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World production of fibres 2000
CELL
PES
PA
PAN
Wool
Others
37%
32%
2%
16%
8%
About 52 Mio tons
of which CEL 19 Mio tons
PES 17 Mio tons
5%
Dyes for CelluloseDyes for Cellulose
Reactive
Vat
Subst.
Indigo
Sulfur
Naphtol
Pigments
7%
12%
8%
2%
2%
60%
or 1.8 bio CHF
9%
Worldwide market 2001Worldwide market 2001 :: 33 billions CHFbillions CHF
Superficial indigo ring dyeing of cotton typical of denim
Vat dyes
Sulfur dyes
Diazo- or Naphtol dyes
BASICS OF REACTIVE DYEING
ABSORBTION AND DIFFUSION OF DYE IN FIBER
• SUBSTANTIVITY: INFLUENCING PARAMETERS
• SPEED OF DIFFUSION: INFLUENCING PARAMETERS
REACTION OF DYE WITH FIBER
• SPEED OF REACTION: INFLUENCING PARAMETERS
• PARASITIC REACTION. DYE INACTIVATION
• BI-REACTIVE DYES
WASHING OFF UNFIXED DYES
• PARAMETERS INFLUENCING SPEED OF WASHING OFF
Adsorbtion of dyes on cotton surface
Reactive dyes
The 3 phases of reactive dyeing
Substantivity of reactive dyes
Parameters influencing substantivity
The π electron system between dye and fiber
Number of double bonds vs. Affinity
Rupture of double bond system = Affinity loss
Cellulose and dye : both have negative charge !
Overcoming the repulsion : Electrolyte screens
Effect of pH on negative load of fiber
Effect of dye concentration on substantivity
Dye adsorbtion on surface
Substantivity: Function of dye conc in CEL & bath
Effect of temperature on substantivity
Effect of liquor ratio on substantivity
Effect of liquor ratio on substantivity
Effect of liquor ratio on substantivity
Summary : Parameters affecting substantivity
Substantivity increases with:
•Increasing Standard Affinity of the dye
•Increasing electrolyte concentration in the dye bath
•Decreasing pH in the dyebath
•Decreasing dye concentration in the dyebath
•Decreasing dyeing temperature
•Decreasing Liquor Ratio
Dye diffusion inside the fiber
Dye diffusion inside the fiber
Substantivity is only one of many diffusion-influencing parameters!
• Fibre type (mercerized-, causticized-, non-mercerized cotton, viscose)
• Dyeing temperature
• Size and shape of the dye molecule
• Substantivity of the dye
• Electrolyte concentration in the bath
• Dye concentration
The speed of diffusion of reactive dyes depends mainly on:
Various CEL structure models
Various CEL structure models
Dye diffusion in the fibre
CEL has heterogeneous structure
Comparison: Un-mercerized vs mercerized cotton
Effect of temperature on dye diffusion
Effect of dye molecule size on diffusion
Effect of dye substantivity on diffusion
Effect of electrolyte on diffusion
Summary: Parameters influencing Diffusion
The speed of diffusion of reactive dyes can be
increased by:
• Raising the dyeing temperature
• Reducing the size and bulkiness of the dye molecule
• Reducing substantivity of the dye in the dyebath
• Causticizing or mercerising the cellulose
BASICS OF REACTIVE DYEING
ABSORBTION AND DIFFUSION OF DYE IN FIBER
• SUBSTANTIVITY: INFLUENCING PARAMETERS
• SPEED OF DIFFUSION: INFLUENCING PARAMETERS
REACTION OF DYE WITH FIBER
• SPEED OF REACTION: INFLUENCING PARAMETERS
• PARASITIC REACTION. DYE INACTIVATION
• BI-REACTIVE DYES
WASHING OFF UNFIXED DYES
• PARAMETERS INFLUENCING SPEED OF WASHING OFF
Exhaust process: Separated diffusion & fixation
Pad dry pad steam: Separated diffusion & fixation
“All-in“ Exhaustion: combined diffusion & fixation
Danger !!
Pad Batch: combined diffusion & fixation
A: Nucleophilic substitution reaction
B: Nucleophilic addition reaction
Reactivity: Speed of reaction
Inactivation reactions: competing with fixation
Inactivation reactions. Competing with fixation
First
release
Reactive Group Inventor Used in Reactivity 5=>1
High=>low
Main usage
1956
Dichlorotriazine (DCT)
ICI PROCION MX 5 Pad batch
1956
Monochlorotriazine (MCT)
ICI
CIBA
PROCION HE,
HEXL
CIBACRON E
clones many
bireactive dyes
2 Exhaust (hot) Pad
thermofix
Printing
1957
„Para Vinylsulfone“ (VS)
HOECHST
REMAZOL
clones
Many bireactive
dyes
3
Pad batch
Pad dry
Pad steam
Exhaust (warm)
Printing
N
H
N
N
N
Cl
Cl
R
N
H
N
N
N
R'
Cl
R
S
O
O
OSO3
H
N
H
R
Commercial reactive groups
First
release
Reactive Group Inventor Used in Reactivity 5=>1
High=>low
Main usage
1960
Trichloropyrimidine
GEIGY
HOECHST
CIBACRON TE 1 Exhaust (hot)
1961
Dichloroquinoxaline (DCQ)
BAYER LEVAFIX E 4 Exhaust (warm)
1971
Difluorochloro-pyrimidine
(DFCP)
BAYER
SANDOZ
LEVAFIX E-A
DRIMARENE K
some bireactive
dyes
4 Exhaust (warm)
N
H
N
N
Cl
Cl
R
Cl
N
N
Cl
Cl
O
N
H
R
N
H
N
N
F
F
R
Cl
Commercial reactive groups
First
release
Reactive Group Inventor Used in Reactivity 5=>1
High=>low
Main usage
1978
Monofluorotriazine (FT)
CIBA
CIBACRON F
Many bireactive
dyes in
CIBACRON C,
FN, CIBACRON
LS, H
4 Exhaust (warm)
Exhaust (hot)
All pad process
1980
„Meta Vinylsulfone“ (VS)
SUMITOMO
SUMIFIX SUPRA
bireactive dyes
Clones
3 Exhaust (warm) Pad
batch
Pad dry
Pad steam
1985
Alkylsulfatoethylsulfone (VS)
CIBA
Many bireactive
dyes in
CIBACRON C
and CIBACRON
FN especially
3 Exhaust (warm)
All pad process
N
H
N
N
N
R'
F
R
N
H
R
S
OO
OSO3H
(Aliph)N
H
R
S
O
O
OSO3
H
Commercial reactive groups
First
release
Reactive Group Inventor Used in Reactivity 5=>1
High=>low
Main usage
1985
Alkyl-Arylsulfatoethylsulfone (VS)
CIBA
Many
bireactive dyes
in CIBACRON
C and
CIBACRON FN
3 Exhaust (warm)
All pad process
1997
Difluoropyrimidine (DFP)
CLARIANT
DYSTAR
Used in
bireactive dyes
in
DRIMARENE
HF
LEVAFIX CA
4 Exhaust (warm)
All pad process
(Aliph)N
H
O
N
H
R
S
O
O
OSO3H
N
H
N
N
F
F
R
Commercial reactive groups
Influence of reactive group on speed of reaction
Reactivity of the group says nothing about
stability of the bond with cellulose!
Influence of reactive group on speed of reaction
Complete, reproducible
Incomplete!
Influence of reactive group on speed of reaction
Influence of chromophore and substituent
on speed of reaction
„Inductive effects“ on reactive group :
„pumping in“ or „pumping out“ electrons
Influence of chromophore on speed of reaction
Factor 30 !
Influence of Substituent on speed of reaction
• Scarlet chromophore
• Fluorotriazine group
• 3 different substituents
Cellulose model
Cellulose model
Site of reaction: ionized alkohol group
Site
Effect of pH on cellulose ionization
Effect of pH on speed of reaction
Example: Reactive group DFCP
Nucleophilic addition: Reaction mechanism
of vinylsulphone dyes
Effect of temperature on speed of reaction
Effect of substantivity on speed of reaction
High substantivity
Low substantivity
Effect of substantivity on speed of reaction
Effect of substantivity on speed of reaction
Summary: Parameters influencing speed of reaction.
Speed of reactions depends on:
• Reactivity of the reactive group
• Inductive effects of the chromophore on reactive group
• Inductive effects of the substituent of the reactive group
• pH of the dyebath (Reaction speed increases when pH increases)
• Temperature of the dye bath
( reaction speed increases as temperature rises)
• Substantivity of the dye in dyebath
Bireactive dyes: Effect on degree of fixation
Bireactive dyes : structures
Mono-reactive dye A
Poor stability of the bond, to acid
Mono-reactive dye B
Poor stability of the bond, to alkali
Bi-reactive dye C
Bond is stable
to both acid and alkali
Bi-reactive dye: possible impact on substantivity
Comparison between bi-reactive MCT/VS and FT/VS dyes
MCT/VS
• MCT has lower speed of
reaction with CEL than VS
• MCT requires a higher pH
than VS for complete fixation
• Bond of MCT with CEL is
stable in alkaline dyeing
conditions
• Bond of VS with CEL is
unstable in alkaline dyeing
conditions
Thus:
Higher dyeing pH necessary
to fix MCT: may distroy VS
bond
or
Lower pH, safe enough for
VS:
FT/VS
• FT has higher speed of
reaction with CEL than VS
• FT does fix completely at
ideal pH of fixation for VS and
at lower pH
• Bond of FT with CEL is stable
in alkaline dyeing conditions
• Bond of VS with CEL is
unstable in alkaline dyeing
conditions
Thus:
The (low) pH, best suitable
for
complete fixation of VS
without significant destruction
of the VS bond, also warrants
complete fixation of FT
Comparison between bi-reactive MCT/VS and FT/VS dyes
Although the MCT/VS combination has led to
several good dyes, it suffers from a basic problem :
Potential for reproducibility issues
choice between 2 risks
• of incomplete fixation of MCT
or
• of hydrolysis of the just formed bond, in dyeing
phase
Destruction of the bond between fiber and dye
Reactive dyes as ion exchangers
Bond destruction : triazine & pyrimidin dyes
Bond destruction: vinylsulphone dyes
Acid bond destruction: Triazine & pyrimidine dyes
Alkaline bond destruction: Vinylsulphone dyes
Oxidative bond destruction: Pyrimidine dyes
Oxidative bond destruction: Pyrimidin dyes
Summary: Stability of the dye –fiber bond
Stability of dye/fibre bond Tendency
In alkaline media MCT, FT, DFCP, DFP better
than VS, DCQ
In acid media VS better than DFCP, FT,
MCT, DCQ, DFP
In per-borate containing
media
MCT, FT, VS better than
DFP, DFCP, DCQ
In chlorine-containing
media (1-5 ppm)
MCT, FT, VS better than
DFP, DFCP, DCQ
BASICS OF REACTIVE DYEING
ABSORBTION AND DIFFUSION OF DYE IN FIBER
• SUBSTANTIVITY: INFLUENCING PARAMETERS
• SPEED OF DIFFUSION: INFLUENCING PARAMETERS
REACTION OF DYE WITH FIBER
• SPEED OF REACTION: INFLUENCING PARAMETERS
• PARASITIC REACTION. DYE INACTIVATION
• BI-REACTIVE DYES
WASHING OFF UNFIXED DYES
• PARAMETERS INFLUENCING SPEED OF WASHING OFF
Why is it necessary to wash-off unfixed dyes ?
Because ,
even small quantities of unfixed dye
remaining inside the fiber
lead to poor wash fastness (bleed)
in usage of the textile
TD 4.5 CTS Exhaust CEL & CEL/PES 02/98 cc-fn12.ppt
Washing fastness test on multifiber band
Performance with short washing off procedure:
(CIBACRON FN procedure as described above)
Washing C4A
....Simulating bleed problems in household washing
Two different phases of washing off:
Extraction of unfixed dye from outside the fiber
Quick process, no need for high temperature
Is only a dilution
Extraction of unfixed dye from inside the fiber
Very slow process
Requires diffusion of dye molecule inside->out of fiber
All parameter favoring diffusion speed,
are favorable to good washing off
PARAMETERS AFFECTING THE WASHING OFF PROCESS
• Amount of unfixed dye which must be extracted from fiber
depends on shade depth, degree of fixation of dye, substantivity in dyebath
• Speed of diffusion of the dye in the washing off bath
depends on size of dye molecule, substantivity in washing off bath
and temperature of washing off bath
• Washing off equipment
Especially number of successive wash baths, strength of flow,
• Substantivity of the dye under the fastness test conditions
Washing off unfixed dyes
Slow diffusion
& high substantivity dye type
Washing off unfixed dye
Quick diffusion &
low substantitivity dye
Washing off unfixed dye
Slow diffusion
& low substantivity dye

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Reactive basics. slides.

  • 1. World production of fibres 2000 CELL PES PA PAN Wool Others 37% 32% 2% 16% 8% About 52 Mio tons of which CEL 19 Mio tons PES 17 Mio tons 5%
  • 2. Dyes for CelluloseDyes for Cellulose Reactive Vat Subst. Indigo Sulfur Naphtol Pigments 7% 12% 8% 2% 2% 60% or 1.8 bio CHF 9% Worldwide market 2001Worldwide market 2001 :: 33 billions CHFbillions CHF
  • 3. Superficial indigo ring dyeing of cotton typical of denim
  • 7. BASICS OF REACTIVE DYEING ABSORBTION AND DIFFUSION OF DYE IN FIBER • SUBSTANTIVITY: INFLUENCING PARAMETERS • SPEED OF DIFFUSION: INFLUENCING PARAMETERS REACTION OF DYE WITH FIBER • SPEED OF REACTION: INFLUENCING PARAMETERS • PARASITIC REACTION. DYE INACTIVATION • BI-REACTIVE DYES WASHING OFF UNFIXED DYES • PARAMETERS INFLUENCING SPEED OF WASHING OFF
  • 8. Adsorbtion of dyes on cotton surface
  • 10. The 3 phases of reactive dyeing
  • 13. The π electron system between dye and fiber
  • 14. Number of double bonds vs. Affinity
  • 15. Rupture of double bond system = Affinity loss
  • 16. Cellulose and dye : both have negative charge !
  • 17. Overcoming the repulsion : Electrolyte screens
  • 18. Effect of pH on negative load of fiber
  • 19. Effect of dye concentration on substantivity
  • 20. Dye adsorbtion on surface
  • 21. Substantivity: Function of dye conc in CEL & bath
  • 22. Effect of temperature on substantivity
  • 23. Effect of liquor ratio on substantivity
  • 24. Effect of liquor ratio on substantivity
  • 25. Effect of liquor ratio on substantivity
  • 26. Summary : Parameters affecting substantivity Substantivity increases with: •Increasing Standard Affinity of the dye •Increasing electrolyte concentration in the dye bath •Decreasing pH in the dyebath •Decreasing dye concentration in the dyebath •Decreasing dyeing temperature •Decreasing Liquor Ratio
  • 27. Dye diffusion inside the fiber
  • 28. Dye diffusion inside the fiber
  • 29. Substantivity is only one of many diffusion-influencing parameters!
  • 30. • Fibre type (mercerized-, causticized-, non-mercerized cotton, viscose) • Dyeing temperature • Size and shape of the dye molecule • Substantivity of the dye • Electrolyte concentration in the bath • Dye concentration The speed of diffusion of reactive dyes depends mainly on:
  • 33. Dye diffusion in the fibre
  • 35. Comparison: Un-mercerized vs mercerized cotton
  • 36. Effect of temperature on dye diffusion
  • 37. Effect of dye molecule size on diffusion
  • 38. Effect of dye substantivity on diffusion
  • 39. Effect of electrolyte on diffusion
  • 40. Summary: Parameters influencing Diffusion The speed of diffusion of reactive dyes can be increased by: • Raising the dyeing temperature • Reducing the size and bulkiness of the dye molecule • Reducing substantivity of the dye in the dyebath • Causticizing or mercerising the cellulose
  • 41. BASICS OF REACTIVE DYEING ABSORBTION AND DIFFUSION OF DYE IN FIBER • SUBSTANTIVITY: INFLUENCING PARAMETERS • SPEED OF DIFFUSION: INFLUENCING PARAMETERS REACTION OF DYE WITH FIBER • SPEED OF REACTION: INFLUENCING PARAMETERS • PARASITIC REACTION. DYE INACTIVATION • BI-REACTIVE DYES WASHING OFF UNFIXED DYES • PARAMETERS INFLUENCING SPEED OF WASHING OFF
  • 42. Exhaust process: Separated diffusion & fixation
  • 43. Pad dry pad steam: Separated diffusion & fixation
  • 44. “All-in“ Exhaustion: combined diffusion & fixation Danger !!
  • 45. Pad Batch: combined diffusion & fixation
  • 51. First release Reactive Group Inventor Used in Reactivity 5=>1 High=>low Main usage 1956 Dichlorotriazine (DCT) ICI PROCION MX 5 Pad batch 1956 Monochlorotriazine (MCT) ICI CIBA PROCION HE, HEXL CIBACRON E clones many bireactive dyes 2 Exhaust (hot) Pad thermofix Printing 1957 „Para Vinylsulfone“ (VS) HOECHST REMAZOL clones Many bireactive dyes 3 Pad batch Pad dry Pad steam Exhaust (warm) Printing N H N N N Cl Cl R N H N N N R' Cl R S O O OSO3 H N H R Commercial reactive groups
  • 52. First release Reactive Group Inventor Used in Reactivity 5=>1 High=>low Main usage 1960 Trichloropyrimidine GEIGY HOECHST CIBACRON TE 1 Exhaust (hot) 1961 Dichloroquinoxaline (DCQ) BAYER LEVAFIX E 4 Exhaust (warm) 1971 Difluorochloro-pyrimidine (DFCP) BAYER SANDOZ LEVAFIX E-A DRIMARENE K some bireactive dyes 4 Exhaust (warm) N H N N Cl Cl R Cl N N Cl Cl O N H R N H N N F F R Cl Commercial reactive groups
  • 53. First release Reactive Group Inventor Used in Reactivity 5=>1 High=>low Main usage 1978 Monofluorotriazine (FT) CIBA CIBACRON F Many bireactive dyes in CIBACRON C, FN, CIBACRON LS, H 4 Exhaust (warm) Exhaust (hot) All pad process 1980 „Meta Vinylsulfone“ (VS) SUMITOMO SUMIFIX SUPRA bireactive dyes Clones 3 Exhaust (warm) Pad batch Pad dry Pad steam 1985 Alkylsulfatoethylsulfone (VS) CIBA Many bireactive dyes in CIBACRON C and CIBACRON FN especially 3 Exhaust (warm) All pad process N H N N N R' F R N H R S OO OSO3H (Aliph)N H R S O O OSO3 H Commercial reactive groups
  • 54. First release Reactive Group Inventor Used in Reactivity 5=>1 High=>low Main usage 1985 Alkyl-Arylsulfatoethylsulfone (VS) CIBA Many bireactive dyes in CIBACRON C and CIBACRON FN 3 Exhaust (warm) All pad process 1997 Difluoropyrimidine (DFP) CLARIANT DYSTAR Used in bireactive dyes in DRIMARENE HF LEVAFIX CA 4 Exhaust (warm) All pad process (Aliph)N H O N H R S O O OSO3H N H N N F F R Commercial reactive groups
  • 55. Influence of reactive group on speed of reaction
  • 56. Reactivity of the group says nothing about stability of the bond with cellulose!
  • 57. Influence of reactive group on speed of reaction Complete, reproducible Incomplete!
  • 58. Influence of reactive group on speed of reaction
  • 59. Influence of chromophore and substituent on speed of reaction „Inductive effects“ on reactive group : „pumping in“ or „pumping out“ electrons
  • 60. Influence of chromophore on speed of reaction Factor 30 !
  • 61. Influence of Substituent on speed of reaction • Scarlet chromophore • Fluorotriazine group • 3 different substituents
  • 64. Site of reaction: ionized alkohol group Site
  • 65. Effect of pH on cellulose ionization
  • 66. Effect of pH on speed of reaction Example: Reactive group DFCP
  • 67. Nucleophilic addition: Reaction mechanism of vinylsulphone dyes
  • 68. Effect of temperature on speed of reaction
  • 69. Effect of substantivity on speed of reaction High substantivity Low substantivity
  • 70. Effect of substantivity on speed of reaction
  • 71. Effect of substantivity on speed of reaction
  • 72. Summary: Parameters influencing speed of reaction. Speed of reactions depends on: • Reactivity of the reactive group • Inductive effects of the chromophore on reactive group • Inductive effects of the substituent of the reactive group • pH of the dyebath (Reaction speed increases when pH increases) • Temperature of the dye bath ( reaction speed increases as temperature rises) • Substantivity of the dye in dyebath
  • 73. Bireactive dyes: Effect on degree of fixation
  • 74. Bireactive dyes : structures
  • 75. Mono-reactive dye A Poor stability of the bond, to acid
  • 76. Mono-reactive dye B Poor stability of the bond, to alkali
  • 77. Bi-reactive dye C Bond is stable to both acid and alkali
  • 78. Bi-reactive dye: possible impact on substantivity
  • 79. Comparison between bi-reactive MCT/VS and FT/VS dyes MCT/VS • MCT has lower speed of reaction with CEL than VS • MCT requires a higher pH than VS for complete fixation • Bond of MCT with CEL is stable in alkaline dyeing conditions • Bond of VS with CEL is unstable in alkaline dyeing conditions Thus: Higher dyeing pH necessary to fix MCT: may distroy VS bond or Lower pH, safe enough for VS: FT/VS • FT has higher speed of reaction with CEL than VS • FT does fix completely at ideal pH of fixation for VS and at lower pH • Bond of FT with CEL is stable in alkaline dyeing conditions • Bond of VS with CEL is unstable in alkaline dyeing conditions Thus: The (low) pH, best suitable for complete fixation of VS without significant destruction of the VS bond, also warrants complete fixation of FT
  • 80. Comparison between bi-reactive MCT/VS and FT/VS dyes Although the MCT/VS combination has led to several good dyes, it suffers from a basic problem : Potential for reproducibility issues choice between 2 risks • of incomplete fixation of MCT or • of hydrolysis of the just formed bond, in dyeing phase
  • 81. Destruction of the bond between fiber and dye
  • 82. Reactive dyes as ion exchangers
  • 83. Bond destruction : triazine & pyrimidin dyes
  • 85. Acid bond destruction: Triazine & pyrimidine dyes
  • 86. Alkaline bond destruction: Vinylsulphone dyes
  • 87. Oxidative bond destruction: Pyrimidine dyes
  • 88. Oxidative bond destruction: Pyrimidin dyes
  • 89. Summary: Stability of the dye –fiber bond Stability of dye/fibre bond Tendency In alkaline media MCT, FT, DFCP, DFP better than VS, DCQ In acid media VS better than DFCP, FT, MCT, DCQ, DFP In per-borate containing media MCT, FT, VS better than DFP, DFCP, DCQ In chlorine-containing media (1-5 ppm) MCT, FT, VS better than DFP, DFCP, DCQ
  • 90. BASICS OF REACTIVE DYEING ABSORBTION AND DIFFUSION OF DYE IN FIBER • SUBSTANTIVITY: INFLUENCING PARAMETERS • SPEED OF DIFFUSION: INFLUENCING PARAMETERS REACTION OF DYE WITH FIBER • SPEED OF REACTION: INFLUENCING PARAMETERS • PARASITIC REACTION. DYE INACTIVATION • BI-REACTIVE DYES WASHING OFF UNFIXED DYES • PARAMETERS INFLUENCING SPEED OF WASHING OFF
  • 91. Why is it necessary to wash-off unfixed dyes ? Because , even small quantities of unfixed dye remaining inside the fiber lead to poor wash fastness (bleed) in usage of the textile
  • 92. TD 4.5 CTS Exhaust CEL & CEL/PES 02/98 cc-fn12.ppt Washing fastness test on multifiber band Performance with short washing off procedure: (CIBACRON FN procedure as described above) Washing C4A ....Simulating bleed problems in household washing
  • 93. Two different phases of washing off: Extraction of unfixed dye from outside the fiber Quick process, no need for high temperature Is only a dilution Extraction of unfixed dye from inside the fiber Very slow process Requires diffusion of dye molecule inside->out of fiber All parameter favoring diffusion speed, are favorable to good washing off
  • 94. PARAMETERS AFFECTING THE WASHING OFF PROCESS • Amount of unfixed dye which must be extracted from fiber depends on shade depth, degree of fixation of dye, substantivity in dyebath • Speed of diffusion of the dye in the washing off bath depends on size of dye molecule, substantivity in washing off bath and temperature of washing off bath • Washing off equipment Especially number of successive wash baths, strength of flow, • Substantivity of the dye under the fastness test conditions
  • 95. Washing off unfixed dyes Slow diffusion & high substantivity dye type
  • 96. Washing off unfixed dye Quick diffusion & low substantitivity dye
  • 97. Washing off unfixed dye Slow diffusion & low substantivity dye