gliding properties
cellulosics and blends
sulfated fats
anionic
BIAVIN GLM
application amount
1.0 - 2.0 g/l
viscosity is increased
higher liquor pick up
slipping effect
friction is reduced
all sorts of fibers
polymeric amides
universally applicable
no ionic character
BIAVIN BPA
application amount
0.5 - 2.0 g/l
exhaust onto the fabric
remains partially
softer handle
better sewability
cellulosics and
synthetic microfibers with EL
polyethylene emulsion
nonionic
BIAVIN TCC
CHT anticrease agents and lubricants
for cellulosics and blends
19
Cellulosic articles with elastane
ladd wetting agent
ladd 2 - 3 g/l BIAVIN TCC
lload fabric into the dyeing machine
lfabric must have good and same wetting
properties
lprescour or prebleach
lrinse
ladd dyebath auxiliaries + 1.0-1.5 g/l BIAVIN TCC
lraise dye temperature slowly and cool down
slowly
20
Demand on dyeing levelness
Levelling agent for reactive dyes ?
Levelling agents in the classical meaning
are not available for reactive dyeings.
Reason for this is the reaction of the
reactive dye with the cellulosic fiber.
Migration of already fixed dye molecules
is not possible ! This would be a
chemical miracle.

How does CHT solve this problem ?
21
CHT solution
22
SARABID LDR = dyebath conditioner
How does SARABID LDR work ?
_ increases the dyestuff solubility and therefore
improves the dye diffusion into the fiber
_ excellent dispersing effect
_ inactivates Ca, Mg in water and on textile
_ prevents dyestuff agglomerations
_ avoids precipitations of all kinds of impurities
brought into the dyebath by fiber or water
_ applicable in cellulosic dyeing with reactive dyes
and CEL/PES blends one-bath dyeing
23
Dyebath conditioner
special polyacrylate and
dispersing agent
anionic
active content: 26%
stable at HT dyeing conditions
application amount: 1 - 2 g/l
24
Visualization of a dyebath conditioner ?
The efficiency of a dyebath conditioner is
difficult to demonstrate.

The following special filter tests show a
combination of dye solubility and
soilings...
25
Filter test method
Treat 100 % greige cotton
fabric
LR 1 : 10
soft water
10 dH (180 ppm CaCO
3
)
20 dH (360 ppm CaCO
3
)
30 minutes at 95C/ 203F
cool down to the
recommended dyeing
temperature of the dye
remove the cotton fabric
In these liquors put
y g/l SARABID LDR
0.1 g/l dyestuff
40 g/l Glaubers salt
5 g/l soda ash
2 ml/l NaOH 38B
treat for 10 minutes at the
recommended dyeing
temperature
filtrate

judge the filters visually
26
Filter test at 80 C / 176 F with 0.1 g/l C.I. Reactive Yellow 138
0 dH
0 ppm
10 dH
180 ppm
20 dH
360 ppm CaCO
3
without auxiliary
2 g/l SARABID LDR
Benefit prevents dyestuff agglomerations
27
0 dH
0 ppm
10 dH
180 ppm
20 dH
360 ppm CaCO
3
without auxiliary
2 g/l SARABID LDR
Filter test at 60 C / 140 F with 0.1 g/l C.I. Reactive Red 106
Benefit increase of dyestuff solubility
28
Filter test at 80 C / 176 F with 0.1 g/l C.I. Reactive Blue 160
0 dH
0 ppm
10 dH
180 ppm
20 dH
360 ppm CaCO
3
without auxiliary
2 g/l SARABID LDR
Benefit good dispersing properties
29
Filter test at 80 C / 176 F with 0.1 g/l C.I. Reactive Blue 71
0 dH
0 ppm
10 dH
180 ppm
20 dH
360 ppm CaCO
3
without auxiliary
2 g/l SARABID LDR
Benefit increase of dye solubility
30
Filter test at 60 C / 140 F 10 dH with 1 g/l C.I. Reactive Blue 21
Dyestuff with
0.1 g/l FELOSAN RG-N
Dyestuff with
0.1 g/l FELOSAN RG-N
2 g/l SARABID LDR
Residues of nonionic detergents from pretreatment can cause problems with dye solubility.
The solution is the addition of SARABID LDR into the dyebath.
+
31
SARABID LDR = dyebath conditioner
Excellent levelling behaviour
for reactive dyes
Increase
of dye
solubility
Good dispersing and
sequestering capacity
32
Demand on end-use
excellent rinse
to remove electrolyte, alkali, residual dyes

wash off
to release and outward diffusion of dye hydrolysates

cationic fixation
to reach the fastness level
Excellent durability of reactive dyed goods can
only be obtained if the fabrics are treated after the
dyeing process in the following way:
33
Demand on a washing agent for reactive dyes
_ good washing off behaviour of reactive dyes
_ speed in washing off
_ blocks renewed uptake of the dye hydrolysate
from the washing liquor
_ good calcium binding and dispersing behaviour
_ no effect on shade
_ no impairment of light fastness
_ good ecological features
_ maximum end use fastness properties
34
Influence on washing performance
_ Dyestuff character and fixation grade of the dye
_ electrolyte content in the soaping bath
_ water quality
_ pH - value
_ temperature and time
_ liquor ratio
_ mechanical effect of the machinery equipment
_ number of soaping baths
_ chemical character of the washing agent
35
Technical performance of our CHT range of soaping agents
for reactive dyeings
COTOBLANC NSR
mixture of organ. & inorganic
compounds, free of tenside
22 %
100 %, powder
anionic
add into hot water and stir
0.2 - 0.5 g/l
state-of-the-art product
best wash off efficiency of
reactive dyeings in soft water <
10dH, high dyestuff affinity
safes wash baths
poor solubility: 70 g/l at 25C/77F
not recommended for
continuous washing machines
with hard water risk of filtrations on
X-bobbins (precipitations with
insoluble Ca-salts)
only for reactive dyeings

Chem. character

P - content
Active
content
Ionic character
Dissolving
Application amount
Product features

MEROPAN DPE
modified polyacrylate &
phosphonates
1,5 %
32 %, liquid
anionic
in each ratio with water soluble
1.0 - 2.0 g/l

excellent soaping behaviour in
hard water because of good
sequestering properties
good dispersing properties
universal product for cellulosics:
suitable as sequestering and
soaping agent for reactive, vat,
sulphur dyes...
36
Technical performance of our CHT range of soaping agents
for reactive dyeings
COTOBLANC CSL
sodium salt of a modified
polycarbonic acid
-
20 %, liquid, non foaming
anionic
1 - 3 g/l
washing agent for reactive
dyeings
good soaping efficiency in hard
water with 3 g/l
suitable for application in
batchwise and continuous ranges

Chem. character

P - content
Active
content
Ionic character
Dissolving
Application amount
Product features

COTOBLANC KRS
mix of polyacrylate + modified
phosphonates
0.62 %
24 %, liquid
anionic
1- 3 g/l
soaping agent for reactive and
vat dyeings
good washing behaviour
designed for continuous
wash off processes
37
Classification of CHT - soaping agents
1. COTOBLANC NSR

2. MEROPAN DPE

3. COTOBLANC CSL

4. COTOBLANC KRS

Best soaping performance

Universal dyeing auxiliary

Cheap product,P-free

Continuous wash off
processes
38
Washing off procedure with COTOBLANC NSR

CO Single Jersey, prebleached
Thies-Roto Stream

LR 1 : 10
Dyeing recipe:
3.0 % Drimaren Turquoise X-B
0.5 % Drimaren Brill.Green X-3G

95C 70C 50C 20C
203F 158F 122F 68F
57
25
14
3,50
2
0,1
0
10
20
30
40
50
60
%

w
a
s
h

o
f
f

d
y
e

c
o
n
t
e
n
t
70C 70C 95C 70C 50C 20C
10 min each
wash off performance of COTOBLANC NSR
95C 70C 70C 70C 50C 20C
203F 158F 158F 158F 122F 68F
COTOBLANC NSR
Conventional anionic surfactant
Benefit
reduced rinsing bath after soaping
39
Determination of the washing off behaviour
Special washing test method to evaluate the removal of reactive
dye hydrolysate from the fiber

Step 1. Hydrolyse reactive dyestuff with alkali
Step 2. Pad the hydrolysed dye solution with hardness on 100 %
cotton fabric under defined conditions = basic fabric

Step 3. Wash test
Treat the basic fabric with white cotton adjacent
fabric in ratio 1 : 1
Soap with x g/l washing agent
LR 1 : 20, 98C / 212F, 2 x 15 min

judge the basic fabric and
the soiling onto the adjacent fabrics
40
Special test method of washing agents for the removal of
reactive dyestuff hydrolysate
Basic fabric
2 x
soaped fabric
adjacent
fabric 1
adjacent
fabric 2

10 dH

without
auxiliary

0.25 g/l
COTOBLANC NSR

0.5 g/l
COTOBLANC NSR
41
Without soaping agent
0.25 g/l COTOBLANC NSR
1.0 g/l MEROPAN DPE
1.0 g/l COTOBLANC KRS
1 2 3 4
10dH
1 = padded fabric
2 = padded fabric
soaped 2 x
3 = staining on
adjacent CO
soaped 1x

4 = staining on
adjacent CO
soaped 2x
42
Demand on the end use of a reactive dyeing
Where wet fastness is
of critical importance

is recommended
as an extra insurance and
an essential operation
cationic aftertreatment
43
Demand on an ideal cationic fixing agent
_ improvement of the wash and contact fastnesses
_ prevents migration during drying
_ protects dye / fiber bound of reactive dyes against hydrolysis
and thermocracking
_ broad application range for different dye classes and fibers
_ no influence on shade and on light fastness
_ no adverse effect on handle
_ no impairment of the sewability
_ no deterioration of rewettability
_ formaldehyde and heavy metal free
_ for application on all kind of machines
_ low price
44
REWIN MRT
Polyammonium compound

^ excellent improvement of contact fastnesses
^ no shade change
^ no deterioration of light fastness
^ prevention of hydrolysis
^ no influence on the handle and the re-wettability
^ free of formaldehyde

- no or only minimum improvement of the wash fastness

application : 2 - 3 %
45
Fastness improvement with REWIN MRT
CO CV
without fixative

2 % REWIN MRT

3 % REWIN MRT
CO WO
Wash fastness 60C EN ISO 105 - C06 - C2S Water fastness EN ISO 105 - E01
4 % Levafix Scarlet E-2GA
without fixative

2 % REWIN MRT

3 % REWIN MRT
46
REWIN MRT
0
1
2
3
4
5
Wash fastness 40 C/104 F
Contact/wet fastness
Reactive dyes
Direct dyes
Stripping behaviour and
redyeability
Shade change
Product costs at saturation
47
REWIN ACP
Polyammonium compound, copolymer
^ good allround product, mainly on reactive dyeings
^ excellent wash fastness levels
^ copolymer = good improvement of washing fastnesses of reactive dyeings
^ good contact fastnesses
^ no deterioration of the light fastness
^ no or only small shade changes
^ free of formaldehyde
^ recommended for discontinuous application

- in pad application dye hydrolysate spots can occur if the reactive dyeings
are not rinsed and washed off satisfactioned
application: 2 - 3 %
48
Fastness improvement with REWIN ACP
Wash fastness 60C EN ISO 105 - C06 - C2S

without fixative

2 % REWIN ACP
CO WO
Water fastness EN ISO 105 - E01

without fixative

2 % REWIN ACP
4 % Bezaktiv Red HE-3B
CA CO PA PES PAN WO
49
REWIN ACP
0
1
2
3
4
5
Wash fastness 60 C/ 140F
Reactive dyes
Direct dyes
redyeability
Shade change
50
REWIN TN
Polyalkylene polyamine
^ best improvement of washing fastnesses of direct and reactive
dyeings
^ excellent improvement of wet/contact fastnesses
^ protection of hydrolysis and migration
^ suitable for exhaust and pad application
^ free of formaldehyde and heavy metal

- no or only small influence on the light fastness possible
- sometimes shade change depending on dyestuff

application: 2 - 3 %
51
Fastness improvement with REWIN TN
Wash fastness 40C EN ISO 105 - C06 - A1S Water fastness EN ISO 105 - E01
2 % Solophenyl Blue BFF
without fixative

2 % REWIN TN

2 % REWIN ST
without fixative

2 % REWIN TN

2% REWIN ST
CO CV CO WO
52
REWIN TN
0
1
2
3
4
5
Wash fastness 40 C/ 104 F
Reactive dyes
Direct dyes
redyeability
Shade change
53
REWIN DWR
Reactive polyammonium compound
^ wash fastness improvement of critical reactive
turquoise and green dyeings
^ good wet fastness properties
^ excellent protection of hydrolysis and
thermocracking
^ no or only minimum shade change

- high application amount of 4 - 6 %
- difficult application: pH 7.5 - 8 %, 40 - 50C/ 104-122F
- difficult stripping behaviour and redyeability

54
REWIN DWR
0
1
2
3
4
5
Wash fastness 40 C/ 104 F
Wash fastness 60C/140F
Reactive dyes
Direct dyes
redyeability
Shade change
55
REWIN OS
Special polyammonium compound with
reactive groups to improve wash and wet
fastness level of selected direct dyeings

application by exhaust method:

3.0 - 3.5 % REWIN OS
2 ml/l NaOH 38 B

treat 20 - 30 mins at 40C / 104F
rinse well and neutralise
56
Wash fastness improvement with REWIN OS
Dyeing ( 1 %), 40 C / 104 F wash test, grade 4 can be reached:
Tubantin yellow GR
Tubantin orange GGLN 200 %
Tubantin pink 2 B
Tubantin red F 3 B conc.
Tubantin bordeaux 2 BL conc.
Tubantin rubine 5 B
Tubantin violet BL 200 %
Tubantin blue BRR h.c.
Tubantin blue GLL 300 %
Tubantin green 5 GL conc.
Tubantin brown GGL
Tubantin brown BL
Tubantin grey CGLL
57
Fastness improvement with REWIN OS
CO WO
Wash fastness 40C EN ISO 105-C06 - A1S

without fixative

3.5 % REWIN OS
Water fastness EN ISO 105 - E01

without fixative

3.5 % REWIN OS
CO WO
1.0 Tubantin orange GGLN 200%
58
Overview of various/important REWIN fixatives
REWIN application field improvement of
saturation
limit in %
reactive direct package continuous contact
fastness
wash
fastness
ACP
(DD)
2.0 3.0
(1.0 1.5)
+ (+) + (+) + +
DWR 4.0 6.0 + - + - + +
MRT 3.0 3.5 + + + + + -
TN 2.0 3.0 + + + + + +
+ well suitable
(+) suitable to a certain extent
- not suitable
59
Dyeing process guideline
for reactive hot dyes on jet
Dyeing recipe
0.1 - 0.3 g/l BIAVIN 109 or
1.0 - 2.0 g/l BIAVIN BPA / TCC
1.0 - 2.0 g/l SARABID LDR
x % reactive dye
y g/l salt
z g/l alkali (NaCO
3
/NaOH)
Wash off
0.2 - 0.5 g/l COTOBLANC NSR
or
1.0 - 2.0 g/l MEROPAN DPE
or
1.0 - 3.0 g/l COTOBLANC CSL
or
1.0 - 3.0 g/l COTOBLANC KRS
Cationic fixing

2.0 - 3.0 % REWIN ACP
or
2.0 - 2.5 % REWIN TN
or ...
0
20
40
60
80
100
0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320
add auxiliaries
add dye
add salt
add alkali
add wash auxiliary add
fixative
212
176
140
104
68
C F
60
Dyeing auxiliaries for cellulosic fibers

Further products ...
61
Faulty dyeings
1 If a cationic aftertreated cellulosic
dyeing (e.g. direct dyeing, reactive
dyeing, sulphur...) has to be redyed
because of spots, unlevelness,
shade...

the cationic fixing agent has to be
removed / stripped in the first step
62
Stripping/Masking of cationic fixatives
5 g/l CHT-DISPERGATOR SMS

x ml/l acetic acid 60 % (pH 4.0 - 4.5)
30 mins at 98C / 212 F
rinse well
repeat the treatment
63
CHT-DISPERGATOR SMS
_ amine salt of naphthalene sulphonic acid
_ anionic
_ liquid
_ easy handling
_ foamfree
_ universally applicable dispersing agent
_ levelling agent
_ special stripping agent
application: 1 - 5 g/l
(according to application procedure)
64
Faulty dyeings
2 Dyed fabrics in rope form with fiber
fluff, pillings, abrasion spots,
fibrillation...

Bio - polish treatment
Surface treatment
65
BEIZYM UL - Surface treatment agent
Cellulase with broad application spectrum

Chemical Character : Special cellulase blend, non ionic

Properties : - removal of fiber fluff, abrasion spots and pillings
- defibrillation of Lyocell fibers
- improvement of the handle
- useful for enzymatic stone wash of jeans
- small influence on tensile strength
66
Application recommendation
Machine equipment: jet, overflow, tumbler
Fibers: all cellulosic fibers
Application amount: 0.5 - 1.5 % BEIZYM UL
(depending on effect)
Liquor ratio: 1 : 5 - 1 : 20
Temperature: 45 - 55C / 113 - 131 F
pH value: 4.5 - 5.5 (adjust before enzyme
addition, mainly with acetic acid and
sodium acetate)
Time: 20 - 60 min (depending on effect)

Enzyme stop: increase pH with soda ash up to 9 or
temperature increase to
85 - 90C / 185 - 194F
67
Bio - polish with BEIZYM UL
basic fabric with pills 1.0 % BEIZYM UL
68
For further questions
Just contact us !

Dyeing of Cellulosic Fabrics With Reactive Dyes

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Dyeing Department Technical Weeks - 03.07. 02 Susanne Ehret

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