PREPARATION OF FIXING AGENTS FOR ANIONIC...
Transcript of PREPARATION OF FIXING AGENTS FOR ANIONIC...
PPRREEPPAARRAATTIIOONN OOFF FFIIXXIINNGG AAGGEENNTTSS FFOORR
AANNIIOONNIICC DDYYEESS
A THESIS SUBMITTED TO
THE DIVISION OF SCIENCE AND TECHNOLOGY
OF
THE UNIVERSITY OF EDUCATION LAHORE
BY
SAIMA SHARIF
ROLL NO. 03-138
REGISTRATION NO. 0499056
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE
DEGREE OF DOCTOR OF PHILOSOPHY
IN CHEMISTRY
JUNE 2007
AAPPPPRROOVVAALL OOFF TTHHEE DDIIVVIISSIIOONN OOFF SSCCIIEENNCCEE AANNDD
TTEECCHHNNOOLLOOGGYY// UUNNIIVVEERRSSIITTYY OOFF EEDDUUCCAATTIIOONN,, LLAAHHOORREE
--------------------------------------
Director
I certify that this thesis satisfies all the requirements as a thesis for the award of
the degree of Doctor of Philosophy.
--------------------------------------
Head of Department
This is to certify that we have read this thesis and that in our opinion it is fully
adequate, in scope and quality, as a thesis for the degree of Doctor of
Philosophy.
------------------------------------------------ -------------------------------------
Dr. Mian Muhammad Izhar-ul-Haq Dr. Saeed Ahmad
(Co-Supervisor) (Supervisor)
iii
The selection of dyes and dyeing auxiliaries is a crucial factor in
optimising dyeing processes. Dyeings often show unsatisfactory wet fastness
properties. This is usually encountered with direct dyes and to a lesser extent
with reactive dyes also. Different cationic fixing agents have been used as
pretreatment or aftertreatment to improve the wet fastness properties of these
dyes but none has proved to be totally satisfactory. Therefore, there is still a
need for novel dyeing processes that improve properties in respect of
application and fastness properties of the dyeings.
The present work is therefore concerned with the synthesis of new
cationic fixing agents and their evaluation as fixing agents in improving the wet
fastness properties of anionic dyes on cellulose fibres. Eight mono-reactive
(28a-d and 29a-d) and four bis-reactive (30a-b and 31a-b) 2,3-epoxy / 3-
chloro-2-hydroxy propyl derivatives of quaternary ammonium chloride have
been synthesised and their structures have been characterised using IR and 1H-
NMR spectroscopy. Purity of these compounds has been checked by thin layer
chromatography (TLC).
One mono-reactive (28c) and two bis-reactive (30a and 30b) 2,3-
epoxypropyl derivatives have been used for the cationisation of cellulosic
AABBSSTTRRAACCTT
iv
fabrics under different pretreatment conditions. Pretreated fabrics were then
dyed with a variety of direct, reactive and acid dyes under neutral and alkaline
conditions in the absence of salt. A bis-reactive derivative compound 30b was
also applied as an aftertreatment to the conventional direct dyeings under
neutral and alkaline conditions. The reflectance values and the corresponding
CIE L*, a*, b*, C* and ho colour coordinates of the samples were measured.
From the reflectance values at the λ max. of the dyeings, colour strength (K/S)
values of the dyeings were calculated using Kubelka-Munk equation. Fastness
properties of the dyeings have been determined by following standard methods
for the determination of colour fastness of textiles and leather.
Pretreatment with mono- and bis-reactive cationic fixing agents (30a,
30b, 28c) has enabled the dyeing of cotton fabrics with anionic (direct, reactive
and acid) dyes under neutral conditions in the absence of salt. Higher colour
strength (K/S) and good wash fastness properties were obtained with the
pretreated fabrics as compared to the untreated fabrics dyed with the same
direct and reactive dyes. Bis-reactive derivatives showed better wet fastness
properties as compared to the mono-reactive derivative. In addition,
pretreatment has significantly reduced the dyeing time, thus becoming a more
environmentally friendly method for the direct and reactive dyeing of cotton
fabrics. Aftertreatment with cationic agents has shown a slight change in the
colour of the direct dyeings but has beneficial effects on the wash fastness
results.
v
Dedicated to
My Beloved Parents
Whose prayers and affections are the source of strength for me in every step of
life and a sign of success for my bright future.
DDEEDDIICCAATTIIOONN
vi
I would like to express deep appreciation to my supervisor Prof. Dr.
Saeed Ahmad, Chairman, Department of Chemistry, University of Science and
Technology, Bannu for his inspiring guidance, encouraging attitude and
valuable suggestions throughout my research work.
I also express sincere appreciation to my co-supervisor Prof. Dr. Mian
Muhammad Izhar-ul-Haq, Principal, University of Education, Township
Campus, Lahore for his guidance and suggestions throughout the research
work.
I would like to thank Muhammad Fauz-ul-Azeem and Mr. Hamood–ur-
Rehman, Scientific Officers, PCSIR Laboratories complex, Lahore for
providing instrumental facilities. Thanks to Muhammad Naeem Khan and Mr.
Farooq Arif for their cooperation.
Thanks to Mr. Islam, Mr. Muhammad Iqbal, other laboratory staff and
the library staff (PCSIR, Lahore) for their cooperation during my research
work. I also acknowledge the cooperation of Sandal Dyestuff Industries
Limited, Pakistan for providing dyes.
Special thanks to my uncle and Dr. Shahina Waheed, Head (Retd.)
/ACRC PCSIR Laboratories Complex, Lahore.
AACCKKNNOOWWLLEEDDGGEEMMEENNTT
vii
Page
ABSTRACT -----------------------------------------------------------------------------iii
DEDICATION ---------------------------------------------------------------------------v
ACKNOWLEDGEMENT -------------------------------------------------------------vi
TABLE OF CONTENTS -------------------------------------------------------------vii
LIST OF TABLES --------------------------------------------------------------------xiv
LIST OF FIGURES -------------------------------------------------------------------xix
LIST OF SYMBOLS / ABBREVIATIONS -------------------------------------xxiii
CHAPTER
1. INTRODUCTION ------------------------------------------------------------------1
1.1 Dyes and dyeing -----------------------------------------------------------------1
1.2 Classification of dyes -----------------------------------------------------------2
1.3 Anionic dyes ---------------------------------------------------------------------3
1.3.1 Direct dyes ---------------------------------------------------------------3
1.3.2 Reactive dyes ------------------------------------------------------------4
1.3.3 Acid dyes ---------------------------------------------------------------- 5
1.4 The need for auxiliaries -------------------------------------------------------- 5
TTAABBLLEE OOFF CCOONNTTEENNTTSS
viii
1.5 Classification of auxiliaries ----------------------------------------------------6
1.5.1 Classification of surfactants -------------------------------------------7
1.6 Pretreatments and aftertreatments for anionic dyes ------------------------8
1.6.1 Cationic fixing agents --------------------------------------------------9
1.6.1.1 Quaternary ammonium salts ---------------------------------11
1.7 Problems encountered with the fixing agents ------------------------------14
1.8 Plan of work --------------------------------------------------------------------14
2. LITERATURE REVIEW ------------------------------------------------------- 17
2.1 General development ----------------------------------------------------------18
2.2 Monomeric quaternary ammonium salts ----------------------------------- 23
2.2.1 Azetidinium chloride ------------------------------------------------- 25
2.2.2 Epoxy and halohydroxy propyl derivatives ------------------------27
2.2.3 Mono- and bis- reactive haloheterocyclic derivatives ------------34
2.3 Polymeric quaternary ammonium salts -------------------------------------38
3. EXPERIMENTAL WORK -----------------------------------------------------49
3.1 General information -----------------------------------------------------------50
3.2 Synthesis of mono- and bis-reactive 2,3-epoxy / 3-chloro-2-
hydroxy propyl derivatives of quaternary ammonium chloride ---------52
3.2.1 General procedure for the synthesis of mono- and bis-reactive
2,3-epoxypropyl derivatives (28a-d and 30a-b) -------------------55
N-Cyanomethyl-N-(2,3-epoxypropyl)-N,N-dimethyl
ammonium chloride (28a) --------------------------------------------55
ix
N-Carboxymethyl-N-(2,3-epoxypropyl)-N,N-dimethyl
ammonium chloride (28b) --------------------------------------------56
N-Cyanoethyl-N-(2,3-epoxypropyl)-N,N-dimethyl
ammonium chloride (28c) --------------------------------------------57
N-Carboxyethyl-N-(2,3-epoxypropyl)-N,N-dimethyl
ammonium chloride (28d) --------------------------------------------57
Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethyl
ammonium chloride] (30a) -------------------------------------------58
Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethyl
ammonium chloride] (30b) -------------------------------------------59
3.2.2 General procedure for the synthesis of mono- and bis-reactive
3-chloro-2-hydroxypropyl derivatives (29a-d and 31a-b) -------59
N-Cyanomethyl-N-(3-chloro-2-hydroxypropyl)-N,N-
dimethylammonium chloride (29a) ---------------------------------60
N-Carboxymethyl-N-(3-chloro-2-hydroxypropyl)-N,N-
dimethylammonium chloride (29b) ---------------------------------61
N-Cyanoethyl-N-(3-chloro-2-hydroxypropyl)-N,N-
dimethylammonium chloride (29c) ---------------------------------62
N-Carboxyethyl-N-(3-chloro-2-hydroxypropyl)-N,N-
dimethylammonium chloride (29d) ---------------------------------62
Methylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-
diethylammonium chloride] (31a) ----------------------------------63
x
Ethylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-
dimethylammonium chloride] (31b) --------------------------------64
3.3 Applications --------------------------------------------------------------------64
3.3.1 Application of cationic fixing agents as pretreatment ------------65
3.3.1.1 Pretreatment of cotton fabrics -------------------------------65
3.3.2 Dyeing conditions for untreated cotton fabrics --------------------66
3.3.2.1 Dyeing of untreated cotton fabrics with direct dyes by
conventional method -----------------------------------------66
3.3.2.2 Dyeing of untreated cotton fabrics with reactive dyes
by conventional method --------------------------------------66
3.3.2.3 Dyeing of wool fabrics with acid dyes ---------------------67
3.3.3 Dyeing conditions for pretreated cotton fabrics -------------------67
3.3.3.1 Dyeing of pretreated cotton fabrics with direct dyes -----67
3.3.3.2 Dyeing of pretreated cotton fabrics with reactive dyes --68
3.3.3.3 Dyeing of untreated and pretreated cotton fabrics with
acid dyes --------------------------------------------------------69
3.3.4 Application of cationic fixing agents as an aftertreatment -------70
3.3.4.1 Dyeing with direct dyes --------------------------------------70
3.3.4.2 Aftertreatment with cationic fixing agent (30b) ----------71
3.4 Colour measurement ----------------------------------------------------------71
3.5 Fastness testing ----------------------------------------------------------------72
3.5.1 Wash fastness ----------------------------------------------------------72
xi
3.5.1.1 Test procedure -------------------------------------------------73
3.5.2 Light fastness ----------------------------------------------------------73
4. RESULTS AND DISCUSSION ------------------------------------------------74
4.1 Synthesis of mono- and bis-reactive 2,3-epoxy and 3-chloro-2-
hydroxy propyl derivatives ---------------------------------------------------75
4.2 Applications --------------------------------------------------------------------77
4.2.1 Pretreatment with cationic fixing agents ---------------------------78
4.2.1.1 Effect of temperature and time on the cationisation of
cotton fabrics --------------------------------------------------78
4.2.1.2 Effect of cationic agent (owf) and sodium hydroxide
(ow cationic agent) concentrations on the cationisation
of cotton fabrics -----------------------------------------------81
4.2.2 Dyeing of untreated and pretreated cotton fabrics with
direct dyes --------------------------------------------------------------84
4.2.2.1 Effect of dyeing temperature --------------------------------84
4.2.2.2 Effect of dyeing time -----------------------------------------87
4.2.2.3 Effect of dye concentration ----------------------------------89
4.2.2.4 Effect of cationic agent concentration ----------------------91
Shades of direct dyes on untreated (C) and pretreated
(C-1, C-2 and C-3; 2% owf) cotton fabrics ----------------97
4.2.3 Dyeing of untreated and pretreated cotton fabrics with
reactive dyes -----------------------------------------------------------99
xii
4.2.3.1 Effect of dyeing temperature --------------------------------99
4.2.3.2 Effect of dyeing time ----------------------------------------102
4.2.3.3 Effect of dye concentration --------------------------------104
4.2.3.4 Effect of cationic agent concentration --------------------106
4.2.3.5 Effect of alkali (anhydrous Na2CO3) ----------------------108
Shades of reactive dyes on untreated (C) and
pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics -114
4.2.4 Dyeing of untreated and pretreated cotton fabrics with
acid dyes --------------------------------------------------------------117
Shades of acid dyes on wool, untreated (C) and pretreated
(C-1, C-2 and C-3; 2% owf) cotton fabrics -----------------------121
4.2.5 Aftertreatment of direct dyes with a bis-reactive cationic
fixing agent -----------------------------------------------------------122
4.2.5.1 Effect of pH on the aftertreatment of direct dyeings ----122
4.2.5.2 Effect of cationic agent concentration on the
aftertreatment of direct dyeings ---------------------------126
Shade change of direct dyeings by aftertreatment
with a bis-reactive derivative (30b) -----------------------127
5. CONCLUSIONS -----------------------------------------------------------------128
REFERENCES ----------------------------------------------------------------------132
VITA -----------------------------------------------------------------------------------144
xiii
Appendix A
Colour strength (K/S) curves of untreated (C) and pretreated (C-1,
C-2 and C-3) cotton fabrics dyed with direct dyes (Table 25) ---------146
Appendix B
Colour strength (K/S) curves of untreated cotton fabrics dyed with
direct dyes by conventional method (Table 26) --------------------------150
Appendix C
Colour strength (K/S) curves of untreated (C) and pretreated (C-1,
C-2 and C-3) cotton fabrics dyed with reactive dyes in the absence
of salt and alkali (Table 32) -------------------------------------------------152
Appendix D
Colour strength (K/S) curves of untreated (C) and pretreated (C-1,
C-2 and C-3) cotton fabrics dyed with reactive dyes in the presence
of alkali (Table 33) -----------------------------------------------------------157
Appendix E
Colour strength (K/S) curves of untreated cotton fabrics dyed
with reactive dyes by conventional method (Table 34) -----------------161
Appendix F
Colour strength (K/S) curves of wool, untreated (C) and pretreated
(C-1, C-2 and C-3) cotton fabrics dyed with acid dyes -----------------163
Appendix G
Publications----------------------------------------------------165
xiv
Page
Table 1 General classification of surfactants ---------------------------------8
Table 2 Properties of acid dyes with cationic cotton using no salt
at pH 7 ------------------------------------------------------------------26
Table 3 Fastness properties of direct, reactive and acid dyes with
nylon, conventional cotton and cationised cotton ----------------30
Table 4 Fastness properties of acid dye on cotton cationised with
different quaternary salts ---------------------------------------------31
Table 5 Fastness properties of direct dyes on untreated and treated
cotton fabrics -----------------------------------------------------------34
Table 6 Fastness properties of direct dyes on untreated (C) and
pretreated cotton fabrics with mono (C-1) and bis-reactive
(C-2) cationic agents --------------------------------------------------37
Table 7 Fastness properties of direct dyes on untreated and treated
(poly epichlorohydrin-dimethylamine) cotton ---------------------41
Table 8 Colour strength and fastness properties of 1:2 metal complex
acid dyes on untreated and pretreated cotton (PT) ----------------43
LLIISSTT OOFF TTAABBLLEESS
xv
Table 9 Fastness properties of acid dyes on cotton -------------------------45
Table 10 Fastness properties of direct dyes on cotton aftertreated with
cationic fixing agents / syntan ---------------------------------------46
Table 11 Fastness properties of direct dyeings aftertreated with
Fixogene CXF and Matexil FC-ER under neutral and
alkaline conditions ----------------------------------------------------47
Table 12 Pretreatment conditions ----------------------------------------------65
Table 13 Dyeing conditions with direct dyes ---------------------------------68
Table 14 Dyeing conditions with reactive dyes ------------------------------69
Table 15 Reaction conditions and yields of salts 28a-d, 29a-d, 30a-b
and 31a-b ---------------------------------------------------------------76
Table 16 λ max. values of the dyes ---------------------------------------------77
Table 17 Effect of temperature on the chlorine content of
cationised fabric -------------------------------------------------------79
Table 18 Effect of pretreatment time on the chlorine content of
cationised fabric ------------------------------------------------------80
Table 19 Effect of cationic agent concentration on the chlorine
content of cationised fabric ------------------------------------------81
Table 20 Effect of NaOH concentration on the chlorine
content of cationised fabric ------------------------------------------82
Table 21 % Reflectance (at λ max. 510 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
xvi
C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange
26 (2% owf) under different temperature conditions -------------85
Table 22 % Reflectance (at λ max. 510 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26
(2% owf) at 100 oC for different time periods ---------------------88
Table 23 % Reflectance (at λ max. 510 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange 26
at 100 oC for 30 minutes using different dye concentrations ----90
Table 24 % Reflectance (at λ max. 510 nm) and the colour strength
(K/S) values of cotton fabrics pretreated with different conc.
of cationic agents (C-1, C-2 and C-3) and dyed with C.I.
Direct Orange 26 (2% owf) at 100 oC for 30 minutes ------------92
Table 25 Colour strength (K/S) and fastness properties of direct dyes
(2% owf) on untreated (C) and pretreated (C-1, C-2 and
C-3; 2% owf) cotton fabrics -----------------------------------------94
Table 26 Colour strength (K/S) and fastness properties of untreated
cotton fabrics dyed with direct dyes (2% owf) by
conventional method --------------------------------------------------96
Table 27 % Reflectance (at λ max. 500 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
xvii
C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange
13 (2% owf) at different temperature conditions ----------------100
Table 28 % Reflectance (at λ max. 500 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
C-3; 2% owf) cotton fabrics dyed with C.I. Reactive Orange
13 (2% owf) at 80 oC for different time periods -----------------103
Table 29 % Reflectance (at λ max. 500 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
C-3; 2% owf) cotton fabrics dyed with different conc. of C.I.
Reactive Orange 13 at 80 oC for 30 minutes -------------------105
Table 30 % Reflectance (at λ max. 500 nm) and the colour strength
(K/S) values of cotton fabrics pretreated with different conc.
of cationic agents (C-1, C-2 and C-3) and dyed with C.I.
Reactive Orange 13 (2% owf) at 80 oC for 30 minutes ---------107
Table 31 % Reflectance (at λ max. 500 nm) and the colour strength
(K/S) values of pretreated cotton fabrics (C-1, C-2 and C-3;
2% owf) dyed with C.I. Reactive Orange 13 (2% owf) at 80
oC for 30 minutes using different amounts of alkali ------------109
Table 32 Colour strength (K/S) and fastness properties of reactive dyes
(2% owf) on untreated (C) and pretreated (C-1, C-2 and C-3;
2% owf) cotton fabrics in the absence of salt and alkali --------111
Table 33 Colour strength (K/S) and fastness properties of reactive
xviii
dyes (2% owf) on pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics in the presence of alkali (anhydrous Na2CO3;
20g/L) -----------------------------------------------------------------112
Table 34 Colour strength (K/S) and fastness properties of reactive
dyes (2% owf) on untreated cotton fabrics dyed by
conventional method ------------------------------------------------113
Table 35 % Reflectance (at λ max. 400 nm) and the colour strength
(K/S) values of untreated (C) and pretreated (C-1, C-2 and
C-3; 2% owf) cotton fabrics dyed with different concentrations
of C.I. Acid Yellow 23 at 100 oC for 60 minutes ----------------118
Table 36 Colour strength and wash fastness properties of acid dyes on
wool, untreated (C) and pretreated (C-1, C-2 and C-3;
2% owf) cotton fabrics ----------------------------------------------120
Table 37 Colorimetric data for untreated and aftertreated direct
dyeings before wash fastness testing ------------------------------123
Table 38 Wash fastness data for untreated and aftertreated direct
dyeings ----------------------------------------------------------------124
Table 39 Colorimetric data for untreated and aftertreated direct
dyeings after wash fastness testing --------------------------------125
xix
Page
Figure 1 Classification of auxiliaries --------------------------------------------7
Figure 2 Fixing agents showing various degrees of functionality ---------10
Figure 3 Modes of reaction of the various fixing agents --------------------11
Figure 4 General scheme for the synthesis of bis-reactive 2,3-epoxy /
3-chloro-2-hydroxy propyl derivatives of quaternary
ammonium chloride ---------------------------------------------------15
Figure 5 General scheme for the synthesis of mono-reactive 2,3-epoxy /
3-chloro-2-hydroxy propyl derivatives of quaternary
ammonium chloride ---------------------------------------------------16
Figure 6 Modification of cotton with N-methylolacrylamide --------------24
Figure 7 Reaction of epoxypropyl derivatives with cellulose --------------27
Figure 8 Reaction of halohydroxy propyl derivatives with cellulose -----28
Figure 9 Synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy
propyl derivatives of quaternary ammonium chloride -----------53
Figure 10 Synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy
propyl derivatives of quaternary ammonium chloride -----------54
LLIISSTT OOFF FFIIGGUURREESS
xx
Figure 11 Dyeing profile of untreated cotton fabric with direct dyes ------66
Figure 12 Dyeing profile of untreated cotton fabric with reactive dyes ----67
Figure 13 Dyeing profile of untreated and pretreated cotton fabrics with
acid dyes ----------------------------------------------------------------70
Figure 14 Aftertreatment of direct dyed cotton fabrics with cationic
fixing agent (30b) -----------------------------------------------------71
Figure 15 Effect of temperature on the chlorine content of cationised
fabric --------------------------------------------------------------------79
Figure 16 Effect of pretreatment time on the chlorine content of
cationised fabric -------------------------------------------------------80
Figure 17 Effect of cationic agent concentration on the chlorine
content of cationised fabric ------------------------------------------83
Figure 18 Effect of NaOH concentration on the chlorine content of
cationised fabric -------------------------------------------------------83
Figure 19 Effect of temperature on the colour strength (K/S) of
untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) -------86
Figure 20 Effect of dyeing time on the colour strength (K/S) of
untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) ------89
Figure 21 Effect of dye conc. on the colour strength (K/S) of untreated
(C) and pretreated (C-1, C-2, C-3; 2% owf) cotton fabrics
xxi
dyed with C.I. Direct Orange 26 ------------------------------------91
Figure 22 Effect of cationic agent concentration on the colour strength
(K/S) of pretreated cotton fabrics (C-1, C-2 and C-3) dyed
with C.I. Direct Orange 26 (2% owf) -------------------------------93
Figure 23 Colour strength (K/S) values of untreated (C) and pretreated
(C-1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I.
Direct Orange 26 ------------------------------------------------------95
Figure 24 Effect of temperature on the colour strength (K/S) values of
untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --101
Figure 25 Effect of dyeing time on the colour strength (K/S) of
untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) --104
Figure 26 Effect of dye conc. on the colour strength (K/S) of
untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Reactive Orange 13 ---------------106
Figure 27 Effect of cationic agent concentration on the colour
strength (K/S) of pretreated (C-1, C-2 and C-3) cotton
fabrics dyed with C.I. Reactive Orange 13 (2% owf) -----------108
xxii
Figure 28 Effect of alkali conc. on the colour strength (K/S) of
pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Reactive Orange 13 (2% owf) --------------------------110
Figure 29 Effect of dye conc. on the colour strength (K/S) of untreated
(C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics dyed with C.I. Acid Yellow 23 ---------------------------119
xxiii
AATCC Review American Association of Textile Chemists and
Colorists Review
Adv. Color. Sci. Tech. Advances in Colour Science and Technology
Am. Dyestuff Rep. American Dyestuff Reporter
C Untreated cotton fabric
C-1 Cotton pretreated with compound 30a
C-2 Cotton pretreated with compound 30b
C-3 Cotton pretreated with compound 28c
Chem. Abs. Chemical Abstract
Color. Technol. Coloration Technology
Conc. Concentration
Conf. Conference
Dyeings dyed textile fibres
J.A.O.C.S. Journal of the American Oil Chemists' Society
J.S.D.C. Journal of the Society of Dyers and Colourists
K/S Colour strength
LLIISSTT OOFF SSYYMMBBOOLLSS //
AABBBBRREEVVIIAATTIIOONNSS
xxiv
owf of weight of fibre
Rev. Prog. Color. Review of Progress in Coloration
SAWTRI. South African Wool Textile Research Institute,
Tech. Rep. Technical Report
Temp. Temperature
Text. Chem. Colorist Textile Chemist and Colorist
Text. Res. J. Textile Research Journal
λ max. Absorbance at the wavelength of maximum
absorption
IINNTTRROODDUUCCTTIIOONN
1
Chapter 1
IINNTTRROODDUUCCTTIIOONN
1.1 DYES AND DYEING
Dyes are intensely coloured substances used for the coloration of
various substrates including paper, leather, fur, hair, foods, drugs, plastics and
textile materials. They are retained in these substrates by physical adsorption,
salt or metal complex formation or by the formation of covalent chemical
bonds [1].
Until the middle of nineteenth century all dyes were natural products,
extracted in most cases from a variety of plants, but also from a few animal
sources. Plant sources include roots, stems, leaves, flowers and fruits while
animal sources include certain dried insects. At present practically all dyes are
coloured organic chemicals synthesised from products of the petro-chemical
and coal-tar industries [2].
2
Dyeing is a process of colouring textile fibres and other materials so that
colouring matter becomes an integral part of the material rather than a surface
coating. The mechanism of dyeing must differ with the nature of the material,
that is, whether it is protein, cellulose or some synthetic substance [3]. The
appropriate dye class for the fibre must be used along with specific dyeing
conditions in order to gain an optimum result [4].
1.2 CLASSIFICATION OF DYES
Dyes are usually classified in two ways [5]:
1. According to the chemical constitution of the dye molecules e.g. azo
dyes, triphenylmethane dyes, stilbene dyes, anthraquinoid dyes etc. or
2. According to the method of application of the dye e.g. direct dyes, acid
dyes, reactive dyes, disperse dyes, vat dyes, sulphur dyes, mordant
dyes, metal complex dyes, basic dyes and azoic dyes.
Dyes are organic molecules and can also be classified as [5]:
1. Anionic dyes-------- in which the colour is caused by the anionic part of
the dye molecule e.g. direct, reactive and acid dyes
2. Cationic dyes------- in which the colour is caused by the cationic part of
the dye molecule e.g. basic dyes
3. Non-ionic dyes----- in which the colour is caused by the whole dye
molecule e.g. disperse dyes
3
1.3 ANIONIC DYES
Textile fibres may be dyed with anionic dyes including direct dyes, acid
dyes and reactive dyes or with cationic dyes. The term anionic dyes is intended
to mean dyes in which coloured ion is anionic in character containing sulphonic
or carboxylic groups. These dyes have long been known for the dyeing of
natural fibres such as wool and cotton as acid and direct dyes [6]. Amongst
anionic dyes, direct and reactive dyes are the most popular dye classes used for
the dyeing of cellulosic fibres which comprise over 40% of world textile
consumption.
1.3.1 DIRECT DYES
All direct dyes are substantive to cellulosic fibres. Substantivity means
the affinity of the dye with the fibre to which it is applied. The substantivity of
direct dyes for cotton is due to the linear and planar structure of the dye
molecules, which enables close alignment with chains of cellulose molecules
resulting in significant hydrogen bonding. However, the wet fastness properties
of direct dyes are inadequate for many end uses and these dyes have been
replaced to a great extent by reactive dyes which have better wet fastness and
exceptional brightness in many hues but the prime advantages of direct dyes
are ease of application, wide range of shade and economy compared with dyes
of higher fastness (reactive, sulphur or vat) [7]. There are still many
applications in the textile industry for goods dyed with direct dyes, particularly
4
where a high standard of wet fastness is not required. The development of
specialised crosslinking aftertreating agents for use with selected direct dyes of
high light fastness has enabled direct dyes to compete more effectively with
reactive dyes in meeting severe wet fastness requirements. In fact, direct dyes
are second only to sulphur dyes in their textile usage worldwide with vat and
fibre reactive dyes well behind [8].
1.3.2 REACTIVE DYES
Reactive dyes are regarded as being substantive as well as reactive to the
textile fibres. These dyes are also widely used for the dyeing of cellulosic fibres
because of their wide shade range and excellent wet fastness which arises from
a covalent bond formed between dye and the fibre. However, reactive dyeing
process requires high salt and alkali concentrations, even then the dyeing
process results in strongly coloured effluents. The fundamental problem of
reactive dyeing is that the reaction of reactive dye with water (hydrolysis)
competes with the formation of the desired covalent bond between the dye and
textile substrates (fixation reaction) and up to 40% of the reactive dye may
hydrolyse in the dyeing process. As this hydrolysed dye cannot react with the
fibre it should be washed off thoroughly in order to achieve the desired
superior wet fastness of the reactive dyeing. This involves expensive washing
off procedures and the treatment of the effluents. Thus, reactive dyes have both
economic and environmental drawbacks [9,10].
5
1.3.3 ACID DYES
Acid dyes, which are primarily used for the dyeing of nitrogenous fibres
such as wool, silk and nylon, are also anionic in nature. The relatively non-
linear structure of these acid dyes does not facilitate close alignment with the
molecular chains in cellulose, which in turn prevents hydrogen bonding.
Therefore, these dyes are not substantive to cellulosic fibres. However,
cationised cellulosic fibres can be dyed with acid dyes of both the non-
metallised and pre-metallised types. This increase in substantivity is due to the
interaction of anionic sulphonic groups in the dye molecules with the cationic
groups in the modified cellulose [11].
Generally, the dyed cellulosic fibres have a fastness to washing that does
not meet the requirements of today's consumers. This is particularly the case
not only for many direct dyes but to a lesser extent for reactive dyes also [12].
1.4 THE NEED FOR AUXILIARIES
The practice of dyeing has recently led to increased requirements in
terms of quality of dyeings and profitability of the dyeing process. There is
hardly a dyeing or printing process of commercial importance that can be
adequately operated by the use of dyes and water alone. Practically every
colorant–substrate system requires the use of additional products known as
auxiliaries.
An auxiliary has been defined [13] as:
6
"A chemical or formulated chemical product which enables a processing
operation in preparation, dyeing, printing or finishing to be carried out more
effectively or which is essential if a given effect is to be obtained."
The selection of dyes and dyeing auxiliaries is a crucial factor in
optimising dyeing processes. Different auxiliaries improve the application
characteristics and performance in terms of penetration, levelling, fixation and
shade deepening to provide brilliant intense dyeings.
The class of auxiliaries which is used to improve the retention of dye by
the fibre is traditionally called fixing agents. These chemicals function by
forming a dye-fixing agent complex of large molecular size and reduced
aqueous solubility and therefore higher wet fastness [14].
1.5 CLASSIFICATION OF AUXILIARIES
It is much harder to device a classification system for auxiliaries than it
is for dyes. The broadest classification of auxiliaries is achieved simply by
dividing them into non-surfactants and surfactants. Non-surfactants include
simple electrolytes, acids and bases, both inorganic and organic whereas
surfactants are defined [13] as:
"An agent, soluble or dispersible in a liquid, which reduces the surface
tension of the liquid"
7
Figure 1 Classification of auxiliaries
1.5.1 CLASSIFICATION OF SURFACTANTS
Surfactants owe their properties to their molecular structure, which
contains both hydrophobic and hydrophilic parts. The surfactants used as
textile auxiliaries can be divided into four major groups (Table 1) depending
on the type and distribution of the polar forces [15].
Auxiliaries
Non-surfactants Surfactants
Simple electrolytes
Acids and bases, both inorganic and organic
Anionic surfactants
Non-ionic surfactants
Amphoteric surfactants
Cationic surfactants
8
Table 1 General classification of surfactants
Class of surfactant Degree of ionic charge on the
_____________________________________________
hydrophobe hydrophile (associated ion)
Anionic surfactants Weakly negative Strongly positive
Cationic surfactants Weakly positive Strongly negative
Non-ionic surfactants Uncharged Uncharged
Amphoteric surfactants These possess balanced negative and positive charges, one or
other of which dominates in solution depending on pH
1.6 PRETREATMENTS AND AFTERTREATMENTS FOR
ANIONIC DYES
The use of pretreatments or aftertreatments to improve the fastness
properties of dyeings has a long and prolific history. Notable improvements in
the wet fastness properties of anionic dyes can be brought about by
pretreatment or aftertreatment of textile fibres [16].
Three main approaches which were adopted for the pretreatment of
cellulose fibres include:
1. Vinyl grafting
2. Reaction with cationic molecules
3. Application of cationic polymers
Different aftertreatment processes include:
1. Diazotization and development
2. Metal salt treatments
9
3. Formaldehyde treatment
4. Cationic fixing agents
5. Crosslinking agents and resin treatments
Amongst various pretreatment and aftertreatment systems cationic fixing
agents are most widely used.
1.6.1 CATIONIC FIXING AGENTS
Cationic fixing agents were initially applied as aftertreatments to the
dyed textile fibres to improve their wet fastness properties [17,18]. However,
the improved fastness was related only to non-detergent agencies. Later on, this
limitation of mono-functional cationic fixing agents has been overcome by the
development of polyfunctional crosslinking fixing agents which carry reactant
groups capable of forming more permanent bonds with other suitable groups in
the dye or fibre [19,20]. The basic mechanism of multifunctional fixing agents
has been well described by Robinson [21] as shown in Figure 2 and 3.
During 1980's there was a great revival of interest in the techniques for
enhancing the dyeability of cellulosic fibres with reactive or direct dyes by
pretreatment with a great variety of cationic products usually based on
nitrogen. This modification of cellulosic fibres with cationic agents resulted in
increased substantivity of anionic dyes for cellulosic fibres by introducing new
cationic sites. Lewis and Lei reviewed numerous chemicals that can be used to
provide cationic charges to cotton fibres [22]. Pretreatment of cellulosic fibres
10
with cationic agents has been reported to enhance the uptake of anionic dyes
and facilitate the fixation of reactive dyes in the absence of either salt or alkali
[23,24]. The cationised fibre not only has improved substantivity for direct and
reactive dyes, but could also be dyed with acid dyes [11].
Amines [25], quaternary ammonium [26], phosphonium [27] and
tertiary sulphonium [28] compounds can be used as dye fixing agents. By far
the most important type of cationic fixing agents used in textile processing is
quaternary ammonium salt.
Figure 2 Fixing agents showing various degrees of functionality
+
+
+
+
Monofunctional type
Bifunctional type
Trifunctional type
Tetrafunctional type
11
Figure 3 Modes of reaction of the various fixing agents
1.6.1.1 QUATERNARY AMMONIUM SALTS
Quaternary ammonium salts have widespread applications in different
fields and are used as surfactants [29], phase transfer catalysts [30,31],
solvents, drugs, herbicides [32], antimicrobials [33-35] and disinfectants [36].
Being surfactants these compounds are used as softeners for textile and paper
(H+)
(OH -)
3OS-D o+ -
3OS-D o
HO
HO
O
HO
O
O
Monofunctional type
Bifunctional type
Trifunctional type
Tetrafunctional type
Cellulose 3OS-D
3OS-D o
+ -
+ -
+ -
12
products, as emulsifiers [37,38], as washing agents for textile materials dyed or
printed with cationic dyes [39] and as fixing agents for cellulose-containing
materials dyed with anionic dyes [40,41]. The positive charge in these
compounds imparts antistatic properties to wool, cotton and other cellulosic
fibres as well as certain synthetic fibres [38,42].
Amongst the manifold applications, one of the primary functions of
these compounds is their use as cationic fixing agents. Different quaternary
ammonium salts [40,43,44] have been applied to the fibres either as
pretreatment or aftertreatment to improve the wet fastness properties of anionic
dyes. These include monomeric or polymeric quaternary ammonium salts
having different reactive groups. The most commonly used quaternary
ammonium salts are:
1. dialkyl azetidinium chloride (1)
2. epoxy / halohydroxy propyl derivatives (2, 3)
3. mono- and bis-reactive haloheterocyclic derivatives (4)
4. poly-epichlorohydrin dialkyl derivatives (5)
The anions in these fixing agents are usually chloride or bromide.
N+
OHR1
R2
-Cl
O
N+
R1
R2R3
X-
N+
R1
R2R3OH
Cl
X-
1 2 3
13
N
N
N
Cl
R NHN
+ R2R1
R3
X-
O
N+
R2
R1HX
-n
4 5
Many of the attempts to fix quaternary ammonium salts to cellulose via
ether linkage have included the use of epoxy / halohydroxy propyl derivatives
[45,46]. Amongst these derivatives, 2,3-epoxypropyl trimethyl ammonium
chloride [47,48] and 3-chloro-2-hydroxy propyl trimethyl ammonium chloride
[49] have been reported to improve the dye exhaustion and fastness properties
but the results left scope for further work.
Mono- and bis-reactive haloheterocyclic derivatives usually based on
cyanuric chloride have also been reported to improve the wet fastness
properties of anionic dyes [50]. However, the reactivity of mono-reactive
haloheterocyclic derivatives to the textile fibres is low and these compounds
are also expensive. So the practical utility of these compounds is low.
Polymeric cationic agents have also been reported in this regard. These
compounds usually show poor penetration and distribution of dyes [22]
resulting in poor light fastness properties of the dyed textile fibres as compared
to fabrics pretreated with lower molecular weight compounds.
14
1.7 PROBLEMS ENCOUNTERED WITH THE FIXING AGENTS
Although a variety of fixing agents have been used to improve the
fastness properties of anionic dyes but to date none has achieved significant
commercial success. All these treatments enhanced the uptake of the dye yet
there are practical drawbacks to all these treatments including hue changes,
poor penetration into the fibre [51] and light fastness limitations [22]. These
areas require further investigations and there is still a need for novel dyeing
processes that improve properties in respect of application and fastness
properties of the dyeings.
1.8 PLAN OF WORK
Although mono-reactive epoxy / halohydroxy propyl derivatives
improved the wet fastness properties of anionic dyes but to the best of our
knowledge, no significant work has been done on bis-reactive epoxy /
halohydroxy propyl derivatives or mono-reactive epoxy / halohydroxy propyl
derivatives of quaternary ammonium salts containing some other reactive
groups.
Keeping this in view and due to our interest in the synthesis of cationic
fixing agents, this research is proposed that pertains to the synthesis of new bis-
reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary
ammonium chloride (Figure 4). We expect that these compounds will bind to
the fibre more permanently and provide more cationic dye sites for anionic
15
dyes, thus showing a higher affinity and reactivity with the fibre than the
mono-reactive epoxy / halohydroxy propyl derivatives. This will not only
enhance the uptake of the dye but also improve the general fastness properties.
In addition, mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl
derivatives containing cyano and carboxylic groups will also be synthesised
(Figure 5). It is expected that these additional groups may further enhance the
exhaustion and fixation ability of these compounds by forming a linkage with
the fibre and /or the dye.
N
R
R (CH2)nN
R
R
Cl-
O
N+
R
R
(CH2)n
N+R
R
O
Cl-
O
Cl
O
ClConc. HCl
Cl-
N+ R
R(CH2)n N
+R
R
OHOH
ClCl
Cl-
Figure 4 General scheme for the synthesis of bis-reactive 2,3-epoxy / 3-
chloro-2-hydroxy propyl derivatives of quaternary ammonium
chloride
16
N
R
R
(CH2)n
X
N+
R
R
(CH2)nX
O
Cl-
N+
R
R
(CH2)n
XOH
ClCl
-
O
Cl
O
ClConc. HCl
Figure 5 General scheme for the synthesis of mono-reactive 2,3-epoxy / 3-
chloro-2-hydroxy propyl derivatives of quaternary ammonium
chloride
Reaction parameters for the synthesis of these compounds will be
optimised. The newly synthesised compounds will be purified by different
purification techniques and the purified compounds will be characterised using
different spectroscopic techniques.
These newly synthesised mono- and bis-reactive quaternary ammonium
compounds will be used as pretreatments and aftertreatments to the cotton
fabrics dyed with anionic dyes (direct, reactive and acid dyes). The colour
strength (K/S) values and fastness properties of the dyeings will be determined
and the effect of fixation on shade change and fastness properties will be
evaluated.
LLIITTEERRAATTUURREE
RREEVVIIEEWW
18
Chapter 2
LLIITTEERRAATTUURREE RREEVVIIEEWW
2.1 GENERAL DEVELOPMENT
Most early dyeing processes used naturally occurring coloured
compounds e.g. dye woods [52], which had no significant affinity for cotton
and silk. These processes required a metal salt mordant before dyeing and after
dyeing, fixation with tannin.
The major growth and establishment of the synthetic dye industry was
initiated with the discovery of Congo Red, the first direct dye for cotton,
in1884 [53]. Although some early direct dyeings were claimed to be fast to
soaping [54] it was soon appreciated that fastness to light and wet treatments
left much to be desired.
From 1930 onwards, complexing of direct dyes, present on the fibre,
with aqueous solutions of cationic fixing agents began to be fully exploited.
The importance and use of these agents was greatly extended by the
19
development of products rising from the condensation of cyanamide (6) or
similar compounds with formaldehyde. These resin fixatives [55] of which
Fibrofix (7) was a classical example [56], could be applied by a simple,
finishing technique to cellulosic fibres dyed or printed with direct dyes. This
resin fixative class was rapidly extended to provide a large number of agents
based on the condensation products of formaldehyde with cyanamide
derivatives [57], which were suitable for aftertreatment of direct dyes on
cellulose fibres. Later on, the reaction products of cyanamide or cyanamide
derivatives with monofunctional or polyfunctional amines and the condensates
of these amines with formaldehyde or N-methylol derivatives were used as an
aftertreatment to improve the wet fastness properties of anionic dyes on
cellulose fibres [58,59]. Other relevant developments in this area have been
reviewed in detail [60].
NH2 C N
NH2
NH
NH
N
CN
+
n
nX-
6 7
Extensive research work has shown that formaldehyde based resin
finished products release formaldehyde into the atmosphere directly or during
processing, handling, garment manufacturing and subsequent wearing of
20
textiles due to the hydrolysis of unreacted or partially crosslinked N-methylol
derivatives present on the fibre. Direct release of formaldehyde into the
working environment causes severe irritation to eyes, nasal passages and
respiratory tract while an unreacted or partially crosslinked resin causes an
allergenic response of the skin upon continuous handling of textiles [61]. For
reasons of these health problems associated with formaldehyde, there was an
increasing demand for non-formaldehyde fixing agents. It has also been
reported that formaldehyde containing fixing agents for direct dyeing could be
substituted by nitrogen containing non-formaldehyde fixatives without
sacrificing the performance properties of the finished goods. Selection of
suitable non-formaldehyde fixatives could actually produce better products
than using the formaldehyde fixative [8]. Nitrogenous-based dye fixing agents
have also been reported to improve overall fastness properties, without
affecting the tone and depth of shades of reactive dyes on cotton substrates.
The results indicated that commercial non-formaldehyde and formaldehyde-
based dye fixing agents could be replaced by laboratory developed
nitrogenous-based dye fixing agents [62].
After the discovery of reactive dyes, dyeing with reactive dyes became
the most versatile method for the coloration of cellulosic fabrics. These dyes
were used instead of aftertreated direct dyes but they have both economic and
environmental drawbacks because of high salt usage and insufficient fixation
caused by hydrolysis leading to pollution of the effluent [9]. However, if an
21
aftertreatment is given prior to the rinsing stage, hydrolysed dye also gets fixed
showing improved wet fastness. Therefore, aftertreatment still remained an
extremely useful way of improving the wet fastness properties of a deep dyeing
that failed to meet the necessary standards.
Developments taking place during the recent decade have enabled direct
dyes to compete with reactive dyes in the field of severe wet fastness
requirements. The production, in the 1960’s, of polyfunctional cross-linking
fixing agents [19,20,63,64] capable of reacting with both dye and fibre was a
significant development. These agents were used to aftertreat dyes on
cellulosic, polyamide and wool fibres.
The use of anionic dyes (acid, direct and reactive dyes) and cationic
fixing agents is widespread in dyeing processes. Many studies have been
devoted to improve the fastness properties of anionic dyes by pretreating or
aftertreating the fibres with amines or reactive cationic agents. Most of these
studies have used monomeric or polymeric quaternary ammonium salts having
different reactive groups. These include dialkyl azetidinium chloride,
epoxypropyl / halohydroxy propyl trialkyl derivatives of ammonium chloride,
mono- and bis-reactive haloheterocyclic compounds and poly-epichlorohydrin
dimethylamine derivatives.
The mechanisms of dyeing cotton textiles pretreated with quaternary
compounds of mono-reactive epoxypropyl type and mono- and bis-reactive
chlorotriazine type were studied. The high reactivity and better thermal
22
stability of chlorotriazine type agents than epoxypropyl type agents made them
suitable for pad-batch or exhaust applications rather than the more costly pad-
bake process and gave effective enhancement of reactive dye uptake [51]. Later
on, it was found that the pretreatment of cotton fabric with bis-reactive cationic
agent promoted higher extents of dye exhaustion and fixation than that with
mono-reactive cationic agent [50]. The low substantivity and poor thermal
stability of mono-reactive epoxypropyl agents made them unsuitable for
exhaust application and was also responsible for the poor dye penetration due
to significant migration of agent during the thermal reaction step of pad-bake
process leading to non-uniform distribution of cationic dye sites on the fibre
[51]. The reactivity of cotton with such type of compounds has been studied
under a variety of conditions [48,65,66] but no best procedure has yet been
established. Recent work has shown that cotton cationised through a pad-batch
process gave excellent dye penetration indicating the uniform distribution of
cationic dye sites through this process. Thus, a pad-batch process seems to be
good for achieving high yields of cationically modified cotton with uniform
distribution of dye sites [67]. The pad-batch dyeing technique has now become
an important dyeing method for its simplicity, low consumption of energy and
water, and excellent reproducibility [68].
Recently, a new method based on the sol-gel process has proved to be an
effective way to improve the wash fastness of direct dyes on cotton without
essential loss of properties such as handle and strength of the fabric [69]. This
23
process involves the fixation of dyes through hydrogen bonding, van der Waal's
forces and covalent bonding. It was also found that a sol prepared from an
epoxy containing precursor exhibited the best results as a fixing agent on dyed
cotton [70].
2.2 MONOMERIC QUATERNARY AMMONIUM SALTS
The use of cationic agents in the form of primary, secondary, tertiary
and quaternary amine residues has been known since 1926 [25,26].
Pretreatment of cotton fabrics with Katamin AB (alkylbenzyldimethyl
ammonium chloride; 8) has been reported to increase the uptake of reactive
dyes and reduce the amount of dye and alkali required for dyeing [71].
N+
CH3
CH3
RCl
-
OH NH
O
CH2
8 9
To investigate systematically the effect of attaching a variety of amines
to the cellulose fibre, cotton was modified by pretreatment with N-
methylolacrylamide (9; Allied Colloids) to introduce pendant-activated double
bond (Figure 6). By introducing amino residues at these new sites good colour
yield and high fixation values of reactive dyes were achieved at pH 5-7 in the
absence of electrolyte but light fastness was lowered. Cellulose modified with
24
only N-methylolacrylamide (9) also gave high colour yields with dyes
containing pendant aliphatic amino residues in the presence of electrolyte under
alkaline conditions [23].
Cell OH + OH NH
O
CH2O NH
O
CH2Cell OH2o
+ZnCl2 / 150 C
Figure 6 Modification of cotton with N-methylolacrylamide
Recently, a new fibre-reactive quaternary compound containing an
acrylamide residue was synthesised and applied to cotton fabrics using a pad–
bake process. It was found that the treated fibre could be dyed with reactive
dyes without the addition of salt or alkali. The reactive dyes were almost
completely exhausted and showed a high degree of covalent bonding with the
pretreated cellulose [72]. A fibre-reactive chitosan derivative, O-
acrylamidomethyl-N-[(2-hydroxy-3-trimethylammonium) propyl] chitosan
chloride, was used for the modification of cotton. Dyeing of this modified fibre
with direct and reactive dyes gave higher colour yields and better wash fastness
properties without the addition of salt but reduced the light fastness as
compared to the untreated cotton [73]. Cationic starch had also been used for
the modification of cotton fabrics. Dyeing of this modified fibre with reactive
dyes using a continuous dyeing method gave improved dye fixation and level
25
dyeing without the presence of salt compared with untreated cotton. The
dyeings also showed good wash and rub fastness [74].
2.2.1 AZETIDINIUM CHLORIDE
An investigation of the direct dyeing of cotton cationised with 1,1-
dimethyl-3-hydroxy azetidinium chloride (10), 1,1-diethyl-3-hydroxy
azetidinium chloride (11) or Sandene 8425 (aliphatic polyamine derivative;
Clariant) showed improved dye absorption and firmness of colour in the
absence of salt in a neutral medium [41,75]. The above-modified fibre also
enhanced the exhaustion and fixation of acid (Table 2) [11] and reactive dyes
[76] on cotton in the absence of salt in a neutral medium. The effect of alkali
pretreatment followed by 1,1-dimethyl-3-hydroxyazetidinium chloride
(DMAC) treatment on the dyeability of cotton yarn with reactive dyes has been
reported to produce a much stronger colour yield than by DMAC treatment
without alkali pretreatment [77].
N+CH3
CH3
OHCl-
N
+H5C2
H5C2
OHCl-
10 11
26
Table 2 Properties of acid dyes with cationic cotton using no salt at pH 7
K/S Fastness properties
_____________ ____________________________
Washinga
After After _________________
Dye Treatmentb wash DMFc A C W Light
C.I. Acid I 3.62 0.95 4 4 3-4 4
Red 73 II 9.34 4.02 2-3 2 2 6
III 1.04 0.39 2-3 4 3-4 5-6
C.I. Acid I 2.51 0.50 2-3 2 2-3 2-3
Orange 7 II 6.18 0.98 2 2-3 2-3 6
III 1.05 0.35 2 4-5 4-5 3
C.I. Acid I 1.23 0.35 2 3-4 2 5
Yellow 36 II 3.25 0.37 2 4 3 4-5
III 0.64 0.21 3 3-4 4-5 4
C.I. Acid I 3.87 2.03 2 3-4 2 5
Green 12 II 7.14 4.76 4 4 3 5
III 1.95 0.41 2 4 3 6
C.I. Acid I 2.72 2.66 3-4 2-3 2-3 6
Red 183 II 12.14 5.88 4 4-5 4 6
III 2.51 0.43 3 4-5 4-5 6
C.I. Acid I 4.63 3.20 2 4 2-3 6
Red 214 II 12.51 7.55 3-4 3-4 3-4 6
III 3.25 0.68 2 2 3 6
a. A, change in colour; C, staining on cotton; W, staining on wool
b. I, Sandene 8425; II, 1,1-dimethyl-3-hydroxy azetidinium chloride (DMA-AC); III, 1,1-diethyl-3-
hydroxy azetidinium chloride (DEA-AC)
c. DMF, dimethylformamide
27
2.2.2 EPOXY AND HALOHYDROXY PROPYL DERIVATIVES
Several patents have covered the preparation of epoxy and halohydroxy
propyl derivatives of ammonium chloride [78-82]. Many attempts have been
made to fix epoxy and halohydroxy propyl derivatives to cellulose via an ether
linkage. Epoxypropyl derivatives of ammonium chloride react with cellulose
under alkaline conditions to form ethers (Figure 7).
O
N+
R3R2
R1Cl
-
Cell OH N+
R1
R2 R3 OH
OCell
Cl-
OH-
+
Figure 7 Reaction of epoxypropyl derivatives with cellulose
However, when halohydroxy propyl derivatives have been used for the
cationisation of cellulosic fabrics under alkaline conditions, an epoxide ring is
first formed in the cationising agent by the action of alkali and it then reacts
with the hydroxyl group of cellulose under alkaline conditions (Figure 8).
Alkali is required both for the formation of epoxide ring and for its reaction
with cellulose. Thus, both epoxy and halohydroxy propyl derivatives have the
same reactive group.
28
N+
R1
R2 R3 OH
Cl
Cl-
O
N+
R3R2
R1 Cl-
OH-
O
N+
R3R2
R1 Cl-
Cell OH N+
R1
R2 R3 OH
OCell
Cl-
OH-
+
Figure 8 Reaction of halohydroxy propyl derivatives with cellulose
The first product of this type was Glytac A (Protex; 12), which reacted
with cellulose via the epoxy group at alkaline pH [83]. The use of 2,3-
epoxypropyl trimethylammonium chloride (12) as pretreatment, a simultaneous
treatment or an aftertreatment increased the fixation and fastness properties
(except rubbing fastness) of direct dyes on cotton textiles. It has been observed
that a pretreatment generally produced better results than an aftertreatment. An
increase in the number of solubilising groups on the direct dye molecules
generally resulted in a deterioration of the rubbing fastness of pretreated fabrics
and an improvement in case of aftertreated fabrics [84]. This treatment has also
been reported to increase the fixation of various reactive dyes on cotton but
reduced the fastness properties of dyed fabrics [85].
A comparative study of the reactive dyeing of unmodified cotton and
cotton cationised with compound (12) with dyes having four different reactive
groups showed that cationic cotton gave the same colorfastness as the
unmodified cotton, but usually with higher colour yields [47]. Cotton modified
29
with this agent through a cold pad-batch process has been reported to show
excellent colour yields and fastness properties for a number of direct
(Crompton & Knowles), reactive and acid dyes (Dystar), without the use of
electrolytes or multiple rinses, which are normally employed in cotton dyeing
(Table 3) [67].
O
N+
CH3
CH3CH3
Cl-
N+
R1
R2R3OH
Cl
Cl-
12 13
R1 = R2 = R3 = CH3, C2H5, C3H7, C5H11
3-chloro-2-hydroxypropyltrialkyl derivatives of ammonium chloride
(13) were synthesised through the reaction of various trialkylamines with
epichlorohydrin and were used for the cationisation of cellulosic fibres under
alkaline conditions. Cationised fibres showed slightly better light fastness than
those on nylon or wool dyed with the same acid dye (Ciba) but their wash
fastness decreased with increasing length of hydrocarbon chain (Table 4). The
cationised fibres also showed excellent antimicrobial activity in spite of the
small amount of cationic agent introduced into the fibre. It was also found that
antimicrobial activity increased with the increase in the hydrocarbon chain
[86].
30
Table 3 Fastness properties of direct, reactive and acid dyes with nylon,
conventional cotton and cationised cotton
Colour fastness
_______________________
Change Light
Dye Cotton fabric K/S in colour Staining a fastnessb
Conventional cotton and cationised cotton
C.I. Direct Blue 78 Untreated 8.67 2 2-3 5
Cationic 13.99 4-5 4 5
C.I. Direct Blue 86 Untreated 8.76 1 2-3 5
Cationic 44.74 5 4-5 5
C.I. Direct Red 80 Untreated 14.16 2 2 3-4
Cationic 20.11 4-5 5 4-5
C.I. Direct Yellow 106 Untreated 10.29 3 3-4 5
Cationic 14.46 5 5 5
C.I. Reactive Blue 21 Untreated 15.08 4-5 5 5
Cationic 53.34 4 5 4-5
C.I. Reactive Blue 203 Untreated 16.37 4-5 4-5 5
Cationic 24.24 4-5 4-5 4-5
C.I. Reactive Red 239 Untreated 8.24 5 4-5 4-5
Cationic 12.40 5 4-5 4-5
C.I. Reactive Orange107 Untreated 6.91 4-5 5 5
Cationic 18.24 4 5 4-5
Nylon and cationised cotton
C.I. Acid Black 172 Nylon 4-5 4-5 5
Cationic cotton 2-3 4-5 5
C.I. Acid Blue 221 Nylon 4-5 4-5 5
Cationic cotton 3-4 4-5 4-5
C.I. Acid Red 260 Nylon 5 4-5 5
Cationic cotton 3-4 3-4 5
C.I. Acid Yellow 79 Nylon 4-5 4-5 5
Cationic cotton 4-5 4-5 5
a. Staining of nylon fabric during laundering and staining on cotton
b. 20h
31
Table 4 Fastness properties of acid dye on cotton cationised with different
quaternary salts
Wash fastness
___________________
Cationic Change Light
Dye Substrate agenta in colour Staining fastness
C.I. Acid Cotton CMAC 4-5 3 4-5
Red 127 CEAC 4 3 4-5
CPAC 3 2-3 4-5
CP5AC 3 2-3 4-5
CDTAC 1-2 2 4-5
Nylon - 4-5 2-3 4
Wool - 4-5 2-3 4
a. CMAC, 3-chloro-2-hydroxypropyltrimethyl ammonium chloride; CEAC, 3-chloro-2-
hydroxypropyltriethyl ammonium chloride; CPAC, 3-chloro-2-hydroxypropyltripropyl ammonium
chloride; CP5AC, 3-chloro-2-hydroxypropyltripentyl ammonium chloride; CDTAC, 3-chloro-2-
hydroxypropyldimethyltetradecyl ammonium chloride
The dyeing behavior of cotton, cationised with 3-chloro-2-
hydroxypropyl trimethyl ammonium chloride (14; Fisher Scientific), with
direct dyes was investigated. Findings revealed that cationised cotton could be
dyed without salt and required less rinsing to remove unfixed dye than cotton
dyed by conventional methods [49]. Dyeing of this cationised cotton with
fibre-reactive dyes showed deeper shades. Moreover, nonlinear colour
behaviour occurred with cationised cotton at lower concentrations than with
unmodified cotton, suggesting that predicting shades on cationised cotton
requires caution [87]. Significant differences in dyeing rates and dye uptake of
acid dyes on this cationic cotton were observed over untreated cotton. Fastness
32
to laundering and light was greatly improved for cationic cotton over untreated
cotton, but remained somewhat lower than the values for nylon [88].
N+
CH3
CH3
CH3OH
Cl
Cl-
14
The printing properties of cationised cotton that had been pretreated
with compound (12) were examined and cationisation was found to be very
effective in reducing fixation (steaming) times and washing off processes, and
in increasing colour yield and wet fastness properties for a number of reactive
[89] and direct dyes [90]. Printing on this cationic cotton with acid dyes could
be carried out at neutral pH because of the presence of cationic charges on the
fibers at all pH values, avoiding the need for a pH regulator in the print paste
and for neutralisation during washing. This technique did not need an intensive
washing procedure, and thus appeared to be a more environmentally friendly
printing process [91]. The effect of cationisation on the quality of ink-jet
printing on cotton fabrics was also investigated. Ink-jet printing with reactive
dyes [92] and reactive inks [93] on cationised cotton was found to have good
potential as a cost-effective and more environmentally friendly printing method
using less dye, less thickener and less alkali without relinquishing outline
sharpness.
33
Epoxy and halohydroxy propyl derivatives of diallylamine (15 and 16)
have also been reported in this regard. Different epoxy and halohydroxy propyl
derivatives of diallylamine were synthesised and applied to cotton fabrics
before dyeing or during dyeing. Cotton fabrics treated with these agents
showed improved fastness properties for a number of direct dyes (Table 5)
[45].
O
N+
CH3
CH2CH2
X-
N+
CH3
OH
Cl
CH2CH2
X-
15 16
X = OSO3CH3, OSO3C2H5, SO3C6H4CH3-
The effect of cationisation on the performance of cotton finishes has also
been investigated. Cationisation of cotton with 2,3-epoxypropyl trimethyl
ammonium chloride (12) [94] and 3-chloro-2-hydroxypropyl trimethyl
ammonium chloride (14) [95] has been reported not to affect adversely the
finishes. However, the alkali required for the process improved the wrinkle
recovery angles of the treated fabrics.
34
Table 5 Fastness properties of direct dyes on untreated and treated cotton
fabrics
ISO C2S Wash fastness
________________________
Cationic Cotton Change Staining
Dye agenta fabric in colour on cotton
C.I. Direct Red 80 I Without 4 2
With 5 3-4
C.I. Direct Blue 71 I Without 4 2
With 5 5
C.I. Direct Violet 66 I Without 4-5 4
With 5 5
C.I. Direct Green 26 I Without 4-5 3-4
With 5 5
a. I, N- (3-chloro-2-hydroxypropyl)-N-methyl-N, N-diallyl ammonium p-toluenesulphonate
2.2.3 MONO- AND BIS-REACTIVE HALOHETEROCYCLIC
DERIVATIVES
Mono- and bis-reactive haloheterocyclic compounds having
monochlorotriazine as the reactive group have also been used for the
cationisation of cellulose. Although these treatments enhanced the uptake of
dye, there are practical drawbacks to all these treatments, including hue
changes, poor penetration into the fibre [51] and light fastness limitations [22].
Monofunctional cationic agents of monochlorotriazine type (17) were
evaluated on cotton yarn in the production of differential dyeing effects. Yarn
pretreated with these cationic agents showed better uptake of acid and direct
35
dyes than does untreated yarn [96]. The stoichiometry of interaction of both
acid and direct dyes with cotton modified with a reactive cationic agent (18)
was examined. The results showed that the presence of the cationic sites
enhanced the amount of dye taken up by diffuse adsorption [97].
N
N
N
NH NHN
+H5C2
R
C2H5
Cl
X-
17
Cl-
N
N
N
NH NHN
+
C2H5
Cl
H5C2
18
Recent developments revealed that cotton fabrics pretreated with mono-
and bis-reactive cationic agents (19 and 20) showed fairly high degrees of
exhaustion and fixation of direct dyes under neutral conditions in the absence
of salt. Improved fastness was achieved for this modified fibre when compared
with untreated samples. Results also indicated that cotton pretreated with the
36
bis-reactive cationic agent showed higher degrees of dye exhaustion and
fixation relative to cotton pretreated with mono-reactive agent (Table 6) [50].
I-
N
N
N
NH NHN
+
C2H5
Cl
H5C2 C2H5
19
NHNH
N
N
N
N
N
N
Cl Cl
NHNH
N+
N+ C2H5
C2H5H5C2C2H5
H5C2
H5C2
I-
I-
20
Reactive cationic agents, phenylmonochlorotriazinyl and epoxypropyl,
were used for cotton pretreatment using a pad–dry–curing technique. The
dyeability of cationised cotton fabrics using CI Acid Red 1 was found to be
dependent on the cationic agent concentration and the appropriate mixture used
[98]. More complex multifunctional structures (21 and 22) have also been
evaluated by exhaust applications and these gave effective enhancement of dye
uptake [99,100].
37
Table 6 Fastness properties of direct dyes on untreated (C) and pretreated
cotton fabrics with mono- (C-1) and bis-reactive (C-2) cationic
agents
Wash fastnessa
__________________________
Cotton Change Light
Dye fabricb F (%) in colour SC SW fastness
C.I. Direct Yellow 50 C - 3-4 3-4 3 4-5
C-1 32 4 4 4 5
C-2 75 4-5 4-5 4-5 4-5
C.I. Direct Orange 61 C 3 3-4 3 3-4 4-5
C-1 45 4 4 4 4-5
C-2 83 4-5 4-5 4-5 4-5
C.I. Direct Blue 71 C 1 3 2 1-2 4
C-1 28 4 4 3-4 4
C-2 68 4 4 4 2
C.I. Direct Green 26 C 2 3-4 3 3 4
C-1 29 4-5 4-5 4-5 3-4
C-2 58 4-5 4-5 4-5 2
a. SC, staining on cotton; SW, staining on wool
b. C-1, Cotton cationised with monochlorotriazine mono-reactive cationic agent; C-2, Cotton
cationised with bischlorotriazine bis-reactive cationic agent
NHNH
N
N
N
N
N
N
Cl Cl
NHNH
N+
N+CH3
CH3CH3 CH3 CH3
CH3
--Cl Cl
21
38
NH
N
N
N
NH
N
N
N
ClCl
NHNH OHOH
N+
N+
CH3
CH3
CH3
CH3
CH3
CH3
Cl-Cl
-
22
2.3 POLYMERIC QUATERNARY AMMONIUM SALTS
Many cationic polymers have been applied to cellulose with a view to
enhance the uptake of anionic dyes and it is considerably more difficult in these
instances to interpret the precise mechanism of the interactions involved, apart
from the obvious participation of electrostatic forces between the dye anions
and the basic groups (often quaternary nitrogen atoms) in the polymer.
Polyamide-epichlorohydrin resin (Hercosett 125; Hercules Powder
Corpn.), having azetidinium cation (23) as the reactive group, was applied to
cotton with a view to produce a modified fibre suitable for the absorption and
fixation of reactive dyes at neutral pH in the absence of salt. Selected highly
reactive dyes gave good colour yield and fixation but lower fixation values
were obtained when dyes of low reactivity were applied to the pretreated cotton
[101].
39
N+
OHCl-
23
A comparative study of the reactive dyeing of cellulosic fibres modified
with Hercosett 125, 1,1-dimethyl-3-hydroxyazetidinium chloride (10) or Glytac
A (12) revealed that fixation of reactive dyes, even under neutral or slightly
acidic conditions, was attributed to the presence of highly nucleophilic
secondary, tertiary or quaternary amino groups. Light fastness of the fibres
pretreated with polymeric compound was poor because of poor penetration and
distribution of dyes. However, pretreatment with lower molecular weight
compound resulted in improved light fastness [22]. It was thought that better
fixation of both high and low reactivity dyes might be achieved by introducing
more highly nucleophilic sites into the cotton. Incorporation of thiourea and
ethylenediamine into the polymer Hercosett 125, during the application process
has beneficial effects on the results obtained. Thiourea addition inhibits the
crosslinking of the resin, leaving more nucleophilic NH groups as sites for dye
reaction [102]. Ethylenediamine promotes crosslinking of the resin but itself
provides extra NH groups as dye reactive sites [103].
Pretreatment of cotton with a cationic / nucleophilic polymer facilitates
the dyeing of cotton with a variety of reactive dyes in the absence of salt and
alkali at neutral pH [104]. The dyeings thus produced were level and of
40
comparable depths to those obtained using the appropriate standard methods.
Pretreated dyeings showed excellent wash fastness but reduction in light
fastness. This pretreatment has also reduced the time and water required for
dyeing, thus becoming a more environmentally friendly method for the reactive
dyeing of cotton [10].
Derivatives of poly-epichlorohydrin, instead of epichlorohydrin were
prepared and used as new cationic agents. Polyepichlorohydrin-dimethylamine
derivative (24) was applied to cotton under alkaline conditions by the
exhaustion method. Pretreatment of cotton with this agent not only reduced the
amount of salt needed, but also increased the exhaustion efficiency and
perspiration fastness of direct dyes (BAY; Table 7) [105].
O
N+
CH3
CH3HCl
-n
24
41
Table 7 Fastness properties of direct dyes on untreated and treated (poly
epichlorohydrin-dimethylamine) cotton
Wash fastness
________________________
Cotton Change Staining Light
Dye fabric K/S in colour on cotton fastness
C.I. Direct Blue 78 Untreated 14.02 3-4 3 4
Treated 14.26 3 3 3-4
C.I. Direct Orange 39 Untreated 11.58 3-4 3-4 4
Treated 11.90 3 3 3-4
C.I. Direct Blue 86 Untreated 6.06 3-4 4-5 4
Treated 11.74 2-3 4-5 3-4
A commercial cationic fixing agent, Solfix E (modified quaternary
polyamine derivative; Ciba) was used to pretreat cotton prior to dyeing with six
commercial direct dyes in the presence of electrolyte. Pretreatment enhanced
the colour strength but wash fastness was similar to their untreated counterparts
[106]. Pretreated fabrics also gave improved printability with pigment and
anionic dyes. The prints obtained on cationised cotton showed better overall
fastness properties than prints obtained on untreated cotton [107]. Three
commercial cationic fixing agents, namely Matexil FC-PN (a phenol
formaldehyde ammonium chloride condensate; ICI), Matexil FC-ER (poly
diallyldimethyl ammonium chloride; 25, ICI) and Solfix E (Ciba), originally
marketed as aftertreating agents for direct dyes, were used as pretreatments for
cotton modification. Pretreatment was found to increase the colour strength of
42
the dyeings when dyeing had been carried out without electrolyte. However,
when electrolyte was used, the pretreated samples exhibited generally lower
colour strength than the standard dyeings. The wash fastness of the dyeings
almost remained unaffected by pretreatment while light fastness was slightly
lowered [108].
The study of the effect of different pretreatment agents on the uptake of
1:2 metal complex acid dyes by samples of cotton / polyamide fabrics showed
excellent dye uptake by the pretreated samples compared with the untreated
samples. The pretreatment using Matexil FC-ER (25, ICI) or a development
cationic fixing agent gave the most uniform results [109]. Modification of
cotton with a polymeric quaternary ammonium compound of 4-vinyl pyridine
(26) has enabled the dyeing of cotton fibre with 1:2 metal complex acid dyes
without salt at neutral or slightly acidic pH values. Pretreated dyeings displayed
high colour strength, good to very good wash fastness and excellent light
fastness (Table 8) [110].
N+
CH3 CH3
Cl-
n
NN+
CH3
Cl-
n n
25 26
43
Table 8 Colour strength and fastness properties of 1:2 metal complex acid
dyes on untreated and pretreated cotton (PT)
Wash fastness
_______________________
Cotton Change Staining Light
Dye fabrica K/S in colour on cotton fastness
C.I. Acid Yellow 137 Untreated 2.1 - - -
PT 14.4 5 5 7
C.I. Acid Red 182 Untreated 1.8 - - -
PT 18.0 5 5 6
C.I. Acid Black 107 Untreated 2.3 - - -
PT 15.8 4-5 5 7
C.I. Acid Orange 144 Untreated 1.5 - - -
PT 12.3 4-5 5 6
C.I. Acid Blue 284 Untreated 1.9 - - -
PT 16.1 4-5 5 6
C.I. Acid Brown 384 Untreated 0.8 - - -
PT 15.7 4 5 6
C.I. Acid Violet 90 Untreated 1.4 - - -
PT 16.3 4 5 6
C.I. Acid Blue 193 Untreated 1.7 - - -
PT 13.8 4 5 7
a. PT, cotton pretreated with poly (4-vinyl-N-ethylpyridine) quaternised polymer
Homopolymer or copolymers of alkyl diallylamine with epichlorohydrin
have also been reported to improve the wet fastness properties of anionic dyes
on textile fibres [12,111]. Aftertreatment with copolymers of mono and
diallylamine enhanced the colour fastness of reactive dyes on cellulosic fabrics
[112,113].
44
Aftertreatment of the dyeings produced on cellulosic fibres, pretreated
with fixing agent 25 and Fixogene CXF (copolymer of dimethylamine and
epichlorohydrin; 27, ICI), with cationic polymers enhanced the light and wash
fastness of acid (Table 9) [114] and reactive dyes [44]. The subsequent
application of syntan (synthetic tanning agent) to the aftertreated dyeings
enhanced the effectiveness of commercial cationic fixing agents, Matexil FC-
ER (25) and Fixogene CXF (27), in improving the wash fastness of three
commercial direct dyes (Ciba- Geigy) on cotton but the effect of syntan was
both dye and fixing agent specific (Table 10) [115]. It has also been examined
that wash fastness was noticeably better when these fixing agents were applied
under alkaline conditions (Table 11) [116].
N(CH3)2
OH
+ Cl-
n
27
45
Table 9 Fastness properties of acid dyes on cotton
Pretreatmenta Aftertreatmentb Wash fastness
___________ ____________ __________________________
Staining
Cotton Mate- Mate- Shade ________________ Light
Sample rial % rial % change C W N K/S fastness
C.I. Acid Green 106
1C - - - - - - 0.9 -
1.1 PT1 2 - - 3/3-4 4-5/5 - - 5.60 6-7
1.2 PT1 2 AT1 2 3-4/4 5 - - 5.78 -
1.3 PT1 2 AT2 2 3-4 5 - - 5.80 -
1.4 PT1 2 AT3 2 4/4-5 5 - - 5.73 -
1.5 PT2 2 - - 2/2-3 4-5/5 - - 6.05 -
1.6 PT2 2 AT1 2 3-4 5 - - 6.01 -
1.7 PT2 2 AT2 2 2-3/3 5 - - 6.06 -
1.8 PT2 2 AT3 2 4-5 5 - - 5.97 -
C.I. Acid Red 315
2C.1 - - - - - - - - 1.96 -
2.1.1 PTI 2 - - 3 2-3 4 3/3-4 9.89 5
2.1.2 PTI 2 AT1 2 3-4 3 4-5 3-4/4 - -
2.1.3 PTI 2 AT3 2 4 3/3-4 4-5 4 - -
2.1.4 PT2 2 - - 2-3 2-3 3-4/4 3/3-4 10.93 -
2.1.5 PT2 2 AT1 2 3-4 3 4 3-4 - -
2.1.6 PT2 2 AT3 2 4 3-4 4-5 4 - -
C.I. Acid Yellow 235
2C.2 - - - - - - - - 2.17 -
2.2.1 PT1 2 - - 3 4-5 3-4 4/4-5 7.23 6-7
2.2.2 PT1 2 AT1 2 3-4 4-5 4/4-5 4-5 - -
2.2.3 PT1 2 AT3 2 3-4/4 5 4-5 4-5 - -
2.2.4 PT2 2 - - 2/2-3 4-5 3/3-4 4 6.54 -
2.2.5 PT2 2 AT1 2 3-4/4 4-5 4 4-5 - -
2.2.6 PT2 2 AT3 2 4 5 4-5 4-5 - -
a. PT1, Matexil FC-ER; PT2, Fixogene CXF;
b. AT1, Matexil FC-ER; AT2, Fixogene CXF; AT3, Copolymer of diallyldimethyl ammonium and
diallyl-2-hydroxy-3-chloropropyl ammonium chloride
46
Table 10 Fastness properties of direct dyes on cotton aftertreated with
cationic fixing agents / syntan
K/S Wash fastnessa
______________ _________________
Before After
Dye Aftertreatmentsb wash wash S C V
C.I. Direct NIL 14.84 11.13 4 1 1-2
Red 89 4% M FC-ER 14.21 12.75 4-5 2-3 3
4% M FC-ER / 2% F AXF 13.77 13.34 4-5 2-3 3
4% F CXF 14.74 12.72 4-5 1-2 2
4% F CXF / 2% F AXF 14.45 13.26 4-5 2 2-3
C.I. Direct NIL 10.98 8.01 3 1 1-2
Yellow 106 4% M FC-ER 10.49 9.94 4 2-3 3
4% M FC-ER / 2% F AXF 10.31 10.11 4 3 3-4
4% F CXF 10.36 8.81 4 1-2 2
4% F CXF / 2% F AXF 10.65 8.73 4 1-2 2
C.I. Direct NIL 17.06 12.42 3 1 1-2
Blue 85 4% M FC-ER 17.06 16.94 4-5 2-3 3
4% M FC-ER / 2% F AXF 16.81 16.14 4-5 2-3 3
4% F CXF 16.08 15.79 4-5 1-2 2
4% F CXF / 2% F AXF 16.81 15.96 4-5 2 2
a. S, change in shade; C, staining of adjacent cotton; V, staining of adjacent viscose
b. M, Matexil; F, Fixogene
47
Table 11 Fastness properties of direct dyeings aftertreated with Fixogene
CXF and Matexil FC-ER under neutral and alkaline conditions
Colour fastness
__________________
Staininga
Shade __________
Dye pH Cationic agent K/S change C V
C.I. Direct Red 89 - NIL 14.84 4 1 1-2
7 4% Fixogene CXF 14.74 4-5 1-2 2
11 4% Fixogene CXF 14.64 4-5 2 2-3
- NIL 14.84 4 1 1-2
7 4% Matexil FC-ER 14.21 4-5 2-3 3
11 4% Matexil FC-ER 13.18 4-5 3 3
C.I. Direct Yellow 106 - NIL 10.98 3 1 1-2
7 4% Fixogene CXF 10.36 4 1-2 2
11 4% Fixogene CXF 10.57 4 2-3 3
- NIL 10.98 3 1 1-2
7 4% Matexil FC-ER 10.49 4 2-3 3
11 4% Matexil FC-ER 10.57 4 3-4 4
C.I. Direct Blue 85 - NIL 17.06 3 1 1-2
7 4% Fixogene CXF 16.08 4-5 1-2 2
11 4% Fixogene CXF 16.68 4-5 2 3
- NIL 17.06 3 1 1-2
7 4% Matexil FC-ER 17.06 4-5 2-3 3
11 4% Matexil FC-ER 17.40 4-5 3 4
a. C, Cotton; V, Viscose
A new fibre modification technique based on a cationic acrylic
copolymer (polymer pL) has been established. Pretreatment of cotton with this
polymer increased both the substantivity and reactivity of the fibre towards
reactive dyes, even under neutral or acidic conditions [117]. Recently, poly
48
(vinylamine chloride) has been investigated as a pretreatment for the salt-free
dyeing of cotton with reactive dyes. Dye fixation was found to be much higher
than by conventional dyeing without pretreatment, even in the presence of a
large amount of salt. Dyed cotton pretreated with poly (vinylamine chloride)
showed excellent wash fastness and good rub fastness [118].
Grafting reactions with cellulose by free radical polymerisation have
been explored for many years but the development of modified cotton fibres
with enhanced dyeability via this route has attracted particular interest recently.
The direct dyeing properties of cotton grafted with 2-vinylpyridine and then
quaternised with alkyl bromides or epichlorohydrin were studied under various
dyeing conditions. The results indicated that grafting with 2-vinylpyridine
increased the dye exhaustion markedly and quaternised grafted specimens
showed a further increase in exhaustion of dyes [119]. The modification and
bleaching of cotton was carried out in a single bath by graft polymerisation of
the cationic monomer, methacrylolaminopropyltrimethyl ammonium chloride.
This modified bleached cotton enhanced the colour strength of reactive dye in
the absence of salt. However, the bleaching performance in the presence of
modifying agent was slightly reduced [120].
EEXXPPEERRIIMMEENNTTAALL
WWOORRKK
50
Chapter 3
EEXXPPEERRIIMMEENNTTAALL WWOORRKK
3.1 GENERAL INFORMATION
N,N,N',N'-tetraethylmethylenediamine was synthesised in the laboratory
by the reported method [121]. Clarke's method [122] was used for the synthesis
of N,N-dimethylglycine hydrochloride while 3-dimethylaminopropionic acid
hydrochloride was prepared by the acidic hydrolysis of 3-
dimethylaminopropionitrile [123]. These hydrochlorides were converted to free
amino acids by Galat's method [124]. Other chemicals and solvents were
obtained from Merck, BDH or Acros and were used after purification through
distillation. Progress of the reactions was monitored by performing chemical
tests and TLC of the reaction mixture. The products were purified through
various methods and vacuum dried before performing spectroscopic analysis.
Purity of the products was checked by thin layer chromatography using
precoated silica gel plates (Merck 60F254). Elemental analysis was performed
51
on Carto Erba MOD-1106 elemental analyser. The structures of the quaternary
ammonium salts were charaterised using IR and 1H–NMR spectroscopy. IR
spectra were recorded on a Thermo Nicolet IR 200 spectrometer. 1H–NMR
spectra were recorded in MeOH-d4 solution on a Bruker DPX-400 instrument
at 400 MHz. Chemical shifts are reported in ppm using TMS as an internal
standard. Mass spectra were recorded on a Jeol SX-102 instrument.
Scoured and bleached cotton fabric was used for dyeing. Commercial
samples of C.I. Direct Orange 26, C.I. Direct Red 31, C.I. Direct Black 22, C.I.
Reactive Orange 13, C.I. Reactive Red 45, C.I. Reactive Blue 5, C.I. Acid
Yellow 23 and C.I. Acid Black 234 were generously supplied by Sandal
Dyestuff Industries Limited, Pakistan and were used without further
purification. All other chemicals used were of laboratory reagent grade. The
absorption maximum (λ max. values) of dyes were measured using UV-1700
Pharmaspec UV-Visible spectrophotometer. Dyeing of cotton samples was
carried out in ATLAS D 400 IR Infrared laboratory dyeing machine. Datacolor
SF 650X Spectraflash was used for colorimetric analysis of the dyed samples
and WASHTEC-P ST 13 8TY was used for the washing of the dyed samples.
Colorfastness to light of the dyed textile fabrics was determined using ATLAS
Ci 3000+ Xenon Weather-Ometer. Grey scales were used for assessing change
in colour and staining of adjacent fabrics.
52
3.2 SYNTHESIS OF MONO- AND BIS-REACTIVE 2,3-EPOXY /
3-CHLORO-2-HYDROXY PROPYL DERIVATIVES OF
QUATERNARY AMMONIUM CHLORIDE
Eight mono-reactive (Figure 9) and four bis-reactive (Figure 10) 2,3-
epoxy / 3-chloro-2-hydroxy propyl derivatives of quaternary ammonium
chloride have been synthesised by reacting epichlorohydrin with suitable
tertiary amines and diamines. Mono-reactive derivatives also contain cyano and
carboxylic groups in addition to 2,3-epoxy / 3-chloro-2-hydroxy propyl groups.
Reaction parameters such as time and temperature have been optimised for the
synthesis of these compounds.
53
N
CH3
CH3
(CH2)n
X
N+
CH3
CH3
(CH2)n
X
H
O
Cl
N+
CH3
CH3
(CH2)n
XO
N+
CH3
CH3
(CH2)n
XOH
Cl
Cl-
Cl-
Cl-
O
Cl30-50 C
Conc. HCl
20 Co
OH2
30-50 C
OH2
o o
28 29
X = CN, COOH
n = 1, 2
Figure 9 Synthesis of mono-reactive 2,3-epoxy / 3-chloro-2-hydroxy
propyl derivatives of quaternary ammonium chloride
28a n = 1, X = CN 29a n = 1, X = CN
28b n = 1, X = COOH 29b n = 1, X = COOH
28c n = 2, X = CN 29c n = 2, X = CN
28d n = 2, X = COOH 29d n = 2, X = COOH
54
N(CH2)n
N
R
R
R
R
N+
(CH2)nN
+
R
R
R
RH HConc. HCl
20 C
O
Cl30-50 C
OH2
30-50 C
OH2
O
Cl
N+
(CH2)nN+
R
RR
RO
O
N+
(CH2)nN+
R
RR
R OH
Cl
OH
Cl
Cl-
Cl-
Cl-
Cl-
Cl-
Cl-
o
oo
30 31
R = CH3, C2H5
n = 1, 2
Figure 10 Synthesis of bis-reactive 2,3-epoxy / 3-chloro-2-hydroxy propyl
derivatives of quaternary ammonium chloride
30a n = 1, R = C2H5 31a n = 1, R = C2H5
30b n = 2, R = CH3 31b n = 2, R = CH3
55
3.2.1 GENERAL PROCEDURE FOR THE SYNTHESIS OF MONO-
AND BIS-REACTIVE 2,3-EPOXYPROPYL DERIVATIVES: (28a-d and
30a-b)
Amine (1.0 mmol) was added dropwise to a mixture of epichlorohydrin
(1.0 mmol) and water (10 ml) over a period of 1 hour with constant stirring and
maintaining the temperature between 30-50 oC. The resulting mixture was
stirred at this temperature for 8-10 hours. After the completion of reaction,
water and unreacted reactants were distilled off under reduced pressure and the
crude product was purified by extraction with chloroform or ether to obtain a
yellow to brown viscous product. Due to its high moisture sensitivity, product
was kept in vacuum desiccator for drying. Same procedure was followed for
the synthesis of compounds 30a-b except that the mole ratio of diamine to
epichlorohydrin was 1: 2 respectively.
The products were identified by performing specific chemical tests for
epoxy group [125], tertiary amines [126] and quaternary ammonium salts
[127].
N-Cyanomethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride
(28a)
N+
CH3
CH3
O
CN
Cl-
56
Pale yellow viscous liquid, IR: 2970, 2230, 1478, 1260, 910 cm–1, 1H-
NMR (MeOH-d4): δ 4.40 (2H, s, CH2-CN), δ 3.45 (1H, dd, J=3.1,16.5 Hz,
CH2-N), δ 3.33 (6H, s, CH3), δ 3.26 (1H, dd, J=4.4,16.5 Hz, CH2-N), δ 3.23
(1H, m, epoxy CH), δ 2.75 (1H, dd, J=4.2,4.9 Hz, epoxy CH2), δ 2.49 (1H, dd,
J=3.3,4.9 Hz, epoxy CH2), MS m/z: 141 [M+], 126 [M+-CH3], HRMS calcd. for
C7H13ClN2O: 176.6439; found: 176.6454, Anal. calcd. for C7H13ClN2O: C,
47.59; H, 7.41; N, 15.85; found: C, 47.55; H, 7.40; N, 15.80.
N-Carboxymethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride
(28b)
N+
CH3
CH3
O
O
OH
Cl-
Pale yellow viscous liquid, IR: 2500-3300, 1726, 1618, 1480, 1395,
1262, 937 cm–1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 4.20 (2H, s,
CH2-COOH), δ 3.45 (1H, dd, J=3.1,16.4 Hz, CH2-N), δ 3.31 (6H, s, CH3), δ
3.26 (1H, dd, J=4.4,16.4 Hz, CH2-N), δ 3.22 (1H, m, epoxy CH), δ 2.77 (1H,
dd, J=4.2,4.9 Hz, epoxy CH2), δ 2.50 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS
m/z: 160 [M+], 145 [M+-CH3], HRMS calcd. for: C7H14ClNO3: 195.6440;
found: 195.6457, Anal. calcd. for C7H14ClNO3: C, 42.97; H, 7.21; N, 7.15;
found: C, 42.94; H, 7.17; N, 7.19.
57
N-Cyanoethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride
(28c)
N+
CH3
CH3
O CN
Cl-
Yellow viscous liquid, IR: 2960, 2248, 1482, 1257, 920 cm–1, 1H-NMR
(MeOH-d4): δ 3.65 (2H, t, J=7.0 Hz, CH2), δ 3.45 (1H, dd, J=3.1,16.5 Hz, CH2-
N), δ 3.33 (6H, s, CH3), δ 3.26 (1H, dd, J=4.4,16.5 Hz, CH2-N), δ 3.23 (1H, m,
epoxy CH), δ 2.82 (2H, t, J=6.9 Hz, CH2-CN), δ 2.75 (1H, dd, J=4.2,4.9 Hz,
epoxy CH2), δ 2.49 (1H, dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 155 [M+], 140
[M+-CH3], HRMS calcd. for: C8H15ClN2O: 190.6705; found: 190.6722, Anal.
calcd. for C8H15ClN2O: C, 50.39; H, 7.92; N, 14.69; found: C, 50.36; H, 7.90;
N, 14.72.
N-Carboxyethyl-N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride
(28d)
N+
CH3
CH3
O
O
OH
Cl-
Yellow viscous liquid, IR: 2500-3300, 1740, 1610, 1475, 1380, 1271,
965 cm-1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 3.53 (2H, t, J=7.0
Hz, CH2), δ 3.45 (1H, dd, J=3.1,16.4 Hz, CH2-N), δ 3.31 (6H, s, CH3), δ 3.26
58
(1H, dd, J=4.4,16.4 Hz, CH2-N), δ 3.22 (1H, m, epoxy CH), δ 2.77 (1H, dd,
J=4.2,4.9 Hz, epoxy CH2), δ 2.67 (2H, t, J=7.2 Hz, CH2–COOH), δ 2.50 (1H,
dd, J=3.3,4.9 Hz, epoxy CH2), MS m/z: 174 [M+], 159 [M+-CH3], HRMS calcd.
for: C8H16ClNO3: 209.6705; found: 209.6721, Anal. calcd. for C8H16ClNO3: C,
45.82; H, 7.69; N, 6.68; found: C, 45.85; H, 7.69; N, 6.64.
Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride]
(30a)
N+
N+
C2H5
H5C2
C2H5H5C2
O
O
Cl-
Cl-
Pale yellow viscous liquid, IR: 2987, 2960, 1472, 1269, 900 cm–1, 1H-
NMR (MeOH-d4): δ 5.20 (2H, s, N+-CH2-N+), δ 3.45 (2H, dd, J=3.1,16.5 Hz,
CH2-N), δ 3.29 (8H, q, J=7.0 Hz, CH2-CH3), δ 3.26 (2H, dd, J=4.4,16.5 Hz,
CH2-N), δ 3.23 (2H, m, epoxy CH), δ 2.75 (2H, dd, J=4.2,4.9 Hz, epoxy CH2),
δ 2.49 (2H, dd, J=3.3,4.9 Hz, epoxy CH2), δ 1.25 (12H, t, J=7.0 Hz, CH3), MS
m/z: 272 [M+], 243 [M+-C2H5], 215 [M+-2,3-epoxypropyl], HRMS calcd. for:
C15H32Cl2N2O2: 343.3328; found: 343.3361, Anal. calcd. for C15H32Cl2N2O2:
C, 52.47; H, 9.39; N, 8.15; found: C, 52.50; H, 9.39; N, 8.10.
59
Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride]
(30b)
Cl-
Cl-N
+
CH3
CH3ON
+
CH3
CH3
O
Reddish-brown viscous liquid, IR: 3010, 2958, 1470, 1272, 920 cm–1,
1H-NMR (MeOH-d4): δ 3.72 (4H, s, CH2), δ 3.45 (2H, dd, J=3.1,16.5 Hz, CH2-
N), δ 3.33 (12H, s, CH3), δ 3.26 (2H, dd, J=4.4,16.5 Hz, CH2-N), δ 3.23 (2H,
m, epoxy CH), δ 2.75 (2H, dd, J=4.2,4.9 Hz, epoxy CH2), δ 2.49 (2H, dd,
J=3.3,4.9 Hz, epoxy CH2), MS m/z: 230 [M+], 215 [M+-CH3], 173 [M+-2,3-
epoxypropyl], HRMS calcd. for: C12H26Cl2N2O2: 301.2530; found: 301.2557,
Anal. calcd. for C12H26Cl2N2O2: C, 47.84; H, 8.69; N, 9.29; found: C, 47.79; H,
8.65; N, 9.26.
3.2.2 GENERAL PROCEDURE FOR THE SYNTHESIS OF MONO-
AND BIS-REACTIVE 3-CHLORO-2-HYDROXYPROPYL
DERIVATIVES: (29a-d and 31a-b)
Conc. HCl (1.0 mmol) was added to the aqueous solution of amine (1.0
mmol) over a period of 1 hour under slow stirring and maintaining the
temperature below 20 oC. After complete addition of HCl, reaction mixture was
stirred for half an hour at this temperature and showed a neutral pH. Then
60
epichlorohydrin was added slowly to the above reaction mixture with
continuous stirring. The temperature was raised to 30-50 oC and the reaction
mixture was stirred at this temperature for 8-10 hours. After the completion of
reaction, water and unreacted reactants were distilled off under reduced
pressure and the crude product was purified by extraction with chloroform or
ether to obtain a clear to yellow viscous product. Due to its high moisture
sensitivity, product was kept in vacuum desiccator for drying. Same procedure
was followed for the synthesis of 31a-b except that the mole ratio of diamine to
Conc. HCl and epichlorohydrin was 1: 2: 2 respectively.
The products were identified by performing specific chemical tests for
epoxy group [125], tertiary amines [126] and quaternary ammonium salts
[127].
N-Cyanomethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium
chloride (29a)
N+
CH3
CH3OH
Cl CN
Cl-
Pale yellow viscous liquid, IR: 3252, 2970, 2230, 1478, 1100, 735 cm–1,
1H-NMR (MeOH-d4): δ 4.40 (2H, s, CH2-CN), δ 4.37 (1H, brs, OH), δ 4.18
(1H, m, CH), δ 3.62 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd, J=3.1,16.5
Hz, CH2), δ 3.40 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.33 (6H, s, CH3), δ 3.27
61
(1H, dd, J=4.3,16.5 Hz, CH2), MS m/z: 177.5 [M+], 162.5 [M+-CH3], 128 [M+-
CH2Cl], HRMS calcd. for: C7H14Cl2N2O: 213.1049; found: 213.1065, Anal.
calcd. for C7H14Cl2N2O: C, 39.45; H, 6.62; N, 13.14; found C, 39.42; H, 6.60;
N, 13.10.
N-Carboxymethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium
chloride (29b)
N+
CH3
CH3OH
Cl
O
OH
Cl-
Yellow viscous liquid, IR: 2500-3300, 1726, 1618, 1480, 1395, 1060,
742 cm-1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 4.38 (1H, brs,
OH), δ 4.20 (2H, s, CH2-COOH), δ 4.18 (1H, m, CH), δ 3.63 (1H, dd,
J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd, J=3.1,16.4 Hz, CH2), δ 3.42 (1H, dd,
J=4.7,6.0 Hz, CH2-Cl), δ 3.31 (6H, s, CH3), δ 3.27 (1H, dd, J=4.4,16.4 Hz,
CH2), MS m/z: 196.5 [M+], 181.5 [M+-CH3], 147 [M+-CH2Cl], HRMS calcd.
for: C7H15Cl2NO3: 232.1049; found: 232.1062, Anal. calcd. for C7H15Cl2NO3:
C, 36.22; H, 6.51; N, 6.03; found: C, 36.18; H, 6.50; N, 6.07.
62
N-Cyanoethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium
chloride (29c)
N+
CH3
CH3OH
ClC
N
Cl -
Yellowish-brown viscous liquid, IR: 3240, 2960, 2248, 1482, 1100, 735
cm–1, 1H-NMR (MeOH-d4): δ 4.37 (1H, brs, OH), δ 4.18 (1H, m, CH), δ 3.65
(2H, t, J=7.0 Hz, CH2), δ 3.62 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd,
J=3.1,16.5 Hz, CH2), δ 3.40 (1H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.33 (6H, s,
CH3), δ 3.27 (1H, dd, J=4.3,16.5 Hz, CH2), δ 2.82 (2H, t, J=6.9 Hz, CH2-CN),
MS m/z: 191.5 [M+], 176.5 [M+-CH3], 142 [M+-CH2Cl], HRMS calcd. for:
C8H16Cl2N2O: 227.1314; found: 227.1329, Anal. calcd. for C8H16Cl2N2O: C,
42.30; H, 7.09; N, 12.33; found: C, 42.27; H, 7.05; N, 12.30.
N-Carboxyethyl-N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium
chloride (29d)
N+
CH3
CH3OH
Cl O
OH
Cl-
Clear viscous liquid, IR: 2500-3300, 1740, 1610, 1475, 1380, 1070, 740
cm–1, 1H-NMR (MeOH-d4): δ 12.40 (1H, brs, COOH), δ 4.38 (1H, brs, OH), δ
4.18 (1H, m, CH), δ 3.63 (1H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (1H, dd,
63
J=3.1,16.4 Hz, CH2), δ 3.53 (2H, t, J=7.0 Hz, CH2), δ 3.42 (1H, dd, J=4.7,6.0
Hz, CH2-Cl), δ 3.31 (6H, s, CH3), δ 3.27 (1H, dd, J=4.4,16.4 Hz, CH2), δ 2.67
(2H, t, J=7.2 Hz, CH2–COOH), MS m/z: 210.5 [M+], 195.5 [M+-CH3], 161
[M+-CH2Cl], HRMS calcd. for: C8H17Cl2NO3: 246.1315; found: 246.1330,
Anal. calcd. for C8H17Cl2NO3: C, 39.03; H, 6.96; N, 5.69; found: C, 39.01; H,
6.90; N, 5.65.
Methylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-diethylammonium
chloride] (31a)
N+
N+
C2H5
H5C2
C2H5H5C2
OH
Cl
OH
Cl
Cl-
Cl-
Pale yellow viscous liquid, IR: 3220, 2987, 2960, 1472, 1095, 740 cm–1,
1H-NMR (MeOH-d4): δ 5.20 (2H, s, N+-CH2-N+), δ 4.37 (2H, brs, OH), δ 4.18
(2H, m, CH), δ 3.62 (2H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (2H, dd, J=3.1,16.5
Hz, CH2), δ 3.40 (2H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.29 (8H, q, J=7.0 Hz,
CH2), δ 3.27 (2H, dd, J=4.4,16.5 Hz, CH2), δ 1.25 (12H, t, J=7.0 Hz, CH3), MS
m/z: 345 [M+], 316 [M+-C2H5], 295.5 [M+-CH2Cl], HRMS calcd. for:
C15H34Cl4N2O2: 416.2547; found: 416.2579, Anal. calcd. for C15H34Cl4N2O2:
C, 43.28; H, 8.23; N, 6.72; found: C, 43.25; H, 8.19; N, 6.75.
64
Ethylene bis-[N-(3-chloro-2-hydroxypropyl)-N,N-dimethylammonium
chloride] (31b)
Cl-
Cl -
N+
CH3
CH3
OH
Cl
N+
CH3
CH3
OH
Cl
Clear viscous liquid, IR: 3224, 3010, 2958, 1470, 1100, 742 cm–1, 1H-
NMR (MeOH-d4): δ 4.37 (2H, brs, OH), δ 4.18 (2H, m, CH), δ 3.72 (4H, s,
CH2), δ 3.62 (2H, dd, J=5.6,6.0 Hz, CH2-Cl), δ 3.55 (2H, dd, J=3.1,16.5 Hz,
CH2), δ 3.40 (2H, dd, J=4.7,6.0 Hz, CH2-Cl), δ 3.33 (12H, s, CH3), δ 3.27 (2H,
dd, J=4.4,16.5 Hz, CH2), MS m/z: 303 [M+], 288 [M+-CH3], 253.5 [M+-CH2Cl],
HRMS calcd. for: C12H28Cl4N2O2: 374.1749; found: 374.1775, Anal. calcd. for
C12H28Cl4N2O2: C, 38.51; H, 7.54; N, 7.48; found: C, 38.55; H, 7.51; N, 7.52.
3.3 APPLICATIONS
The synthesised compounds were applied to cotton fabrics as
pretreatments and optimum conditions for the cationisation of cotton fabric
with these compounds have been determined. Dyeing properties of these
pretreated fabrics with direct, reactive and acid dyes have also been
investigated. These compounds were also applied to the dyed cotton fabrics as
aftertreatments and the effect of different pH conditions and concentration on
the effectiveness of these compounds as fixing agents has been studied.
65
Since both epoxy and halohydroxy propyl derivatives of quaternary
ammonium salts react with cellulose under alkaline conditions and have the
same reactive group as shown in Figure 7 and 8 therefore, epoxy derivatives
have been applied to the cotton fabrics as pretreatments and aftertreatments and
their effects on the colour strength (K/S) and fastness properties of dyed fabrics
have been evaluated.
3.3.1 APPLICATION OF CATIONIC FIXING AGENTS AS
PRETREATMENT
3.3.1.1 Pretreatment of cotton fabrics
Cotton fabrics were pretreated with compounds 30a, 30b and 28c using
the exhaust method (Table 12). Pretreatment was carried out in a laboratory
dyeing machine at a liquor ratio of 25:1. Afterwards, the fabrics were rinsed in
tap water and then neutralised with 2% CH3COOH for 5 minutes at 40o C.
Neutralised fabrics were again rinsed in tap water and dried at room
temperature.
Table 12 Pretreatment conditions
Pretreatment Temperature Time Conc. of NaOH Conc. of cationic
method (oC) (min.) (% ow cationic agent) agenta (% owf)
1. 40-100 30 30 2
2. 80 20-50 30 2
3. 80 30 30 2-10
4. 80 30 10-40 2
a. 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-dimethylammonium chloride]
66
3.3.2 DYEING CONDITIONS FOR UNTREATED COTTON FABRICS
3.3.2.1 Dyeing of untreated cotton fabrics with direct dyes by
conventional method
Untreated cotton fabrics were dyed with direct dyes in a laboratory
dyeing machine at a liquor ratio of 25:1 using 15-30g/L of sodium chloride
under neutral conditions. Dyeing was started at 30 oC and temperature of the
dye bath was raised to 100 oC over 20 minutes. Dyeing was continued at this
temperature for a further 50 minutes. Dye bath was then cooled and discarded
(Figure 11). Dyed fabrics were rinsed thoroughly in tap water and dried at
room temperature.
Figure 11 Dyeing profile of untreated cotton fabric with direct dyes
3.3.2.2 Dyeing of untreated cotton fabrics with reactive dyes by
conventional method
Untreated cotton fabrics were dyed with reactive dyes in a laboratory
dyeing machine according to the dyeing profile shown in Figure 12. Dyed
samples were rinsed in tap water, then rinsed in hot water at 60 oC for 5
15-30 g/L NaCl
30 oC
25: 1
100 oC50 min.
Rinsing
67
minutes and again rinsed in tap water. Dyed samples were squeezed and dried
at room temperature.
Figure 12 Dyeing profile of untreated cotton fabric with reactive dyes
3.3.2.3 Dyeing of wool fabrics with acid dyes
Wool fabrics were dyed with acid dyes (2% owf) at a liquor ratio of
30:1. The pH of the bath was adjusted to 3 with acetic acid prior to adding the
fabric. The bath was then heated to 100 oC in 25 minutes and held at this
temperature for 1 hour. The bath was then cooled and discarded. The fabric
was rinsed in tap water and dried.
3.3.3 DYEING CONDITIONS FOR PRETREATED COTTON FABRICS
3.3.3.1 Dyeing of pretreated cotton fabrics with direct dyes
Pretreated cotton fabrics were dyed with direct dyes in the absence of
salt in a laboratory dyeing machine at a liquor ratio of 25:1 under neutral
conditions (Table 13). Dye bath was then cooled and dyed fabrics were rinsed
20g/ L Na2CO3
60 g/ L NaCl
25: 1
45 min. 80 oC
30 oC
Rinsing
68
thoroughly in tap water and dried at room temperature. The effect of
temperature, time, dye concentration and fixing agent concentration on the
dyeing behaviour of pretreated cotton fabrics has been investigated. For
comparison, untreated cotton fabrics were also dyed under the same conditions.
Table 13 Dyeing conditions with direct dyes
Dyeing Temperature Time Conc. of dyea Conc. of cationic agentb method (oC) (min.) (% owf) (% owf)
1. 60-100 30 2 2
2. 100 20-50 2 2
3. 100 30 2-6 2
4. 100 30 2 1-4
a. C. I. Direct Orange 26
b. 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride], 30b Ethylene bis-[N-
(2,3-epoxypropyl)-N,N-dimethylammonium chloride], 28c N-Cyanoethyl-N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride
3.3.3.2 Dyeing of pretreated cotton fabrics with reactive dyes
Pretreated cotton fabrics were dyed with reactive dyes in a laboratory
dyeing machine at a liquor ratio of 25:1 (Table 14). Dye bath was then cooled
and dyed fabrics were rinsed thoroughly in tap water and dried at room
temperature. The effect of dyeing conditions on the pretreated fabrics has been
investigated in detail. For comparison, untreated cotton fabrics were also dyed
with reactive dyes under the same conditions.
69
Table 14 Dyeing conditions with reactive dyes
Dyeing Temperature Time Na2CO3 Conc. of dyea Conc. of cationic method (oC) (min.) (g/L) (% owf) agentb (% owf)
1. 60-100 30 - 2 2
2. 80 15-45 - 2 2
3. 80 30 - 2-6 2
4. 80 30 - 2 1-4
5. 80 30 10-20 2 2
a. C. I. Reactive Orange 13
b. 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium chloride], 30b Ethylene bis-[N-
(2,3-epoxypropyl)-N,N-dimethylammonium chloride], 28c N-Cyanoethyl-N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride
3.3.3.3 Dyeing of untreated and pretreated cotton fabrics with acid dyes
Untreated and pretreated (2% owf) cotton fabrics were dyed with acid
dyes (1-4% owf) in a laboratory dyeing machine according to the dyeing
profile shown in Figure 13. Dyed samples were then rinsed in tap water,
squeezed and dried at room temperature.
70
Dye 1-4% owf
pH Neutral
Liquor ratio 30:1
Figure 13 Dyeing profile of untreated and pretreated cotton fabrics with acid
dyes
3.3.4 APPLICATION OF CATIONIC FIXING AGENTS AS AN
AFTERTREATMENT
A bis-reactive derivative of quaternary ammonium salt (Compound 30b)
was applied to cotton fabrics dyed with direct dyes. The effect of different pH
conditions and concentration on the effectiveness of this cationic fixing agent
has been investigated.
3.3.4.1 Dyeing with direct dyes
Cotton fabrics were dyed with direct dyes (2% owf) in a laboratory
dyeing machine at a liquor ratio of 25:1 using 15g/L of sodium chloride.
Dyeing was started at 30 oC and then temperature was raised to 100 oC over 20
minutes. Dyeing was continued at this temperature for a further 50 minutes.
100 oC
60 min.
30 oC Rinsing
71
Dye bath was then cooled to 70 oC and discarded. Dyed fabrics were rinsed
thoroughly and dried at room temperature.
3.3.4.2 Aftertreatment with cationic fixing agent (30b)
2% and 4% (owf) of bis-reactive cationic agent (30b) was applied to the
dyed fabrics (2% owf) in a laboratory dyeing machine at a liquor ratio of 25:1.
The cationic agent was applied both at pH 7 and pH 11. The method used is
given in Figure 14.
A Dyed cotton fabric (2% owf)
Cationic fixing agent (2% or 4% owf)
Either pH 7 or pH 11 using 1% NaOH soln.
Liquor ratio 25:1
Figure 14 Aftertreatment of direct dyed cotton fabrics with cationic fixing
agent (30b)
3.4 COLOUR MEASUREMENT
The reflectance values and the corresponding CIE L*, a*, b*, C* and ho
colour coordinates of the samples were measured using Datacolor SF 650X
40 oC
30 minutes
A
72
Spectraflash attached to a personal computer under illuminant D65 using a 10o
standard observer. From the reflectance values at the λ max. of the dyeings (R),
the colour strength (K/S) values of the samples were calculated using Kubelka-
Munk equation (Eqn. 1).
3.5 FASTNESS TESTING
Colour fastness is the fundamental requirement of dyed textile materials.
It is defined [128] as "Resistance to the change in colour of the dyed textile
material when subjected to a particular set of conditions." Colour fastness is
usually assessed with respect to change in colour of the fabric in the test and
with respect to staining of adjacent fabrics.
3.5.1 WASH FASTNESS
Wash fastness of the dyeings was determined according to standard ISO
methods [129]. Samples were subjected to ISO 105: C06/C2S wash test (60
oC).
2R
(1 – R) 2 K/S = Eqn. 1
73
3.5.1.1 Test procedure
The composite specimen (fabric under test stitched with adjacent fabric)
along with 25 steel balls was placed in each container and necessary amount of
detergent solution, previously heated to 60 ± 2 oC, was added to give a liquor
ratio of 50:1. The specimen was run at this temperature for 30 minutes. The
composite specimen was removed, rinsed twice for a period of 1 minute in
separate 100 ml portions of water at 40 oC. The specimen was squeezed,
unstitched and dried at room temperature. After drying, samples were visually
assessed for shade change and staining on adjacent fabric using grey scale. The
grey scale ranges from 5 for no shade change (or no stain on adjacent fiber)
down to 1 for a severe shade change (or staining) with half points in between.
3.5.2 LIGHT FASTNESS
Colour fastness to light of the dyeings was tested according to AATCC
test method 16-2003 [130]. The dyed samples were exposed to xenon arc using
AATCC Blue Wool Light Fastness Standards as a reference. The
colourfastness to light of the specimens was evaluated by comparison of the
colour change of the exposed portion to the masked portion of the test
specimen or unexposed original material using grey scale for colour change.
RREESSUULLTTSS AANNDD
DDIISSCCUUSSSSIIOONN
75
Chapter 4
RREESSUULLTTSS AANNDD DDIISSCCUUSSSSIIOONN
4.1 SYNTHESIS OF MONO- AND BIS-REACTIVE 2,3-EPOXY
AND 3-CHLORO-2-HYDROXY PROPYL DERIVATIVES
It has been found that below 30 oC either little or no product is formed
even after stirring for long hours. High temperature was avoided due to the
cleavage of epoxy ring of epichlorohydrin and the synthesised products. In
addition high temperature may lead to the polymerisation of product. A
temperature range of 30–50 oC was found to be most suitable to get the
products using stoichiometric ratio of reactants. Reaction conditions and yields
of these compounds are given in Table 15. Reactions were monitored by
performing specific chemical tests for epoxy group [125], tertiary amines [126]
and quaternary ammonium salts [127]. Epoxy compounds (28a-d and 30a-b)
gave negative test for tertiary amines and positive test for quaternary amines
whereas halohydroxy compounds (29a-d and 31a-b) showed positive test for
76
quaternary amines and negative test for tertiary amines and epoxy group. The
IR and 1H–NMR data, which have been given in experimental section, also
confirmed the identity of the compounds.
Table 15 Reaction conditions and yields of salts 28a-d, 29a-d, 30a-b and 31a-b
Salt Reaction conditions Yield (%) Salt Reaction conditions Yield (%)
28a 30 oC, 9 hrs. 57 29a 40-50 oC, 8 hrs. 59
28b 40-50 oC, 8 hrs. 72 29b 40-50 oC, 8 hrs. 69
28c 30 oC, 9 hrs. 75 29c 40-50 oC, 8 hrs. 78
28d 40 oC, 8 hrs. 65 29d 40 oC, 7 hrs. 73
30a 40-50 oC, 10 hrs. 53 31a 40-50 oC, 10 hrs. 40
30b 40-50 oC, 9 hrs. 86 31b 30-40 oC, 8 hrs. 84
Solubility of these compounds has been checked in different solvents.
All the compounds were soluble in methanol, DMSO and water while they
were insoluble in ether and chloroform. Purity of these compounds has been
checked by thin layer chromatography using precoated silica gel plates (Merck
60F254) and following the method of Bluhm and Li [131]. It has further been
verified by elemental analysis and results of elemental analysis have been
given in experimental section.
The products obtained were in the form of viscous liquid due to their
hygroscopic nature. However under anhydrous conditions using chloroform as
a solvent, products were obtained as white crystalline solid. These crystalline
products again turned into viscous liquid on exposure to air/ atmosphere after a
77
short while. Therefore, the products were dried before elemental analysis by
keeping in vacuum desiccator for several days.
4.2 APPLICATIONS
The synthesised quaternary ammonium chlorides have been applied to
the cotton fabrics as pretreatments and aftertreatments and promising results
have been obtained. The absorption maximum (λ max.) values of the dyes
(used in this work) in aqueous solution were measured by UV-Visible
Spectrophotometer and the λ max. values of the cotton fabrics dyed with these
dyes were measured by datacolor. The λ max. values of the dyes in aqueous
solution and on the dyed fabrics are given in Table 16.
Table 16 λ max. values of dyes
λ max. (nm) λ max. (nm) λ max. (nm)
Dye in water of fabrics dyed under of fabrics dyed under
neutral conditions alkaline conditions
C. I. Direct Orange 26 507 510 -
C. I. Direct Red 31 524 540 -
C. I. Direct Black 22 658 630 -
C. I. Reactive Orange 13 492 500 500
C. I. Reactive Red 45 520 520 540
C. I. Reactive Blue 5 598 600 610
C. I. Acid Yellow 23 416 400 -
C. I. Acid Black 234 608 610 -
78
4.2.1 PRETREATMENT WITH CATIONIC FIXING AGENTS
Cotton fabrics were cationised by pretreatment with mono-reactive
(compound 28c) and bis-reactive derivatives (compound 30a and 30b) under
alkaline conditions using the exhaust method. A bis-reactive derivative,
compound 30b was used to determine the optimum conditions for the
pretreatment of cotton fabrics. The amount of cationic agent (compound 30b)
introduced into the cotton fabric was evaluated from the chlorine content of the
fabric. The chlorine content of the cationised fabrics under different
pretreatment conditions have been given in Table 17-20 and graphically
represented in Figure 15-18.
4.2.1.1 Effect of temperature and time on the cationisation of cotton
fabrics
As shown in Table 17, chlorine content of the fabric increased with the
increase in temperature up to 80 oC and then decreased rapidly. From Table 18,
it can also be observed that chlorine content of the fabric increased with time
up to 30 minutes and then decreases rapidly. The decrease in chlorine content
may be due to the partial hydrolysis of the cationic agent that occurs at high
temperature prior to its reaction with cellulose. Therefore, further study of the
pretreatment conditions was carried out at 80o C for 30 minutes.
79
Table 17 Effect of temperature on the chlorine
content of cationised fabric
Temperature Chlorine content
(oC) of the fabric (%)
40 0.2838
60 0.2950
80 0.3308
100 0.2662
0
0.1
0.2
0.3
0.4
0 20 40 60 80 100 120
Temp. (oC)
Chl
orin
e co
nten
t (%
)
Figure 15 Effect of temperature on the chlorine content of cationised cotton
fabric [Cationisation conditions: Compound 30b; 2% (owf), NaOH
30% (ow cationic agent), Liquor ratio 25:1, Time 30 min.]
80
Table 18 Effect of pretreatment time on the
chlorine content of cationised fabric
Time Chlorine content
(min.) of the fabric (%)
20 0.2844
30 0.3308
40 0.2917
50 0.2623
0
0.1
0.2
0.3
0.4
0 10 20 30 40 50 60
Time (min.)
Chl
orin
e co
nten
t (%
)
Figure 16 Effect of pretreatment time on the chlorine content of cationised
cotton fabric [Cationisation conditions: Compound 30b; 2% (owf),
NaOH 30% (ow cationic agent), Liquor ratio 25:1, Temp. 80 oC]
81
4.2.1.2 Effect of cationic agent (owf) and sodium hydroxide (ow cationic
agent) concentrations on the cationisation of cotton fabrics
The effect of cationic agent concentration (based on the weight of the
fabric) and sodium hydroxide concentration (based on the weight of cationic
agent) on the chlorine content of the cationised fabric has also been
investigated. It was found that chlorine content of the fabric increases with the
increase in the conc. of the cationic agent (Table 19). However, the rate of
increase of chlorine content decreases with the increase in the conc. of the
cationic agent above 2% (owf).
Table 19 Effect of cationic agent concentration on
the chlorine content of cationised fabric
Conc. of cationic agent Chlorine content
(% owf) of the fabric (%)
2 0.3308
4 0.3459
6 0.3678
8 0.3806
10 0.3986
From Table 20, it can also be seen that chlorine content of the fabric
increases with the increase in the conc. of sodium hydroxide up to 30% (ow
cationic agent). A further increase in the conc. of sodium hydroxide decreases
82
the chlorine content of the fabric suggesting that a conc. of 30% (ow cationic
agent) was sufficient for the fixation of cationic agent with the fabric.
Table 20 Effect of NaOH concentration on the
chlorine content of cationised fabric
Conc. of NaOH Chlorine content
(% ow cationic agent) of the fabric (%)
10 0.2741
20 0.2844
30 0.3308
40 0.2940
The use of high concentration of alkali or the fixing agent increases the
rate of hydrolysis of the cationic agent which in turn decreases the chlorine
content of the fabric. Thus, cationic agent 2% (owf) and sodium hydroxide
30% (ow cationic agent) were chosen as optimum conditions for the
pretreatment of cotton fabrics. The effect of cationic agent and NaOH
concentration on the chlorine content of cationised cotton fabric has been
graphically represented in Figure 17 and 18.
Under the above mentioned conditions, cotton fabrics were cationised
by pretreatment with bis-reactive derivatives 30a (C-1) and 30b (C-2). A
mono-reactive derivative, 28c was also used for the cationisation of cotton
fabrics under the same conditions (C-3). This compound contains cyano group,
hydrolysis of which might take place during pretreatment.
83
0
0.1
0.2
0.3
0.4
0.5
0 2 4 6 8 10 12
Conc. of cationic agent (% owf)
Chl
orin
e co
nten
t (%
)
Figure 17 Effect of cationic agent concentration on the chlorine content of
cationised cotton fabric [Cationisation conditions: Compound 30b;
NaOH 30% (ow cationic agent), Liquor ratio 25:1, Temp. 80 oC,
Time 30 min.]
0
0.1
0.2
0.3
0.4
0 10 20 30 40 50
Conc. of NaOH (% ow cationic agent)
Chl
orin
e co
nten
t (%
)
Figure 18 Effect of NaOH conc. on the chlorine content of cationised cotton
fabric [Cationisation conditions: Compound 30b; 2% (owf), Temp.
80 oC, Time 30 min., Liquor ratio 25:1]
84
4.2.2 DYEING OF UNTREATED AND PRETREATED COTTON
FABRICS WITH DIRECT DYES
Untreated cotton fabric (C) and cotton fabrics pretreated with compound
30a (C-1), 30b (C-2) and 28c (C-3) were dyed with direct dyes in the absence
of salt under neutral conditions (Table 13). The effect of pretreatment on the
direct dyeing properties of cotton fabrics was studied in detail. This study was
carried out with C.I. Direct Orange 26 (λ max. 510 nm). The % Reflectance
values (%R) of the dyeings were measured using datacolor. From the
reflectance values at the λ max. of the dyeings (R), the colour strength (K/S)
values of the dyed fabrics were calculated using Kubelka-Munk equation (See
Eqn.1 on page 72).
4.2.2.1 Effect of dyeing temperature
The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt
under neutral conditions at different temperature conditions. The % Reflectance
values (%R) of the dyeings were measured and from the reflectance values at
the λ max. of the dyeings (R), the colour strength (K/S) values of the dyed
fabrics were calculated and are given in Table 21.
85
Table 21 % Reflectance (at λ max. 510 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) under
different temperature conditions
Temperature Cotton % Reflectance at Reflectance Colour strength
(oC) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
60 C 8.22 0.0822 5.12
C-1 4.85 0.0485 9.33
C-2 3.94 0.0394 11.71
C-3 3.66 0.0366 12.67
70 C 7.25 0.0725 5.93
C-1 4.29 0.0424 10.67
C-2 3.49 0.0349 13.34
C-3 3.35 0.0335 13.94
80 C 6.13 0.0613 7.18
C-1 3.86 0.0386 11.97
C-2 3.05 0.0305 15.40
C-3 3.13 0.0313 14.99
90 C 5.21 0.0521 8.62
C-1 3.34 0.0334 13.98
C-2 2.78 0.0278 16.99
C-3 2.91 0.0291 16.19
100 C 4.56 0.0456 9.98
C-1 3.00 0.0300 15.68
C-2 2.49 0.0249 19.09
C-3 2.68 0.0268 17.67
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
86
The dyeing behaviour of untreated cotton (C) and cotton cationised with
30a (C-1), 30b (C-2) and 28c (C-3) with direct dyes has shown that an increase
in temperature is accompanied by an increase in the colour strength (K/S) of
the dyeings (Figure 19).
0
5
10
15
20
25
50 60 70 80 90 100 110
Temp. (oC)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 19 Effect of temperature on the colour strength (K/S) of untreated
(C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Direct Orange 26 (2% owf)
This may be due to the increase in the disaggregation of the dye
molecules and /or increase in the rate of dye penetration into the fibre. During
the normal dyeing process of untreated cotton fabric, an equilibrium is
established between the dye in the fibre and dye in the solution. However,
during the dyeing of cationised cotton, this equilibrium is shifted towards
87
cationic cotton due to increased dye uptake as a result of interaction between
the dye anions and cations in the fibre. The cationised cotton fabrics C-1 and
C-2 would have higher content of cationic dye sites relative to C-3 due to their
bis-reactive and bis-cationic nature. However, C-1 showed lower colour
strength than C-2 and C-3 because of the steric hindrance of the cationic agent
with the dye molecules. In other words, increase in the length of hydrocarbon
chain attached to the ammonium group decreased the colour strength of the
dyeings. Generally, higher content of the cationic dye sites in the fibre results
in greater dye exhaustion and fixation, thus enhancing the colour strength of
the dyeings.
4.2.2.2 Effect of dyeing time
The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics were dyed with C.I. Direct Orange 26 (2% owf) in the absence of salt
under neutral conditions at 100 oC for different time periods. The %
Reflectance values (%R) of the dyeings were measured and from the
reflectance values at the λ max. of the dyeings (R), the colour strength (K/S)
values of the dyed fabrics were calculated and are given in Table 22.
88
Table 22 % Reflectance (at λ max. 510 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Direct Orange 26 (2% owf) at 100 oC
for different time periods
Dyeing time Cotton % Reflectance at Reflectance Colour strength
(min.) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
20 C 5.38 0.0538 8.32
C-1 3.99 0.0399 11.55
C-2 3.12 0.0312 15.04
C-3 3.37 0.0337 13.85
30 C 4.56 0.0456 9.98
C-1 3.00 0.0300 15.68
C-2 2.49 0.0249 19.09
C-3 2.68 0.0268 17.67
40 C 4.02 0.0402 11.45
C-1 3.36 0.0336 13.89
C-2 2.78 0.0278 16.99
C-3 2.74 0.0274 17.26
50 C 3.83 0.0383 12.07
C-1 3.72 0.0372 12.45
C-2 3.14 0.0314 14.93
C-3 2.81 0.0281 16.80
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
An increase in dyeing time also results in an increase in the colour
strength (K/S) of the dyeings (Figure 20). Results revealed that a dyeing time
of 30 minutes was sufficient to achieve the maximum colour strength for
cationised cotton fabrics (C-1, C-2 and C-3). A further increase in dyeing time
89
resulted in a decrease in the colour strength of cationised fabrics in all cases.
This may be due to the deterioration of the fixing agent-fibre bonds and / or
dye-fixing agent complex on prolonged heating.
0
5
10
15
20
25
0 10 20 30 40 50 60
Time (min.)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 20 Effect of dyeing time on the colour strength (K/S) of untreated (C)
and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Direct Orange 26 (2% owf)
4.2.2.3 Effect of dye concentration
The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics were dyed with different concentrations (2-6% owf) of C.I. Direct
Orange 26 in the absence of salt under neutral conditions at a temperature of
100 oC for 30 minutes. The % Reflectance values (%R) of the dyeings were
measured and from the reflectance values at the λ max. of the dyeings (R), the
colour strength (K/S) values of the dyed fabrics were calculated and are given
in Table 23.
90
Table 23 % Reflectance (at λ max. 510 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Direct Orange 26 at 100 oC for 30
minutes using different dye concentrations
Dye conc. Cotton % Reflectance at Reflectance Colour strength
(% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
2 C 4.56 0.0456 9.98
C-1 3.00 0.0300 15.68
C-2 2.49 0.0249 19.09
C-3 2.68 0.0268 17.67
3 C 4.23 0.0423 10.84
C-1 2.98 0.0298 15.79
C-2 2.46 0.0246 19.33
C-3 2.57 0.0257 18.46
4 C 3.90 0.0390 11.84
C-1 2.94 0.0294 16.02
C-2 2.42 0.0242 19.67
C-3 2.47 0.0247 19.25
5 C 3.53 0.0353 13.18
C-1 2.61 0.0261 18.17
C-2 2.37 0.0237 20.10
C-3 2.19 0.0219 21.84
6 C 3.20 0.0320 14.64
C-1 2.31 0.0231 20.65
C-2 2.18 0.0218 21.94
C-3 1.97 0.0197 24.39
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
91
From Figure 21, it is clear that an increase in the dye concentration
increases the colour strength for both the untreated (C) and pretreated fabrics
(C-1, C-2 and C-3). This may be due to the excess of dye anions in the dye
solution at higher conc. which form hydrogen bonds with the fabric in addition
to those having electrostatic interactions with the cationic dye sites of the
pretreated fabrics.
0
5
10
15
20
25
30
0 1 2 3 4 5 6 7
Dye conc. (% owf)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 21 Effect of dye conc. on the colour strength (K/S) of untreated (C)
and pretreated (C-1, C-2, C-3; 2% owf) cotton fabrics dyed with
C.I. Direct Orange 26
4.2.2.4 Effect of cationic agent concentration
The cotton fabrics pretreated with different concentrations of compound
30a (C-1), 30b (C-2) and 28c (C-3) were dyed with C.I. Direct Orange 26 (2%
owf) in the absence of salt under neutral conditions at a temperature of 100 oC
92
for 30 minutes. The % Reflectance values (%R) of the dyeings were measured
and from the reflectance values at the λ max. of the dyeings (R), the colour
strength (K/S) values of the dyed fabrics were calculated and are given in
Table 24.
Table 24 % Reflectance (at λ max. 510 nm) and the colour strength (K/S)
values of cotton fabrics pretreated with different conc. of cationic
agents (C-1, C-2 and C-3) and dyed with C.I. Direct Orange 26
(2% owf) at 100 oC for 30 minutes
Cationic agent Cotton % Reflectance at Reflectance Colour strength
conc. (% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
1 C-1 3.59 0.0359 12.94
C-2 3.56 0.0356 13.06
C-3 3.03 0.0303 15.51
2 C-1 3.00 0.0300 15.68
C-2 2.49 0.0249 19.09
C-3 2.68 0.0268 17.67
3 C-1 3.11 0.0311 15.09
C-2 2.78 0.0278 16.99
C-3 2.77 0.0277 17.06
4 C-1 3.22 0.0322 14.54
C-2 3.17 0.0317 14.78
C-3 2.87 0.0287 16.43
a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium
chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-
dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
93
The effect of cationic agent concentration on the uptake of direct dyes is
shown in Figure 22. The results indicated that an increase in the concentration
of cationic agent above 2% owf causes a decrease in the colour strength of the
pretreated dyeings. This may be due to the partial hydrolysis of the cationic
agent that occurs at higher concentrations under alkaline conditions during the
pretreatment step, resulting in a decrease in the cationic dye sites in the fibre
which in turn decreased the colour strength of the dyeings.
0
5
10
15
20
25
0 1 2 3 4 5
Conc. of cationic agent (% owf)
K/S
K/S C-1K/S C-2K/S C-3
Figure 22 Effect of cationic agent concentration on the colour strength (K/S)
of pretreated cotton fabrics (C-1, C-2 and C-3) dyed with C.I.
Direct Orange 26 (2% owf)
On the basis of the results obtained, untreated (C) and pretreated (C-1,
C-2 and C-3; 2% owf) cotton fabrics were dyed with three direct dyes (2%
owf) in the absence of salt at neutral pH. The colour strength and fastness
properties of these dyeings are given in Table 25. The results indicated that
94
pretreated fabrics C-1, C-2 and C-3 have higher colour strength (K/S) values
than the untreated fabrics (Figure 23). The wash fastness properties of
pretreated fabrics were comparable or slightly better than the untreated fabrics
but with higher colour strength. However, pretreatment has caused a slight
decrease in the light fastness of the pretreated dyeings. This is common with
such treatments [16].
Table 25 Colour strength (K/S) and fastness properties of direct dyes (2%
owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics
Wash fastness
_________________
Shade Staining Light
Dye Cotton fabrica K/S change on cotton fastness
C.I. Direct Orange 26 C 9.98 3-4 3-4 4-5
C-1 15.68 3 3-4 4
C-2 19.09 3-4 4 4
C-3 17.67 3 3 3-4
C.I. Direct Red 31 C 8.94 2-3 4 3-4
C-1 14.58 2-3 3-4 3
C-2 15.83 3 3 3
C-3 15.68 1-2 2-3 3
C.I. Direct Black 22 C 12.56 4 3-4 5
C-1 13.67 3 4 5
C-2 14.96 3-4 3-4 5
C-3 14.64 3 3 4-5
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
95
The effect of additional group in mono-reactive cationic agent (28c) has
also been investigated. The presence of additional group enhanced the colour
strength of the dyeings (C-3) as a result of the interaction with other suitable
groups in the dye molecules. Since these interactions still relies on electrostatic
forces therefore, the wash fastness properties of the dyeings were inferior to the
fabrics pretreated with bis-reactive cationic agents (C-1 and C-2).
0
5
10
15
20
25
0 1 2 3 4 5 6
Dye conc. (% owf)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 23 Colour strength (K/S) values of untreated (C) and pretreated (C-1,
C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Direct Orange
26
A comparison of the direct dyeing of pretreated cotton fabrics (C-1, C-2
and C-3; 2% owf) (Table 25) with untreated cotton fabrics dyed by
conventional method (Table 26) has indicated that pretreated fabrics showed
slightly lower colour strength as compared to the untreated cotton fabrics dyed
96
by conventional method. However, the wash fastness results of pretreated
fabrics were comparable or better than those of untreated fabrics. The colour
strength values of the pretreated fabrics could be enhanced by increasing the
dye conc. as shown in Figure 21.
Table 26 Colour strength (K/S) and fastness properties of untreated cotton
fabrics dyed with direct dyes (2% owf) by conventional method
Wash fastness
________________________________ Light
Dye K/S Shade change Staining on cotton fastness
C.I. Direct Orange 26 23.04 3-4 3 4-5
C.I. Direct Red 31 16.31 2 3 4
C.I. Direct Black 22 18.77 3-4 3-4 5
The above findings revealed that cationised cotton fabrics could be dyed
with direct dyes without salt and require less dyeing time as compared to the
cotton fabrics dyed by conventional methods. Thus, high salt concentrations
can be avoided in the direct dyeing of cotton fabrics which leads to the
pollution of the effluents. Pretreatment of cotton fabrics with cationic fixing
agents has shown good colour strength and comparable wash fastness
properties without adversely affecting the light fastness of the dyeings. In short,
the bis-reactive agents have proved to be more effective than the mono-reactive
agent. Amongst bis-reactive derivatives, the compound with lower steric
hindrance has shown superior results.
97
SSHHAADDEESS OOFF DDIIRREECCTT DDYYEESS OONN UUNNTTRREEAATTEEDD ((CC)) AANNDD
PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33;; 22%% oowwff )) CCOOTTTTOONN
FFAABBRRIICCSS
C.I. DIRECT ORANGE 26
Untreated cotton (C)
(With salt) (Without salt)
Pretreated cotton
C-1 C-2 C-3
C.I. DIRECT RED 31
Untreated cotton (C)
(With salt) (Without salt)
Pretreated cotton
C-1 C-2 C-3
98
C.I. DIRECT BLACK 22
Untreated cotton (C)
(With salt) (Without salt)
Pretreated cotton
C-1 C-2 C-3
99
4.2.3 DYEING OF UNTREATED AND PRETREATED COTTON
FABRICS WITH REACTIVE DYES
Untreated cotton fabric (C) and cotton fabrics pretreated with compound
30a (C-1), 30b (C-2) and 28c (C-3) were dyed with reactive dyes in the
absence of salt and alkali (Table 14). The effect of pretreatment on the reactive
dyeing properties of cotton fabrics was studied in detail. This study was carried
out with C.I. Reactive Orange 13 (λ max. 500 nm). The % Reflectance values
(%R) of the dyeings were measured using datacolor. From the reflectance
values at the λ max. of the dyeings (R), the colour strength (K/S) values of the
dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on
page 72).
4.2.3.1 Effect of dyeing temperature
The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt
and alkali at different temperature conditions. The % Reflectance values (%R)
of the dyeings were measured and from the reflectance values at the λ max. of
the dyeings (R), the colour strength (K/S) values of the dyed fabrics were
calculated and are given in Table 27.
100
Table 27 % Reflectance (at λ max. 500 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at
different temperature conditions
Temperature Cotton % Reflectance at Reflectance Colour strength
(oC) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
60 C 51.79 0.5179 0.2243
C-1 44.97 0.4497 0.3367
C-2 28.57 0.2857 0.8929
C-3 17.05 0.1705 2.0178
70 C 52.38 0.5238 0.2164
C-1 43.65 0.4365 0.3637
C-2 27.04 0.2704 0.9843
C-3 16.51 0.1651 2.1110
80 C 53.58 0.5358 0.2010
C-1 42.87 0.4287 0.3806
C-2 26.10 0.2610 1.0462
C-3 16.03 0.1603 2.1993
90 C 54.06 0.5406 0.1951
C-1 42.89 0.4289 0.3802
C-2 26.39 0.2639 1.0266
C-3 17.48 0.1748 1.9478
100 C 54.53 0.5453 0.1895
C-1 42.92 0.4292 0.3795
C-2 26.49 0.2649 1.0199
C-3 19.15 0.1915 1.7067
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
101
The dyeing behaviour of untreated (C) and pretreated (C-1, C-2 and C-
3) cotton fabrics with reactive dyes has shown that colour strength values of
pretreated cotton fabrics (C-1, C-2 and C-3) increase with the increase in
temperature up to 80 oC and then decrease whereas in case of untreated cotton
fabrics (C) colour strength values gradually decrease with the increase in
temperature (Figure 24).
0
0.5
1
1.5
2
2.5
50 60 70 80 90 100 110
Temp. (oC)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 24 Effect of temperature on colour strength (K/S) values of untreated
(C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Reactive Orange 13 (2% owf)
The increase in colour strength with temperature in case of pretreated
fabrics results from the greater exhaustion and fixation of reactive dyes due to
the cationic sites present in the fibre while the deterioration of the dye
molecules in case of untreated fabrics and the breaking of fixing agent-fibre
102
bonds or dye-fixing agent complex in case of pretreated fabrics at high
temperature results in a decrease in the colour strength of the dyeings.
However, pretreated fabrics showed higher colour strength values as compared
to the untreated fabrics at all temperatures in all cases due to the greater affinity
of cationic fabrics with the anionic dye molecules. Superior results were
obtained when dyeing was carried out with cotton fabric pretreated with
compound 28c (C-3). This may be the result of interaction between the dye
molecules and the additional group in compound 28c.
4.2.3.2 Effect of dyeing time
The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt
and alkali at 80 oC for different time periods. The % Reflectance values (%R)
of the dyeings were measured and from the reflectance values at the λ max. of
the dyeings (R), the colour strength (K/S) values of the dyed fabrics were
calculated and are given in Table 28.
103
Table 28 % Reflectance (at λ max. 500 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with C.I. Reactive Orange 13 (2% owf) at 80
oC for different time periods
Time Cotton % Reflectance at Reflectance Colour strength
(min.) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
15 C 54.44 0.5444 0.1906
C-1 43.53 0.4353 0.3662
C-2 28.37 0.2837 0.9042
C-3 17.19 0.1719 1.9946
30 C 53.58 0.5358 0.2010
C-1 42.87 0.4287 0.3806
C-2 26.10 0.2610 1.0462
C-3 16.03 0.1603 2.1993
45 C 51.56 0.5156 0.2275
C-1 46.53 0.4653 0.3072
C-2 29.32 0.2932 0.8519
C-3 18.01 0.1801 1.8662
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
Results indicated that the colour strength (K/S) values of pretreated
fabrics (C-1, C-2 and C-3) decrease with the increase in dyeing time above 30
minutes which may be the result of deterioration of dye-fixing agent complex
and/or fixing agent-fibre bonds on prolonged heating at high temperature.
However, the colour strength (K/S) values of untreated cotton fabrics (C)
gradually increase with the increase in dyeing time (Figure 25).
104
0
0.5
1
1.5
2
2.5
0 15 30 45 60
Time (min.)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 25 Effect of dyeing time on the colour strength (K/S) of untreated (C)
and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Reactive Orange 13 (2% owf)
4.2.3.3 Effect of dye concentration
The untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf) cotton
fabrics were dyed with different concentrations (2-6% owf) of C.I. Reactive
Orange 13 in the absence of salt and alkali at a temperature of 80 oC for 30
minutes. The % Reflectance values (%R) of the dyeings were measured and
from the reflectance values at the λ max. of the dyeings (R), the colour strength
(K/S) values of the dyed fabrics were calculated and are given in Table 29.
105
Table 29 % Reflectance (at λ max. 500 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with different conc. of C.I. Reactive Orange 13
at 80 oC for 30 minutes
Dye conc. Cotton % Reflectance at Reflectance Colour strength
(% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
2 C 53.58 0.5358 0.2010
C-1 42.87 0.4287 0.3806
C-2 26.10 0.2610 1.0462
C-3 16.03 0.1603 2.1993
3 C 51.27 0.5127 0.2315
C-1 38.32 0.3832 0.4964
C-2 25.99 0.2599 1.0537
C-3 15.92 0.1592 2.2203
4 C 50.26 0.5026 0.2461
C-1 37.81 0.3781 0.5114
C-2 25.55 0.2555 1.0846
C-3 15.62 0.1562 2.2791
5 C 49.96 0.4996 0.2506
C-1 35.12 0.3512 0.5992
C-2 20.89 0.2089 1.4979
C-3 13.87 0.1387 2.6742
6 C 49.70 0.4970 0.2545
C-1 33.07 0.3307 0.6772
C-2 17.97 0.1797 1.8722
C-3 12.57 0.1257 3.0405
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
106
From Figure 26, it is clear that increase in the concentration of the dye
resulted in an increase in the colour strength values of the untreated (C) and
pretreated (C-1, C-2 and C-3) cotton fabrics. This may be due to the excess of
dye anions in the dye solution at higher concentrations which interact with the
fabric in addition to those having electrostatic interactions with the cationic dye
sites of the pretreated fabrics.
0
0.5
1
1.5
2
2.5
3
3.5
0 1 2 3 4 5 6 7
Dye conc. (% owf)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 26 Effect of dye conc. on the colour strength (K/S) of untreated (C)
and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Reactive Orange 13
4.2.3.4 Effect of cationic agent concentration
The cotton fabrics pretreated with different concentrations of compound
30a (C-1), 30b (C-2) and 28c (C-3) were dyed with C.I. Reactive Orange 13
(2% owf) in the absence of salt and alkali at a temperature of 80 oC for 30
107
minutes. The % Reflectance values (%R) of the dyeings were measured and
from the reflectance values at the λ max. of the dyeings (R), the colour strength
(K/S) values of the dyed fabrics were calculated and are given in Table 30.
Table 30 % Reflectance (at λ max. 500 nm) and the colour strength (K/S)
values of cotton fabrics pretreated with different conc. of cationic
agents (C-1, C-2 and C-3) and dyed with C.I. Reactive Orange 13
(2% owf) at 80 oC for 30 minutes
Cationic agent Cotton % Reflectance at Reflectance Colour strength
conc. (% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
1 C-1 49.23 0.4923 0.2617
C-2 34.88 0.3488 0.6078
C-3 24.86 0.2486 1.1355
2 C-1 42.87 0.4287 0.3806
C-2 26.10 0.2610 1.0462
C-3 16.03 0.1603 2.1993
3 C-1 43.57 0.4357 0.3654
C-2 26.88 0.2688 0.9945
C-3 17.40 0.1740 1.9605
4 C-1 43.88 0.4388 0.3588
C-2 27.12 0.2712 0.9792
C-3 18.84 0.1884 1.7481
a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium
chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-
dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
The effect of cationic agent concentration on the uptake of reactive dyes
indicated that an increase in the concentration of cationic agent above 2% (owf)
108
causes a decrease in the colour strength of the pretreated dyeings (Figure 27).
This may be due to the partial hydrolysis of the cationic agent that occurs at
higher concentrations under alkaline conditions during the pretreatment step,
resulting in a decrease in the cationic dye sites in the fibre which in turn
decreased the colour strength of the dyeings.
0
0.5
1
1.5
2
2.5
0 1 2 3 4 5
Cationic agent conc. (% owf)
K/S
K/S C-1K/S C-2K/S C-3
Figure 27 Effect of cationic agent concentration on the colour strength (K/S)
of pretreated (C-1, C-2 and C-3) cotton fabrics dyed with C.I.
Reactive Orange 13 (2% owf)
4.2.3.5 Effect of alkali (anhydrous Na2CO3)
The effect of alkali on the reactive dyeing properties of pretreated
fabrics was investigated. The pretreated cotton fabrics (C-1, C-2 and C-3; 2%
owf) were dyed with C.I. Reactive Orange 13 (2% owf) in the absence of salt
but in the presence of alkali at a temperature of 80 oC for 30 minutes. The %
Reflectance values (%R) of the dyeings were measured and from the
109
reflectance values at the λ max. of the dyeings (R), the colour strength (K/S)
values of the dyed fabrics were calculated and are given in Table 31.
Table 31 % Reflectance (at λ max. 500 nm) and the colour strength (K/S)
values of pretreated cotton fabrics (C-1, C-2 and C-3; 2% owf)
dyed with C.I. Reactive Orange 13 (2% owf) at 80o C for 30
minutes using different amounts of alkali
Amount of Cotton % Reflectance at Reflectance Colour strength
alkali (g/L) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
NIL C-1 42.87 0.4287 0.3806
C-2 26.10 0.2610 1.0462
C-3 16.03 0.1603 2.1993
10g/L C-1 23.74 0.2374 1.2248
C-2 20.56 0.2056 1.5347
C-3 13.08 0.1308 2.8880
20g/L C-1 12.58 0.1258 3.0374
C-2 12.40 0.1240 3.0942
C-3 12.28 0.1228 3.1330
a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium
chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-
dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
The pretreated cotton fabrics (C-1, C-2 and C-3) have shown more
pronounced results when the dyeing was carried out in the presence of alkali
(Figure 28). The use of anhydrous sodium carbonate in the reactive dyeing of
pretreated fabrics enhanced the colour strength of the dyeings even in the
110
absence of salt as a result of fixation of the dye with the fibre under alkaline
conditions.
0
0.5
1
1.5
2
2.5
3
3.5
NIL 10g/L 20g/L
Amount of alkali (Na2CO3 anhydrous)
K/S
K/S C-1K/S C-2K/S C-3
Figure 28 Effect of alkali (Na2CO3) on the colour strength (K/S) of pretreated
(C -1, C-2 and C-3; 2% owf) cotton fabrics dyed with C.I. Reactive
Orange 13 (2% owf)
As shown in Figure 28, colour strength values increase with the
increase in the concentration of alkali. It is also clear that at higher alkali
concentration, colour strength values of the pretreated fabrics (C-1, C-2 and C-
3) were independent of the cationic agent used. This indicates that the cationic
agents used for the pretreatment of cotton fabrics have exhausted the dyes on to
the fabric due to the interaction between cationic agents and anionic dye
molecules and then fixation is brought about under alkaline conditions. Thus,
the exhaustion of reactive dyes onto cotton fabrics can be obtained by the
111
pretreatment of cotton fabrics with cationic fixing agents instead of using high
salt concentrations which is usually required for reactive dyeing.
Using the above mentioned dyeing conditions, untreated (C) and
pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics were dyed with three
reactive dyes (2% owf) in the absence of salt and alkali (Table 32).
Table 32 Colour strength (K/S) and fastness properties of reactive dyes (2
% owf) on untreated (C) and pretreated (C-1, C-2 and C-3; 2%
owf) cotton fabrics in the absence of salt and alkali
Wash fastness
________________
Shade Staining Light
Dye Cotton fabrica K/S change on cotton fastness
C.I. Reactive Orange 13 C 0.2010 2-3 5 5
C-1 0.3806 2 5 4
C-2 1.0462 1 5 3-4
C-3 2.1993 1 4-5 3
C.I. Reactive Red 45 C 0.0820 2 5 5
C-1 0.1455 1-2 5 3-4
C-2 0.5602 1 5 3-4
C-3 0.7816 1 5 3
C.I. Reactive Blue 5 C 0.079 3 5 5
C-1 0.2838 4 5 4
C-2 0.7353 4-5 4-5 4
C-3 1.39 2-3 4-5 3-4
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
112
Dyeing of pretreated fabrics (C-1, C-2 and C-3; 2% owf) was also
carried out without salt but in the presence of alkali (anhydrous Na2CO3;
20g/L) at the same time. The colour strength and fastness properties of these
dyeings are given in Table 33.
Table 33 Colour strength (K/S) and fastness properties of reactive dyes (2
% owf) on pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics
in the presence of alkali (anhydrous Na2CO3; 20g/L)
Wash fastness
________________
Shade Staining Light
Dye Cotton fabrica K/S change on cotton fastness
C.I. Reactive Orange 13 C-1 3.23 2-3 5 5
C-2 3.09 3-4 5 5
C-3 3.13 4 5 4-5
C.I. Reactive Red 45 C-1 1.09 2-3 5 4-5
C-2 1.16 4 5 4-5
C-3 1.14 2-3 5 4
C.I. Reactive Blue 5 C-1 3.82 3 5 4-5
C-2 4.71 4 5 4-5
C-3 5.25 4-5 5 4
a. C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-diethylammonium
chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-N,N-
dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
A comparative study of the reactive dyeing of pretreated cotton fabrics
in the presence of alkali (Table 33) and untreated fabrics dyed by conventional
113
method (Table 34) revealed that cationic cotton showed lower colour strength
but similar wash fastness results as compared to untreated fabrics dyed by
conventional method.
Table 34 Colour strength (K/S) and fastness properties of reactive dyes (2
% owf) on untreated cotton fabrics dyed by conventional method
Wash fastness
________________
Shade Staining Light
Dye Cotton fabric K/S change on cotton fastness
C. I. Reactive Orange 13 Untreated 9.86 3-4 5 5
C. I. Reactive Red 45 Untreated 5.02 3-4 5 5
C. I. Reactive Blue 5 Untreated 12.14 4-5 5 5
The overall results indicate that pretreated fabrics C-1, C-2 and C-3
could be dyed with reactive dyes in the absence of salt and alkali. Reactive
dyeing of pretreated cotton fabrics without salt and alkali gave higher colour
strength and comparable wash fastness properties relative to the corresponding
untreated fabrics (Table 32). Although the use of alkali has further enhanced
the colour strength values of pretreated dyeings (Table 33) yet the results were
lower than the fabrics dyed by conventional method. On the contrary, the wash
fastness results of the pretreated dyeings were similar to the untreated
conventional dyeings. Thus, high electrolyte concentration can be avoided by
the pretreatment of cotton fabrics with cationic fixing agents. The presence of
some suitable groups in the cationic agents may further improve the results.
114
SSHHAADDEESS OOFF RREEAACCTTIIVVEE DDYYEESS OONN UUNNTTRREEAATTEEDD ((CC)) AANNDD
PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33;; 22%% oowwff )) CCOOTTTTOONN
FFAABBRRIICCSS
C.I. REACTIVE ORANGE 13
Untreated cotton (C)
(With salt and alkali) (Without salt and alkali)
Pretreated cotton
With alkali Without salt and alkali
C-1
C-2
C-3
115
C.I. REACTIVE RED 45
Untreated cotton (C)
(With salt and alkali) (Without salt and alkali)
Pretreated cotton
With alkali Without salt and alkali
C-1
C-2
C-3
116
C.I. REACTIVE BLUE 5
Untreated cotton (C)
(With salt and alkali) (Without salt and alkali)
Pretreated cotton
With alkali Without salt and alkali
C-1
C-2
C-3
117
4.2.4 DYEING OF UNTREATED AND PRETREATED COTTON
FABRICS WITH ACID DYES
Untreated cotton fabric (C) and cotton fabrics pretreated with compound
30a (C-1), 30b (C-2) and 28c (C-3) were dyed with acid dyes (1-4% owf)
under neutral conditions (Figure 13). The effect of pretreatment on the dyeing
properties of cotton fabrics with acid dyes was studied. This study was carried
out with C.I. Acid Yellow 23 (λ max. 400 nm). The % Reflectance values
(%R) of the dyeings were measured using datacolor and from the reflectance
values at the λ max. of the dyeings (R), the colour strength (K/S) values of the
dyed fabrics were calculated using Kubelka-Munk equation (See Eqn.1 on
page 72) and are given in Table 35.
118
Table 35 % Reflectance (at λ max. 400 nm) and the colour strength (K/S)
values of untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics dyed with different concentrations of C.I. Acid
Yellow 23 at 100 oC for 60 minutes
Dye conc. Cotton % Reflectance at Reflectance Colour strength
(% owf) fabrica λ max. (% R) R = % R / 100 K/S = (1 - R)2 / 2R
1 C 53.36 0.5336 0.2038
C-1 51.88 0.5188 0.2231
C-2 51.73 0.5173 0.2252
C-3 42.66 0.4266 0.3853
2 C 52.46 0.5246 0.2154
C-1 47.57 0.4757 0.2889
C-2 47.28 0.4728 0.2939
C-3 33.41 0.3341 0.6636
3 C 52.34 0.5234 0.2169
C-1 46.83 0.4683 0.3018
C-2 44.74 0.4474 0.3412
C-3 29.16 0.2916 0.8604
4 C 51.99 0.5199 0.2216
C-1 45.12 0.4512 0.3337
C-2 42.09 0.4209 0.3983
C-3 25.57 0.2557 1.0832
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
From Figure 29, it can be observed that colour strength increased with
increase in dye concentration applied to the cationised fabrics whereas in case
of untreated fabric colour strength was very low because acid dyes have low
119
affinity for cellulose. It was also observed that colour strength (K/S) of the
cotton fabric modified with compound 28c (C-3) was higher as compared to the
other pretreated fabrics (C-1 and C-2) suggesting that additional group in
compound 28c has also developed some interactions with the dye molecules.
0
0.2
0.4
0.6
0.8
1
1.2
0 1 2 3 4 5
Conc. of dye (% owf)
K/S
K/S CK/S C-1K/S C-2K/S C-3
Figure 29 Effect of dye conc. on the colour strength (K/S) of untreated (C)
and pretreated (C-1, C-2 and C-3; 2% owf) cotton fabrics dyed
with C.I. Acid Yellow 23
The colour strength and wash fastness results of acid dyeings (2% owf)
(Table 36) revealed that cationic cotton could be dyed with acid dyes.
Although the colour strength (K/S) values of cationic cotton were lower than
that of wool dyed with the same acid dye however, the wash fastness results of
acid dyes on cationic cotton were comparable to those on wool dyed with the
same acid dye except the colour change of pretreated cotton fabrics dyed with
120
C.I. Acid Black 234. On the contrary, the colour change of untreated and
pretreated cotton fabrics dyed with C.I. Acid Yellow 23 was better than that on
wool dyed with the same acid dye. This difference of colour change during
wash fastness testing indicated that C.I. Acid Yellow 23 was more firmly
attached to the cationised cotton fibre as compared to C.I. Acid Black 234. This
behaviour of acid dyes seems to be dependant on the structure of dyes.
Table 36 Colour strength (K/S) and wash fastness properties of acid dyes
on wool, untreated (C) and pretreated (C-1, C-2 and C-3; 2% owf)
cotton fabrics
Wash fastness
___________________________
Staining
Shade ____________ Light
Dye Fabrica K/S change Cotton Wool fastness
C.I. Acid C 0.21 2 4 4-5 4-5
Yellow 23 C-1 0.28 4 3-4 4-5 4
C-2 0.29 2 3-4 4-5 4
C-3 0.66 2 4 4-5 4
Wool 30.45 1 4-5 4-5 4
C.I. Acid C 1.65 1 4-5 4-5 5
Black 234 C-1 4.01 1 4 4 4
C-2 4.85 1 4 4 4-5
C-3 6.57 1 3-4 4 4-5
Wool 39.65 4-5 3 4 5
a. C, Untreated cotton; C-1, Cotton pretreated with 30a Methylene bis-[N-(2,3-epoxypropyl)-N,N-
diethylammonium chloride]; C-2, Cotton pretreated with 30b Ethylene bis-[N-(2,3-epoxypropyl)-
N,N-dimethylammonium chloride]; C-3, Cotton pretreated with 28c N-Cyanoethyl-N-(2,3-
epoxypropyl)-N,N-dimethylammonium chloride
121
SSHHAADDEESS OOFF AACCIIDD DDYYEESS OONN WWOOOOLL,, UUNNTTRREEAATTEEDD ((CC))
AANNDD PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33;; 22%% oowwff )) CCOOTTTTOONN
FFAABBRRIICCSS
C.I. ACID YELLOW 23
Wool Untreated cotton (C)
Pretreated cotton
C-1 C-2 C-3
C.I. ACID BLACK 234
Wool Untreated cotton (C)
Pretreated cotton
C-1 C-2 C-3
122
4.2.5 AFTERTREATMENT OF DIRECT DYES WITH A BIS-
REACTIVE CATIONIC FIXING AGENT
Cotton fabrics dyed with direct dyes (2% owf) were aftertreated with a
bis-reactive cationic agent compound 30b under neutral and alkaline
conditions. The % Reflectance (%R) values and the colour coordinates of the
dyeings before and after wash fastness test were measured using datacolor.
From the reflectance values at the λ max. of the dyeings (R), the colour
strength (K/S) values of the dyed fabrics were calculated and are given in
Table 37 and 39.
4.2.5.1 Effect of pH on the aftertreatment of direct dyeings
Visual comparison of untreated and aftertreated dyeings have revealed a
slight change in colour of the dyeings aftertreated with cationic fixing agent.
This is usually encountered with such treatments [16]. The extent of this colour
change imparted by aftertreatment at pH 7 varied only slightly than by
aftertreatment at pH 11. This visual assessment was supported by colorimetric
data obtained for untreated and aftertreated dyeings (Table 37).
The results of Table 37 show a decrease in the colour strength (K/S) of
the aftertreated dyeings indicating their low wet fastness due to the bleeding of
some dye during warm (40 oC) aqueous aftertreatment process. However, this
decrease in colour strength (K/S) was found to be dependant on the pH of the
aftertreatment. Results indicated that colour strength (K/S) values of
aftertreated dyeings were higher at pH 11 than at pH 7.
123
Table 37 Colorimetric data for untreated and aftertreated direct dyeings
before wash fastness testing
Aftertreatment
Dye pH conc. (% owf) L* a* b* C* ho K/S
C.I. Direct 0 49.54 60.40 51.78 79.55 40.61 23.04
Orange 26 7 2 50.93 59.69 52.82 79.70 41.51 21.53
4 50.65 60.11 52.88 80.06 41.34 22.15
11 2 49.81 61.39 51.97 80.43 40.25 22.70
4 50.07 61.09 51.56 79.94 40.16 21.84
C.I. Direct 0 34.80 46.97 0.73 46.98 0.89 16.31
Red 31 7 2 34.59 45.34 1.04 45.35 1.31 15.30
4 34.78 45.69 1.01 45.71 1.27 15.46
11 2 34.65 45.86 1.42 45.89 1.77 15.79
4 34.91 46.12 1.43 46.14 1.78 15.62
C.I. Direct 0 19.69 -1.55 -1.86 2.42 230.17 18.77
Black 22 7 2 19.90 -0.67 -2.28 2.38 253.74 17.39
4 19.34 -0.41 -2.33 2.36 260.06 18.09
11 2 19.45 -1.05 -2.04 2.30 242.87 18.54
4 19.55 -1.02 -1.99 2.23 242.84 18.31
The wash fastness results of untreated and aftertreated dyeings
are shown in Table 38, from which it is apparent, that aftertreatment either
under neutral or alkaline conditions improved the wash fastness of the dyeings.
However, wash fastness imparted by aftertreatment at pH 11 was superior to
that imparted by aftertreatment at pH 7. These findings are also supported by
the colorimetric data of untreated and aftertreated dyeings after wash fastness
testing (Table 39).
124
Table 38 Wash fastness data for untreated and aftertreated direct dyeings
Wash fastness ______________________________________
Staining
Aftertreatment Shade ________________________
Dye pH conc. (% owf) change Cotton Viscose
C.I. Direct Orange 26 0 3-4 3 3-4
7 2 4 3-4 4
4 3 4 4
11 2 4-5 4 4-5
4 4-5 4 4-5
C.I. Direct Red 31 0 2 3 3-4
7 2 3 3-4 4
4 2-3 3 3-4
11 2 3 4 4-5
4 3 4 4-5
C.I. Direct Black 22 0 3-4 3-4 4
7 2 4 4 4-5
4 4-5 4 4
11 2 4-5 4-5 4-5
4 4-5 4 4-5
125
Table 39 Colorimetric data for untreated and aftertreated direct dyeings
after wash fastness testing
Aftertreatment
Dye pH conc. (% owf) L* a* b* C* ho K/S
C.I. Direct 0 51.79 59.65 50.61 78.23 40.31 18.85
Orange 26 7 2 50.73 59.64 51.16 78.58 40.62 20.56
4 50.33 58.94 49.95 77.26 40.28 19.93
11 2 50.61 61.11 51.10 79.66 39.90 20.84
4 50.49 61.11 50.74 79.43 39.71 20.75
C.I. Direct 0 39.83 48.45 -2.17 48.50 357.43 11.45
Red 31 7 2 36.69 45.95 -0.93 45.96 358.83 12.26
4 38.25 46.11 -1.59 46.14 358.02 11.71
11 2 37.33 46.23 -1.58 46.26 358.04 12.49
4 37.69 46.64 -1.58 46.67 358.06 12.42
C.I. Direct 0 21.99 -2.31 -2.43 3.35 226.50 16.13
Black 22 7 2 20.79 -1.19 -2.43 2.71 243.89 16.68
4 20.57 -1.17 -2.43 2.70 244.24 16.99
11 2 19.18 -0.87 -2.18 2.35 248.13 18.39
4 19.86 -0.86 -2.55 2.69 251.36 17.88
A comparison of the colour strength (K/S) values of untreated and
aftertreated dyeings after wash fastness testing clearly indicates that dyeings
aftertreated under alkaline conditions have higher K/S values than the untreated
and aftertreated dyeings under neutral conditions. This can be explained on the
basis of reactive nature of cationic fixing agent being used as an aftertreatment.
Under neutral conditions, cationic fixing agent interacts electrostatically with
the anionic dye molecules forming a large complex of reduced aqueous
solubility within the dyed substrate. While under alkaline conditions, cationic
126
fixing agent not only interacts electrostatically with the anionic dye molecules
but also forms a covalent linkage with the hydroxy groups of cellulose as
shown in Figure 7, explaining the observed higher wash fastness.
4.2.5.2 Effect of cationic agent concentration on the aftertreatment of
direct dyeings
The effect of cationic agent concentration on the aftertreated dyeings has
also been investigated. Colorimetric data before wash fastness testing (Table
37) has shown that an increase in the concentration of cationic agent increases
the colour strength of the aftertreated dyeings under neutral conditions.
However under alkaline conditions, an increase in the concentration of cationic
agent causes a decrease in the colour strength of the aftertreated dyeings. This
is believed to be due to the partial hydrolysis of the cationic fixing agent that
occurs at higher concentrations prior to its reaction with cellulose.
127
SSHHAADDEE CCHHAANNGGEE OOFF DDIIRREECCTT DDYYEEIINNGGSS BBYY
AAFFTTEERRTTRREEAATTMMEENNTT WWIITTHH AA BBIISS--RREEAACCTTIIVVEE
DDEERRIIVVAATTIIVVEE ((3300bb))
C.I. Direct C.I. Direct C.I. Direct Orange 26 Red 31 Black 22
Untreated dyeings
Aftertreatment 2%
at pH 7
4%
Aftertreatment 2%
at pH 11
4%
CCOONNCCLLUUSSIIOONNSS
129
Chapter 5
CCOONNCCLLUUSSIIOONNSS
Eight mono-reactive and four bis-reactive 2,3-epoxy / 3-chloro-2-
hydroxy propyl derivatives of quaternary ammonium chloride were synthesised
and evaluated as cationic fixing agents for improving the colour strength (K/S)
and fastness properties of anionic dyes on cellulosic fabrics. The structures of
the synthesised compounds were characterised using IR and 1H-NMR
spectroscopy. Optimum conditions for the fixation of these cationic agents to
the cotton fabrics were determined from the chlorine content of the fabric using
compound 30b.
It was found that pretreatment with cationic fixing agents (30a, 30b,
28c) has enabled the dyeing of cotton fabrics with anionic (direct, reactive and
acid) dyes under neutral conditions in the absence of salt. Higher colour
strength (K/S) and good wash fastness properties were obtained with the
pretreated fabrics as compared to the untreated fabrics dyed with the same
130
direct and reactive dyes. The results showed that increase in the length of
hydrocarbon chain attached to the quaternary nitrogen in bis-reactive
derivatives decreased the colour strength of the dyeings but their wash fastness
remained unaffected. It was interesting to note that colour strength of the
dyeings pretreated with a mono-reactive derivative (28c) was comparable (in
case of direct dyes) or superior (in case of reactive and acid dyes) to the fabrics
pretreated with bis-reactive derivatives (30a and 30b). On the contrary, the
wash fastness of the dyeings pretreated with a mono-reactive derivative
(compound 28c) was comparable (in case of reactive dyes) or inferior (in case
of direct dyes) to the dyeings pretreated with bis-reactive agents (compound
30a and 30b). These findings suggest that an additional group in the cationic
agent may enhance the colour strength of the dyeings due to its interaction with
the dye or the fibre but the wash fastness of the dyeings was related to its
reactivity. Bis-reactive derivatives showed better wash fastness because of their
greater fixation to the fabrics as compared to the mono-reactive derivatives.
In comparison with conventional dyeings with direct and reactive dyes,
pretreated fabrics required less dyeing time and showed similar wash fastness
but slightly lower colour strength (K/S) values. Results also indicated that
pretreated cotton fabrics could also be dyed with acid dyes which otherwise
have little substantivity towards cotton. However, the colour strength and wash
fastness comparable to acid-dyed wool was not obtained. It was also found that
light fastness of the dyeings was lowered by pretreatment.
131
Aftertreatment of direct dyeings with a bis-reactive derivative (30b)
improved the colour strength and wash fastness properties under neutral and
alkaline conditions. However, aftertreatment under alkaline conditions
produced dyeings with better wash fastness than by aftertreatment under
neutral conditions.
It could be concluded that pretreatment with cationic fixing agents has
become an environmentally friendly and energy saving process for the direct
and reactive dyeing of cotton fabrics by reducing the amount of salt & alkali
and time taken for dyeing. Aftertreatment with cationic agents has slightly
changed the colour of the direct dyeings but has beneficial effects on the wash
fastness results.
RREEFFEERREENNCCEESS
133
RR EEFF EERR EENN CC EESS
1. Shah, K. M. Handbook of synthetic dyes and pigments, 2nd edition, Multi-tech publishing co., India, 1998, Vol. 1: Synthetic dyes, pp 3.
2. Duff, D. G.; Sinclair, R. S. Giles's Laboratory course in dyeing, 4th edition, Society of Dyers and Colourists: England, 1989.
3. Noller, C. R. Chemistry of organic compounds, 2nd edition, W. B. Saunders Company: London, 1957, pp 673.
4. Welham, A. The theory of dyeing and the secret of life, J.S.D.C. 2000, 116, 141.
5. Gohl, E.P.G.; Vilensky, L.D. Textile science, 2nd edition, CBS Publishers & Distributors: India, 1983, pp 125-132.
6. Hadfield, H. R.; Sokol, W. M. Improvements in or relating to dyed textile materials, G.B. Patent 835,649, 1960.
7. Colorants and auxiliaries; Organic Chemistry and application properties; Shore, J., Ed.; Society of Dyers and Colourists: England, 1990; Vol. 2: Auxiliaries, pp 446.
8. Yang, Y.; Carman, E. F. Non-formaldehyde nitrogen containing fixing agent for direct dyeing, Am. Dyestuff Rep. 1996, 85, 39-44.
9. Sekar, N. Reactive cellulose fibres for no-salt dyeing- a conceptual development towards redressal of environmental issues in reactive dyeing: an update, Colourage 1999, 46, 29-31.
10. Blackburn, R. S.; Burkinshaw, S. M. A greener approach to cotton dyeings with excellent wash fastness, Green Chemistry 2002, 4, 47-52.
134
11. Kamel, M.; Kamel, M. M.; Youssef, B. M.; Shokry, G. M. Dyeing of cationised cotton with acid dyes, J.S.D.C. 1998, 114, 101-104.
12. Danner, B.; Heller, J. Textile dye fixing agents, U.S. Patent 5,908,474, 1999.
13. Colour terms and definitions, Society of Dyers and Colourists: Bradford, 1988.
14. SBP Board of Consultants and Engineers, Manufacture of textile auxiliaries and chemicals; Small Business Publications: India, pp 123-133.
15. Colorants and auxiliaries; Organic Chemistry and application properties; Shore, J., Ed.; Society of Dyers and Colourists: England, 1990; Vol. 2: Auxiliaries, pp 375-386.
16. Cellulosic dyeing, Shore, J., Ed. Society of Dyers and Colourists, Bradford: UK, 1995.
17. Kissiling, B.; Robinson, T. Textile aftertreatment agent and uses thereof, E.P. Patent 0,280,655, 1988.
18. Topfl, R.; Binz, J. Process for the aftertreatment of dyed cellulose fibers, U.S. Patent 4,822,374, 1989.
19. Kamel, M.; Kamel, M. M.; El- Kashouti, M. A. Dye fixation using hexahydro-1,3,5-triacryloyl-s-triazine, Am. Dyestuff Rep. 1971, 60 (3), 33.
20. Kamel, M.; Kamel, M. M.; El- Kashouti, M. A. Fixation using hexahydro-1,3,5-triacryloyl-s-triazine, Am. Dyestuff Rep. 1971, 60 (4), 44.
21. Robinson, T. New trends in the cationic pre- and aftertreatment of reactive dyeings, Melliand Textilber. 1987, 68(2), 137-141.
22. Lewis, D. M.; Lei, X. P. Improved cellulose dyeability by chemical modification of the fibre, Text. Chem. Colorist 1989, 21(10), 23-29.
23. Lewis, D. M.; Lei, X. P. New methods for improving the dyeability of cellulose fibres with reactive dyes, J.S.D.C. 1991, 107, 102-109.
135
24. Lei, X. P.; Lewis, D. M. The dyeing behaviour of cotton modified with chloropropionyl chloride and related compounds, Dyes Pigments 1991, 16 (4), 273-289.
25. Carpmael, A. The production of improved dyeings, G.B. Patent 383,634, 1932.
26. Cuvelier, G.; Wattiez, D. Reactive dyeing of epoxy alkyl quaternary ammonium cellulose or polyvinyl alcohol textiles, U.S. Patent 3,778,225, 1973.
27. John, G. E.; Henry, A. P.; Clarence, S. W. Process of dyeing, G.B. Patent 437,273, 1935.
28. Carpmael, A. Process for improving the fastness of dyeings, G.B. Patent 460,961, 1937.
29. Ha, J. W.; Kim, D.; Kim, T. S.; Rang, M. J. Preparation of cationic surfactants containing ester group in molecules, U.S. Patent 6,414,170, 2002.
30. Halpern, M. Phase-Transfer Catalysis Overview; PTC Organics, Inc. New Jersey: USA.
31. Skow, C. A. R.; Bicking, M. K. L. Direct alkylation of carboxylic in aqueous samples, Chromatographia 1986, 21, 157-160.
32. Smith, K. R.; Sauer, J. D.; Borland, J. E. Quaternary ammonium compounds, U.S. Patent 4,883,917, 1989.
33. Thorsteinsson, T. et al. Soft antimicrobial agents: Synthesis and activity of labile environmentally friendly long chain quaternary ammonium compounds, J. Med. Chem. 2003, 46, 4173-4181.
34. Pera, J. D. Microbicidal compositions of dimethylamine-epichlorohydrin amine polymers, E.P. Patent 0,431,739, 1991.
35. Rabasco, J. J.; Sagl, D. Polymer emulsion preservation using cationic compounds, U.S. Patent 6,890,969, 2005.
36. Haase, J. Quaternary ammonium salts of diepoxides and diamines, their preparation and use, U.S. Patent 4,668,273, 1987.
37. Ogata, Y. Process for the preparation of quaternary ammonium salts, U.S. Patent 3,872,138, 1975.
136
38. Fenyes, J. G.; Pera, J. D. Polymeric quaternary ammonium compounds and their uses, U.S. Patent 4,506,081, 1985.
39. Lang, F. P.; Berenbold, H.; Wesling, M. Washing agents such as detergents contain dye transfer inhibitors which are polyamine/ cyanamide/amidosulfuric acid, cyanamide/aldehyde/ammonium salt or amine/epichlorohydrin reaction products, D.E. Patent 10,150,724, 2003.
40. Horn, U.; Perrin, P.; Hegar, G.; Seiler, H.; Siegrist, G. Process for improving the color yield and fastness properties of dyeings produced with anionic dyes on cellulose fibre material and fluorine-containing cationic compounds, U.S. Patent 4,171,955, 1979.
41. Kamel, M. M.; Youssef, B. M.; Shokry, G. M. Dyeing of cationised cotton. Part II: direct dyes, Am. Dyestuff Rep. 1999, 88(6), 28-31.
42. Arugonda, S. K. Quaternary ammonium compounds; International Programme on Chemical Safety Poisons Information Monograph; Dunedin: New Zealand, 1999.
43. Gipp, R.; Berenstecher, O.; Renziehausen, H. Quaternary N-(2,3-epoxyalkyl)-ammonium compounds, U.S. Patent 4,035,145, 1977.
44. Burkinshaw, S. M.; Gordon, R.; Collins, G. W. Dyeing of textiles, U.S. Patent 2,001,054,209, 2001.
45. Topfl, R. Process for improving the yield and the wet fastness properties of dyeings or prints produced with anionic dyes on cellulose fibre material using alkyl diallyl or halo-hydroxy propyl ammonium salts, U.S. Patent 5,147,411, 1992.
46. Cuvelier, G.; Wattiez, D. Dry heat reaction of quaternised epoxides and quaternised chlorohydrins with hydroxylated textiles, U.S. Patent 3,685,953, 1972.
47. Hauser, P. J.; Tabba, A. H. Dyeing cationic cotton with fibre reactive dyes: effect of reactive chemistries, AATCC Review 2002, 2 (5), 36-39.
48. Hall, D. M.; Leonard, T. M.; Cofield, C. D.; Barrow, H. W. Method of salt free dyeing, U.S. Patent 5,330,541, 1994.
137
49. Draper, S. L.; Beck, K. R.; Smith, C. B.; Hauser, P. J. Characterisation of the dyeing behaviour of cationic cotton with direct dyes, AATCC Review 2002, 2 (10), 24-27.
50. Youssef, Y. A. Direct dyeing of cotton fabrics pre-treated with cationising agents, J.S.D.C. 2000, 116, 316-322.
51. Evans, G. E.; Shore, J.; Stead, C. V. Dyeing behaviour of cotton after pretreatment with reactive quaternary compounds, J.S.D.C. 1984, 100 (10), 304-315.
52. Beyerbach, E. J.S.D.C. 1890, 6, 119; J.S.D.C. 1890, 6, 98.
53. Rattee, I. D. J.S.D.C. 1985, 101, 46.
54. Hurst, G. H. J.S.D.C. 1888, 4, 14.
55. Gill, R. The fixation of direct cotton dyes, J.S.D.C. 1955, 71, 380-389.
56. Wilcock, C. C.; Tattersfield, C. P. Fibrofix, J.S.D.C. 1943, 59, 119-124.
57. Gortvai, A. F. United Merchants and Manufacturers, U.S. Patent 2,973,239, 1961.
58. Knobel, W.; Kissling, B.; Robinson, T. Dyeing auxiliaries and process for the dyeing of cellulose fibres, D.E. Patent 3,105,897, 1982.
59. Valenti, S.; Muller, C.; Heller, J.; Kissling, B.; Robinson, T. Cationic polycondensates useful for improving the fastness of dyeings on textiles, U.S. Patent 4,764,585, 1988.
60. Cook, C. C. Aftertreatments for improving the fastness of dyes on textile fibres, Rev. Prog. Color. 1982, 12, 73-89.
61. Hewson, M. Formaldehyde in textiles, J.S.D.C. 1994, 110, 140-142.
62. Lokhande, H. T.; Kabra, R. S. Development of non-formaldehyde dye fixative agents for reactive dyes, Am. Dyestuff Rep. 1998, 87 (12) 40-44.
63. Lutzel, G. J.S.D.C. 1966, 82, 293.
138
64. Ellis, J. R.; Gantz, G.M. Fibre improving process and product, U.S. Patent 3,178,250, 1965.
65. Patton, R. T.; Kitchens, J. D.; Hall, D. M. Process for improving the dyeability and whiteness of cellulosic fabrics, U.S. Patent 5,006,125, 1991.
66. Hauser, P. J.; Helfrich, S. G. Heather dyed fabric and method for producing same, U.S. Patent 5,667,533, 1997.
67. Hauser, P. J.; Tabba, A. H. Improving the environmental and economic aspects of cotton dyeing using a cationised cotton, Color. Technol. 2001, 117, 282-288.
68. Yao, J; Lewis, D. M. Covalent fixation of hydroxyethyl sulphone dye on cotton by the use of crosslinking agent via a pad-batch process. J.S.D.C. 2000, 116, 198-203.
69. Min, L.; Xiaoli, Z.; Shuilin, C. Enhancing the wash fastness of dyeings by a sol-gel process. Part 1; Direct dyes on cotton, Color. Technol. 2003, 119(5), 297-300.
70. Juan, D.; Li, Z.; Shuilin, C. Wash fastness of dyed fabric treated by the sol-gel process, Color. Technol. 2005, 121(1), 29-36.
71. Konovalova, M. V.; Sazonova, L. V. Preliminary treatment of fabrics in solutions of quaternary ammonium compounds to improve dyeing with reactive dyes, lzv. vuzov.Tekhnol. tekstil prom-sti 1997, 6, 75-78.
72. Wang, H.; Lewis, D. M. Chemical modification of cotton to improve fibre dyeability, Color. Technol. 2002, 118 (4), 159-168.
73. Lim, S. H.; Hudson, S. M. Application of a fibre-reactive chitosan derivative to cotton fabric as a zero-salt dyeing auxiliary, Color. Technol. 2004, 120 (3), 108.
74. Zhang, S.; Ma, W.; Ju, B.; Dang, N.; Zhang, M.; Wu, S.; Yang, J. Continuous dyeing of cationised cotton with reactive dyes, Color. Technol. 2005, 121 (4), 183-186.
75. Youssef, B. M.; Kamel, M. M.; Shokry, G. M. Cotton modified by cation-exchangers; Dyeing with direct dyes: Part II, Tinctoria 1997, 94 (11), 61-65.
139
76. Youssef, B. M.; Kamel, M. M.; Allam, E.; Shokry, G. M. Dyeing of cationised cotton. Part I: reactive dyes, Am. Dyestuff Rep. 1998, 87 (6), 18; Tinctoria 1997, 94 (10), 42-45.
77. Guo, G. Y.; Chen, Y. L. Improving the dyeability of cotton with reactive dyes, Am. Dyestuff Rep. 1994, 83, 58-61.
78. McClure, J. D.; Williams, P. H. A process of producing a glycidyl trialkyl ammonium halide, G.B. Patent 1,056,587, 1967.
79. Klem, R. E.; Doughty, J. B. Process for making quaternary amines of epichlorohydrin, U.S. Patent 4,066,673, 1978.
80. Roerden, D. L.; Childers, L. P. Process for the production of low color 2,3-epoxy propyl trialkyl ammonium halide, U.S. Patent 6,123,738, 2000.
81. Van Der Mass, H. J. H. Method of manufacturing anhydrous 2-hydroxy-3-chloropropane trimethyl ammonium chloride, U.S. Patent 4,450,295, 1984.
82. Deavenport, J. L.; Lopez, B. I. Process for the preparation of halohydroxy propyl trialkyl ammonium halides, U.S. Patent 5,463,127, 1995.
83. Rupin, M. Dyeing with direct and fibre reactive dyes, Text. Chem. Colorist 1976, 8, 54-58.
84. Herbert, D. F.; Barkhuysen, F. A.; Van Rensburg, N. J. J. The use of N-2,3-epoxypropyltrimethylammonium chloride to improve the fixation of dyes to cotton. Part II: Direct dyes, SAWTRI Tech. Rep. 1983, 524, 14.
85. Herbert, D. F.; Barkhuysen, F. A.; Van Rensburg, N. J. J. The use of N-2,3-epoxypropyltrimethylammonium chloride to improve the fixation of dyes to cotton. Part I: Reactive dyes, SAWTRI Tech. Rep. 1983, 523, 24.
86. Seong, H. S.; Ko, S. W. Synthesis, application and evaluation of cationising agents for cellulosic fibres, J.S.D.C. 1998, 114, 124-129.
87. Cannon, K. M.; Hauser, P. J. Color assessment of cationic cotton dyed with fibre reactive dyes, AATCC Review 2003, 3 (5), 21-23.
140
88. Draper, S. L.; Beck, K. R.; Smith, C. B. Characterisation of the dyeing behaviour of cationic cotton with acid dyes, AATCC Review 2003, 3 (8), 51-55.
89. Kanik, M.; Hauser, P. J. Printing of cationised cotton with reactive dyes, Color. Technol. 2002, 118 (6), 300-306.
90. Kanik, M.; Hauser, P. J. Printing cationised cotton with direct dyes, Text. Res. J. 2004, 74 (1), 43-50.
91. Hauser, P. J.; Kanik, M. Printing of cationised cotton with acid dyes, AATCC Review 2003, 3 (3), 25-28.
92. Kanik, M.; Hauser, P. J.; Parrillo-Chapman, L. Effect of cationisation on inkjet printing properties of cotton fabrics, AATCC Review, 2004, 4 (6), 22-25.
93. Kanik, M.; Hauser, P. J. Ink-jet printing of cationised cotton using reactive inks, Color. Technol. 2003, 119 (4), 230-234.
94. Hauser, P. J. Finishing cationised cotton, Magic world of textiles, Book of the proceedings of the international textile, clothing and design conference, 2002, 274-277; Chem. Abs., 2003, 139, 118643d.
95. Morris, H.; Hauser, P. J. The effects of a cationic reagent on typical finishes, AATCC Review 2003, 3(11), 17-19.
96. Clipson, J. A.; Roberts, G. A. F. Differential dyeing cotton.1–Preparation and evaluation of differential dyeing cotton yarn, J.S.D.C. 1989, 105, 158-162.
97. Clipson, J. A.; Roberts, G. A. F. Differential dyeing cotton. Par 2–stoichiometry of interaction with acid and direct dyes, J.S.D.C. 1994, 110, 69-73.
98. El-Shishtawy, R. M.; Youssef, Y. A.; Ahmed, N. S. E.; Mousa, A. A. Acid dyeing isotherms of cotton fabrics pretreated with mixtures of reactive cationic agents, Color. Technol. 2004, 120 (4), 195-200.
99. Stead, C. V.; Evans, G. E.; Shore, J. Triazine dye fixing agents, G.B. Patent 2,119,367, 1983.
100. Virkler, H. E.; Lewis, D. M.; Broadbent, P. J. Salt free dyeing of cellulosic fibres with anionic dyes, U.S. Patent 6,350,872, 2002.
141
101. Burkinshaw, S. M.; Lei, X. P.; Lewis, D. M. Modification of cotton to improve its dyeability. Part 1–pretreating cotton with reactive polyamide-epichlorohydrin resin, J.S.D.C. 1989, 105, 391-398.
102. Burkinshaw, S. M.; Lei, X. P.; Lewis, D. M.; Easton, J. R.; Parton, B.; Phillips, D. A. S. Modification of cotton to improve its dyeability. Part 2-pretreating cotton with a thiourea derivative of polyamide-epichlorohydrin resins, J.S.D.C. 1990, 106, 307-315.
103. Lei, X. P.; Lewis, D. M. Modification of cotton to improve its dyeability. Part 3-polyamide-epichlorohydrin resins, J.S.D.C. 1990, 106 (11), 352.
104. Blackburn, R. S.; Burkinshaw, S. M.; Gordon, R. Pretreatment of cotton to facilitate no salt, no alkali, neutral pH dyeing with a range of reactive dyes, AATCC Conf. 2000, 8.
105. Wu, T. S.; Chen, K. M. New cationic agents for improving the dyeability of cellulose fibres. Part 1–pretreating cotton with polyepichlorohydrin-amine polymers for improving dyeability with direct dyes, J.S.D.C. 1992, 108, 388-394.
106. Koo, B. C.; Burkinshaw, S. M. The pretreatment of cotton to enhance its dyeability. Part III–repeated wash fastness of direct dyes, Adv. Col. Sci. Technol. 1998, 1(3), 76-79.
107. El-Shishtawy, R. M.; Nassar, S. H. Cationic pretreatment of cotton fabric for anionic dye and pigment printing with better fastness properties, Color. Technol. 2002, 118 (3), 115-120.
108. Burkinshaw, S. M.; Gotsopoulos, A. Pretreatment of cotton to enhance its dyeability; Part 2. Direct dyes, Dyes Pigments 1999, 42(2), 179-195.
109. Blackburn, R. S.; Burkinshaw, S. M.; Gordon, R. Dyeing cotton /polyamide blend fabrics with 1:2 metal complex acid dyes, Text. Chem. Colorist and Am. Dyestuff Rep. 2000, 32 (12), 44-48.
110. Blackburn, R. S.; Burkinshaw, S. M. A greener approach to cotton dyeings. Part 2: application of 1:2 metal complex acid dyes, Green Chemistry 2002, 4, 261-265.
142
111. Schleusener, E. High molecular weight linear polymers of diallylamines and process for making same, U.S. Patent 4,864,007, 1989.
112. Harada, S.; Ueda, T.; Kageno, K. Method for improving color fastness: mono- and di-allylamine copolymer for reactive dyes on cellulose, U.S. Patent 4,583,989, 1986.
113. Harada, S.; Ueda, T.; Kageno, K. Method for improving color fastness of reactive dyes on cellulose with allylamine copolymer, U.S. Patent 4,678,474, 1987.
114. Burkinshaw, S. M.; Gordon, R.; Collins, G. W. Dyeing of textile, U.S. Patent 6,200,354, 2001.
115. Burkinshaw, S. M.; Collins, G. W. An attempt to enhance the effectiveness of the aftertreatment of direct dyeings with cationic fixing agents, J.S.D.C. 1998, 114, 12-15.
116. Blackburn, R. S.; Burkinshaw, S. M.; Collins, G. W. The application of cationic fixing agents to cotton dyed with direct dyes under different pH conditions, J.S.D.C. 1998, 114, 317 -320.
117. Cai, Y.; Pailthorpe, M. T.; David, S. K. A new method for improving the dyeability of cotton with reactive dyes, Text. Res. J. 1999, 69(6), 440-446.
118. Ma, W.; Zhang, S.; Tang, B.; Yang, J. Pretreatment of cotton with poly (vinylamine chloride) for salt-free dyeing with reactive dyes, Color. Technol. 2005, 121(4), 193-197.
119. Eleftheriadis, I. C.; Pegiadou-Koemtzopoulou, S. A.; Papazoglou, V. M.; Kehayoglou, A. H. Direct dyes on cotton grafted with 2-vinylpyridine and quaternised with alkyl bromides or epichlorohydrin, J.S.D.C. 1996, 112 , 375-378.
120. Srikulkit, K.; Larpsuriyakul, P. Process of dyeability, modification and bleaching of cotton in a single bath, Color. Technol. 2002, 118(2), 79-84.
121. Organic Synthesis, An annual publication of satisfactory methods for the preparation of organic chemicals, Newman, M. S. Ed., Vol. 40, John Wiley and Sons, Inc. New York, 1960, pp 32.
143
122. Clarke, H. T.; Gillespie, H. B.; Weisshaus, S. Z. The action of formaldehyde on amines and amino acids, J. Am. Chem. Soc. 1933, 55, 4579.
123. Bue, S. R.; Ford, J. H.; Wise, E. C. An improved synthesis of β–alanine, J. Am. Chem. Soc. 1945, 67, 92-94.
124. Galat, A. A new synthesis of β–alanine, J. Am. Chem. Soc. 1945, 67, 1414-1415.
125. Encyclopedia of Industrial Chemical Analysis, Snell, F. D.; Ettre, L. S. Eds. Vol. 12, Interscience Publishers: New York, 1968, pp 196.
126. Feigl, F. Spot Tests in Organic Analysis, Elsevier Publishing Company: Amsterdam, 1966, pp 251.
127. Kortland, C.; Dammers, H. F. Qualitative and quantitative analysis of mixtures of surface-active agents with special reference to synthetic detergents, J.A.O.C.S. 1955, 32, 58-64.
128. The dyeing of synthetic polymer and acetate fibres, Nunn, D. M. Ed. Dyers Company Publications Trust, 1979, pp 53.
129. Standard Methods for the Determination of the Colour Fastness of Textiles and Leather, Society of Dyers and Colourists, Bradford: UK, 5th edition, 1990.
130. AATCC Technical Manual, Vol. 79, American Association of Textile Chemists and Colorists, USA, 2004.
131. Bluhm, L. H.; Li, T. Chromatographic purification of quaternary ammonium and pyridinium compounds on normal phase silica gel, Tetrahedron Lett. 1998, 39, 3623-3626.
144
VVIITTAA Saima Sharif was born on January 02, 1975 in Lahore, Pakistan. She
received Bachelor of Science degree from the University of Punjab in 1994. In
1996, she joined the Department of Chemistry, Government College Lahore
and received Master of Science degree in 1997. In March 1999, she was
appointed as a Lecturer in Chemistry at Govt. Islamia Degree College for
Women, Hafizabad. Since then she has been working as a Lecturer.
She enrolled in the University of Education, Lahore in 2003 and started
her studies towards the Doctor of Philosophy degree under the supervision of
Dr. Saeed Ahmad/ Chairman, Department of Chemistry, University of Science
and Technology, Bannu-NWFP, Pakistan.
Publications
♦ Role of quaternary ammonium salts in improving the fastness
properties of anionic dyes on cellulose fibres, Saima Sharif, Saeed
Ahmad and Mian Muhammad Izhar-ul-Haq, Coloration Technology,
2007, 123(1), 8-17. (U.K) (Review article)
♦ Synthesis and spectroscopic characterisation of epoxy / halohydroxy
propyl derivatives of quaternary ammonium salts, Saima Sharif,
145
Saeed Ahmad and Mian Muhammad Izhar-ul-Haq, Chinese Journal
of Chemistry. (Accepted)
♦ Aftertreatment of direct dyes on cotton with a bis-reactive cationic
fixing agent, Saima Sharif, Saeed Ahmad, Mian Muhammad Izhar-ul-
Haq, Muhammad Naeem Khan and Muhammad Fauz-ul-Azeem,
(Submitted)
♦ Effect of cationic fixing agents on the direct dyeing properties of
cotton fabrics. (Submitted)
146
AAppppeennddii xx AA
CCOOLLOOUURR SSTTRREENNGGTTHH ((KK//SS)) CCUURRVVEESS OOFF UUNNTTRREEAATTEEDD
((CC)) AANNDD PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33)) CCOOTTTTOONN
FFAABBRRIICCSS DDYYEEDD WWIITTHH DDIIRREECCTT DDYYEESS ((TTaabbll ee 2255))
CC // CC.. II .. DDii rreecc tt OOrraa nn ggee 2266
CC-- 11 // CC.. II .. DD ii rreecc tt OOrraa nnggee 2266
147
CC-- 22 // CC.. II .. DD ii rreecc tt OOrraa nnggee 2266
CC-- 33 // CC.. II .. DD ii rreecc tt OOrraa nnggee 2266
CC // CC.. II .. DDii rreecc tt RR eedd 33 11
148
CC--11 // CC.. II .. DD ii rreecc tt RR eedd 33 11
CC--22 // CC.. II .. DD ii rreecc tt RR eedd 33 11
CC--33 // CC.. II .. DD ii rreecc tt RR eedd 33 11
149
CC // CC.. II .. DDii rreecc tt BBllaa cckk 2222
CC-- 33 // CC.. II .. DD ii rreecc tt BBllaa cckk 2222
150
AAppppeennddii xx BB
CCOOLLOOUURR SSTTRREENNGGTTHH ((KK//SS)) CCUURRVVEESS OOFF UUNNTTRREEAATTEEDD
CCOOTTTTOONN FFAABBRRIICCSS DDYYEEDD WWIITTHH DDIIRREECCTT DDYYEESS BBYY
CCOONNVVEENNTTIIOONNAALL MMEETTHHOODD ((TTaabbll ee 2266))
CC .. II .. DD ii rreecc tt OO rraann gg ee 22 66
CC .. II .. DD ii rreecc tt RR eedd 3311
151
CC .. II .. DD ii rreecc tt BBll aa cckk 2222
152
AAppppeennddii xx CC
CCOOLLOOUURR SSTTRREENNGGTTHH ((KK//SS)) CCUURRVVEESS OOFF UUNNTTRREEAATTEEDD
((CC)) AANNDD PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33)) CCOOTTTTOONN
FFAABBRRIICCSS DDYYEEDD WWIITTHH RREEAACCTTIIVVEE DDYYEESS IINN TTHHEE
AABBSSEENNCCEE OOFF SSAALLTT AANNDD AALLKKAALLII ((TTaabbllee 3322))
CC // CC.. II .. RReeaa cc tt ii vvee OOrraa nn ggee 1133
CC--11 // CC.. II .. RR eeaa cc tt ii vvee OOrraa nn ggee 1133
153
CC--22 // CC.. II .. RR eeaa cc tt ii vvee OOrraa nn ggee 1133
CC--33 // CC.. II .. RR eeaa cc tt ii vvee OOrraa nn ggee 1133
CC // CC.. II .. RReeaacc tt ii vv ee RReedd 4455
154
CC--11 // CC.. II .. RR eeaacc tt ii vv ee RR eedd 4455
CC--22 // CC.. II .. RR eeaacc tt ii vv ee RR eedd 4455
CC--33 // CC.. II .. RR eeaacc tt ii vv ee RR eedd 4455
155
CC // CC.. II .. RReeaa cc tt ii vvee BBlluuee 55
CC-- 11 // CC.. II .. RR eeaa cc tt ii vvee BBlluu ee 55
CC-- 22 // CC.. II .. RR eeaa cc tt ii vvee BBlluu ee 55
156
CC-- 33 // CC.. II .. RR eeaa cc tt ii vvee BBlluu ee 55
157
AAppppeennddii xx DD
CCOOLLOOUURR SSTTRREENNGGTTHH ((KK//SS)) CCUURRVVEESS OOFF UUNNTTRREEAATTEEDD
((CC)) AANNDD PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33)) CCOOTTTTOONN
FFAABBRRIICCSS DDYYEEDD WWIITTHH RREEAACCTTIIVVEE DDYYEESS IINN TTHHEE
PPRREESSEENNCCEE OOFF AALLKKAALLII ((TTaabbll ee 3333))
CC--11 // CC.. II .. RR eeaa cc tt ii vvee OOrraa nn ggee 1133
CC--22 // CC.. II .. RR eeaa cc tt ii vvee OOrraa nn ggee 1133
158
CC--33 // CC.. II .. RR eeaa cc tt ii vvee OOrraa nn ggee 1133
CC--11 // CC.. II .. RR eeaacc tt ii vv ee RR eedd 4455
CC--22 // CC.. II .. RR eeaacc tt ii vv ee RR eedd 4455
159
CC--33 // CC.. II .. RR eeaacc tt ii vv ee RR eedd 4455
CC-- 11 // CC.. II .. RR eeaacc tt ii vv ee BBll aa cckk 55
CC-- 22 // CC.. II .. RR eeaacc tt ii vv ee BBll aa cckk 55
160
CC-- 33 // CC.. II .. RR eeaacc tt ii vv ee BBll aa cckk 55
161
AAppppeennddii xx EE
CCOOLLOOUURR SSTTRREENNGGTTHH ((KK//SS)) CCUURRVVEESS OOFF UUNNTTRREEAATTEEDD
CCOOTTTTOONN FFAABBRRIICCSS DDYYEEDD WWIITTHH RREEAACCTTIIVVEE DDYYEESS BBYY
CCOONNVVEENNTTIIOONNAALL MMEETTHHOODD ((TTaabbll ee 3344))
CC .. II .. RR eeaa cctt ii vvee OOrraannggee 1133
CC .. II .. RR eeaacctt ii vv ee RR eedd 4455
162
CC .. II .. RR eeaa cc tt ii vv ee BBllaacckk 55
163
AAppppeennddii xx FF
CCOOLLOOUURR SSTTRREENNGGTTHH ((KK//SS)) CCUURRVVEESS OOFF WWOOOOLL,,
UUNNTTRREEAATTEEDD ((CC)) AANNDD PPRREETTRREEAATTEEDD ((CC--11 ,, CC--22 aanndd CC--33))
CCOOTTTTOONN FFAABBRRIICCSS DDYYEEDD WWIITTHH AACCIIDD DDYYEESS
CC // CC.. II .. AAcc iidd BBllaacckk 22 33 44
CC-- 11 // CC.. II .. AAcc iidd BBllaacckk 22 33 44
164
CC-- 22 // CC.. II .. AAcc iidd BBllaacckk 22 33 44
CC-- 33 // CC.. II .. AAcc iidd BBllaacckk 22 33 44
WWoo oo ll // CC .. II .. AA cc iidd BBllaa cckk 22 33 44
Role of quaternary ammonium salts inimproving the fastness properties ofanionic dyes on cellulose fibres
Saima Sharif,a,b Saeed Ahmadb,* and Mian MuhammadIzhar-ul-Haqa
aDivision of Science and Technology, University of Education, Township Campus, CollegeRoad, Township, Lahore-54770, Pakistan
bApplied Chemistry Research Centre, PCSIR Laboratories Complex, Ferozepur Road,
Lahore-54600, Pakistan
Email: [email protected]
The object of this study was to review the developments taking place during 1990–2005 regarding theuse of quaternary ammonium salts as dye fixing agents for improving the fastness properties of anionicdyes on cellulose fibres. As far as fastness properties are concerned, this review is restricted only tofastness to light, washing and water treatments.
IntroductionThe practice of dyeing has recently led to increased
requirements in terms of quality of dyeings and
profitability of the dyeing process. There is still a need for
novel dyeing processes that improve properties, in respect
of application and fastness properties of the dyeings.
Cellulose fibres can be dyed with direct and reactive
dyes. The affinity of direct dyes for cotton is due to the
linear and planar structure of the dye molecules, which
enables close alignment with chains of cellulose
molecules resulting in significant hydrogen bonding.
Generally, the dyed cellulosic fibres have a fastness to
washing that does not meet the requirements of today’s
consumers. This is particularly the case not only for
many direct dyes but to a lesser extent for reactive dyes
also [1]. Although direct dyes possess inadequate wet
fastness properties they are still widely used for their
ease of application, comparatively low cost and wide
range of shades [2]. Acid dyes, which are primarily used
for the dyeing of nitrogenous fibres such as wool, silk and
nylon, are also anionic in nature. The relatively nonlinear
structure of these acid dyes does not facilitate close
alignment with the molecular chains in cellulose, which
in turn prevents hydrogen bonding. Therefore, these dyes
are not substantive to cellulosic fibres. However,
cationised cellulosic fibres can be dyed with acid dyes of
both the non-metallised and premetallised types. This
increase in substantivity is due to the interaction of
anionic sulphonic groups in the dye molecules with the
cationic groups in the modified cellulose [3].
Notable improvements in the wet fastness properties of
anionic dyes can be brought about by pretreatment or
aftertreatment of textile fibres. The use of pretreatments
or aftertreatments to improve the fastness properties of
dyeings has a long and prolific history. Various
pretreatment and aftertreatment systems have been
developed but at the moment most widely used are
cationic fixing agents. These chemicals function by
forming a complex of high molecular weight and low
aqueous solubility and therefore high wet fastness [4].
Amines [5], quaternary ammonium [6], phosphonium
[7] and tertiary sulphonium compounds [8] can be used
as dye fixing agents. By far the most important type of
cationic fixing agents used in textile processing is
quaternary ammonium salt. Different quaternary
ammonium salts [9,10] have been applied to the fibres
either as pretreatment or aftertreatment to improve the
fastness properties of anionic dyes.
There has been significant new developments in this
area with respect to developing commercially feasible
fixing agents in the last one and half decade. These new
developments during the period from 1990 to 2005 form
the subject matter of this review article. As far as the
fastness properties are concerned, this review is restricted
only to fastness to light, washing and water treatments.
General developmentMost early dyeing processes used naturally occurring
coloured compounds, e.g. dye woods [11], which had no
significant affinity for cotton and silk. These processes
required a metal salt mordant before dyeing and after
dyeing, fixation with tannin.
The major growth and establishment of the synthetic
dye industry was initiated with the discovery of Congo
Red, the first direct dye for cotton, in 1884 [12]. Although
some early direct dyeings were claimed to be fast to
soaping [13] it was soon appreciated that fastness to light
and wet treatments left much to be desired.
From 1930 onwards, complexing of direct dyes, present
on the fibre, with aqueous solutions of cationic fixing
agents began to be fully exploited. The importance and
use of these agents was greatly extended by the
development of products rising from the condensation of
cyanamide (1) or similar compounds with formaldehyde.
These resin fixatives [14] of which Fibrofix (2) was a
doi: 10.1111/j.1478-4408.2006.00053.x
8 ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17
classical example [15], could be applied by a simple,
finishing technique to cellulosic fibres dyed or printed
with direct dyes. This resin fixative class was rapidly
extended to provide a large number of agents based on
the condensation products of formaldehyde with
cyanamide derivatives [16], which were suitable for
aftertreatment of direct dyes on cellulose fibres. Later on,
the reaction products of cyanamide or cyanamide
derivatives with monofunctional or polyfunctional amines
and the condensates of these amines with formaldehyde
or N-methylol derivatives were used as an aftertreatment
to improve the wet fastness properties of anionic dyes on
cellulose fibres [17,18]. Other relevant developments in
this area have already been reviewed in detail [19].
Extensive research work has shown that formaldehyde-
based resin finished products release formaldehyde into
the atmosphere directly or during processing, handling,
garment manufacturing and subsequent wearing of
textiles due to the hydrolysis of unreacted or partially
crosslinked N-methylol derivatives present on the fibre.
Direct release of formaldehyde into the working
environment causes severe irritation to eyes, nasal
passages and respiratory tract while an unreacted or
partially crosslinked resin causes an allergenic response
of the skin upon continuous handling of textiles [20]. For
reasons of these health problems associated with
formaldehyde, there was an increasing demand for
non-formaldehyde fixing agents. It has also been reported
that formaldehyde containing fixing agents for direct
dyeing could be substituted by nitrogen containing
non-formaldehyde fixatives without sacrificing the
performance properties of the finished goods. Selection of
suitable non-formaldehyde fixatives could actually
produce better products than using the formaldehyde
fixative [21]. Nitrogenous-based dye fixing agents have
also been reported to improve overall fastness properties,
without affecting the tone and depth of shades of reactive
dyes on cotton substrates. The results indicated that
commercial non-formaldehyde and formaldehyde-based
dye-fixing agents could be replaced by laboratory
developed nitrogenous-based dye fixing agents [22].
After the discovery of reactive dyes, dyeing with reactive
dyes became the most versatile method for the coloration
of cellulosic fabrics. These dyes were used instead of
aftertreated direct dyes. However, the fundamental
problem of reactive dyeing is that the reaction of reactive
dye with water (hydrolysis) competes with the formation of
the desired covalent bond between the dye and textile
substrates (fixation reaction). As the hydrolysed dye cannot
react with the fibre it should be washed off thoroughly in
order to achieve the desired superior wet fastness of the
reactive dyeing. This involves expensive washing off
procedures and the treatment of the effluent. Thus, reactive
dyes have both economic and environmental drawbacks
because of high salt usage and insufficient fixation caused
by hydrolysis leading to pollution of the effluent [23].
However, if an aftertreatment is given prior to the rinsing
stage, hydrolysed dye also gets fixed showing improved
wet fastness. Therefore, aftertreatment still remained an
extremely useful way of improving the wet fastness
properties of a deep dyeing that failed to meet the
necessary standards.
Developments taking place during the recent decade
have enabled direct dyes to compete with reactive dyes in
the field of severe wet fastness requirements. The
production, in the 1960s, of polyfunctional crosslinking
fixing agents [24,25] capable of reacting with both dye
and fibre was a significant development. These agents
were used to after-treat dyes on cellulosic, polyamide and
wool fibres.
During 1980s there was a great revival of interest in the
techniques for enhancing the dyeability of cellulosic fibres
with reactive or direct dyes by pretreatment with a great
variety of cationic products usually based on nitrogen.
This modification of cellulosic fibres with cationic agents
resulted in increased substantivity of anionic dyes for
cellulosic fibres by introducing new cationic sites. Lewis
and Lei reviewed numerous chemicals that can be used to
provide cationic charges to cotton fibres [26]. Pretreatment
of cellulosic fibres with cationic agents has been reported
to enhance the uptake of anionic dyes and facilitate the
fixation of reactive dyes in the absence of either salt or
alkali [27,28]. The cationised fibre not only has improved
substantivity for direct and reactive dyes, but could also
be dyed with acid dyes [3].
The use of anionic dyes (acid, direct and reactive dyes)
and cationic fixing agents is widespread in dyeing
processes. Many studies have been devoted to improve the
fastness properties of anionic dyes by pretreating or
aftertreating the fibres with amines or reactive cationic
agents. Most of these studies have used monomeric or
polymeric quaternary ammonium salts having different
reactive groups. These include dialkyl azetidinium
chloride, epoxypropyl/halo-hydroxypropyl trialkyl
derivatives of ammonium chloride, mono- and bis-reactive
haloheterocyclic compounds and poly-epichlorohydrin
dimethylamine derivatives.
The mechanisms of dyeing cotton textiles pretreated
with quaternary compounds of epoxypropyl type and
mono- and bis-reactive chlorotriazine type were studied.
The high reactivity and better thermal stability of
chlorotriazine type agents than epoxypropyl type agents
made them suitable for pad–batch or exhaust applications
rather than the more costly pad–bake process and gave
effective enhancement of reactive dye uptake [29]. Later
on, it was found that the pretreatment of cotton fabric with
bis-reactive cationic agent promoted higher extents of dye
exhaustion and fixation than that with mono-reactive
cationic agent [30]. The presence of heterocyclic ring and
imino groups in the chloroazine type agents contributes
towards the higher substantivity of these agents for
cellulose substrates than the epoxypropyl type agents. The
low substantivity and poor thermal stability of
H2N C N1
NH2
HNN
Xn
NHCNn
2
Sharif et al. Role of quaternary ammonium salts
ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17 9
epoxypropyl agents made them unsuitable for exhaust
application and was also responsible for the poor dye
penetration due to significant migration of agent during the
thermal reaction step of pad–bake process leading to non-
uniform distribution of cationic dye sites on the fibre [29].
The reactivity of cotton with such types of compounds has
been studied under a variety of conditions [9,31,32] but no
best procedure has yet been established. Recent work has
shown that cotton cationised through a pad–batch process
gave excellent dye penetration indicating the uniform
distribution of cationic dye sites through this process.
Thus, a pad–batch process seems to be good for achieving
high yields of cationically modified cotton with uniform
distribution of dye sites [33]. The pad–batch dyeing
technique has now become an important dyeing method
for its simplicity, low consumption of energy and water,
and excellent reproducibility [34].
Monomeric quaternary ammonium saltsThe use of cationic agents in the form of primary,
secondary, tertiary and quaternary amino residues has
been known since 1926 [5,6]. To investigate systematically
the effect of attaching a variety of amines to the cellulose
fibre, cotton was modified by pretreatment with N-
methylolacrylamide (3; Allied Colloids) to introduce a
pendant-activated double bond (Scheme 1). By introducing
amino residues at these new sites good colour yield and
high fixation values of reactive dyes were achieved at pH
5–7 in the absence of electrolyte but light fastness was
lowered. Cellulose modified with only N-methyl-
olacrylamide also gave high colour yields with dyes
containing pendant aliphatic amino residues in the
presence of electrolyte under alkaline conditions [27].
Recently, a new fibre-reactive quaternary compound
containing an acrylamide residue was synthesised and
applied to cotton fabrics using a pad–bake process. It was
found that the treated fibre could be dyed with reactive
dyes without the addition of salt or alkali. The reactive
dyes were almost completely exhausted and showed a
high degree of covalent bonding with the pretreated
cellulose [35]. Cationic starch had also been used for the
modification of cotton fabrics. Dyeing of this modified
fibre with reactive dyes using a continuous dyeing method
gave improved dye fixation and level dyeing without the
presence of salt compared with untreated cotton. The
dyeings also showed good wash and rub fastness [36].
Azetidinium chloride
An investigation of the direct dyeing of cotton cationised
with 1,1-dimethyl-3-hydroxy azetidinium chloride (4),
1,1-diethyl-3-hydroxy azetidinium chloride (5) or
Sandene 8425 (aliphatic polyamine derivative; Clariant)
showed improved dye absorption and firmness of colour
in the absence of salt in a neutral medium [37,38]. The
above-modified fibre also enhanced the exhaustion and
fixation of acid (Table 1) [3] and reactive dyes [39] on
cotton in the absence of salt in a neutral medium. The
effect of alkali pretreatment followed by 1,1-dimethyl-3-
hydroxyazetidinium chloride (DMAC) treatment on the
dyeability of cotton yarn with reactive dyes has been
reported to produce a much stronger colour yield than by
DMAC treatment without alkali pretreatment [40].
Epoxy and halohydroxy propyl derivatives
Several patents have covered the preparation of epoxy
and halohydroxy propyl derivatives of ammonium
chloride [41–45]. Many attempts have been made to fix
epoxy and halohydroxy propyl derivatives to cellulose via
an ether linkage. Epoxypropyl derivatives of ammonium
chloride react with cellulose under alkaline conditions
to form ethers (Scheme 2). However, when
halohydroxypropyl derivatives have been used for the
cationisation of cellulosic fabrics under alkaline
conditions, an epoxide ring is first formed in the
cationising agent by the action of alkali and it then reacts
with the hydroxyl group of cellulose under alkaline
conditions (Scheme 3). Alkali is required both for the
formation of epoxide ring and for its reaction with
cellulose. Thus, both epoxy and halohydroxy propyl
derivatives have the same reactive group.
The first product of this type was Glytac A (Protex; 6),
which reacted with cellulose via the glycidyl group at
alkaline pH [46]. 3-Chloro-2-hydroxypropyltrialkyl
derivatives of ammonium chloride (7) were synthesised
through the reaction of various trialkylamines with
epichlorohydrin and were used for the cationisation of
cellulosic fibres under alkaline conditions. Cationised
fibres showed slightly better light fastness than those on
nylon or wool dyed with the same acid dye (Ciba) but
their wash fastness decreased with increasing length
of hydrocarbon chain (Table 2) [47]. The use of
2,3-epoxypropyltrimethyl ammonium chloride (6) as
pretreatment, a simultaneous treatment or an
aftertreatment increased the fixation and fastness
properties (except rubbing fastness) of direct dyes on
cotton textiles. It has been observed that a pretreatment
generally produced better results than an aftertreatment.
An increase in the number of solubilising groups on the
HO NH
O
CH2
3
Cell OH HO NH
O
CH2 O NH
OCH2Cell H2OZnCl2 / 150 °C
Scheme 1
MeN
MeOH
4
Cl
EtN
EtOH
5
Cl
Sharif et al. Role of quaternary ammonium salts
10 ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17
direct dye molecules generally resulted in a deterioration
of the rubbing fastness of pretreated fabrics and an
improvement in the case of aftertreated fabrics [48]. This
treatment has also been reported to increase the fixation
of various reactive dyes on cotton but reduced the
fastness properties of dyed fabrics [49]. A comparative
study of the reactive dyeing of unmodified cotton and
cotton cationised with compound 6 with dyes having four
different reactive groups showed that cationic cotton gave
the same colour fastness as the unmodified cotton, but
usually with higher colour yields [50]. Cotton modified
with this agent through a cold pad–batch process has
been reported to show excellent colour yields and
fastness properties for a number of direct (Crompton &
Knowles), reactive and acid dyes (Dystar), without the
use of electrolytes or multiple rinses, which are normally
employed in cotton dyeing (Table 3) [32,33].
Table 1 Properties of acid dyes with cationic cotton using no salt at pH 7
Dye Treatmentb
K/S Fastness properties
After wash After DMFc
Washinga
LightA C W
CI Acid Red 73 I 3.62 0.95 4 4 3–4 4II 9.34 4.02 2–3 2 2 6III 1.04 0.39 2–3 4 3–4 5–6
CI Acid Orange 7 I 2.51 0.50 2–3 2 2–3 2–3II 6.18 0.98 2 2–3 2–3 6III 1.05 0.35 2 4–5 4–5 3
CI Acid Yellow 36 I 1.23 0.35 2 3–4 2 5II 3.25 0.37 2 4 3 4–5III 0.64 0.21 3 3–4 4–5 4
CI Acid Green 12 I 3.87 2.03 2 3–4 2 5II 7.14 4.76 4 4 3 5III 1.95 0.41 2 4 3 6
CI Acid Red 183 I 2.72 2.66 3–4 2–3 2–3 6II 12.14 5.88 4 4–5 4 6III 2.51 0.43 3 4–5 4–5 6
CI Acid Red 214 I 4.63 3.20 2 4 2–3 6II 12.51 7.55 3–4 3–4 3–4 6III 3.25 0.68 2 2 3 6
a A, change in colour; C, staining on cotton; W, staining on woolb I, Sandene 8425; II, 1,1-dimethyl-3-hydroxy azetidinium chloride (DMA-AC); III, 1,1-diethyl-3-hydroxy azetidinium chloride (DEA-AC)c DMF, dimethyl formamide
R1
NR2
R3 OCell OH
OH R1
NR2 R3
OH
OCell
ClCl
Scheme 2
R1
NR2
R3 OCell OH
OH R1
NR2 R3
OH
OCell
R1
NR2
R3 O
OHR1
NR2 R3
OH
Cl
Cl
ClCl
Cl
Scheme 3
ON
Me
MeMe
6
Cl
ClOH
NR1
R2
R3
C2H5
C3H7
CH3
C5H11
R1 = R2 = R3 =
7
Cl
Table 2 Fastness properties of acid dye on cotton cationisedwith different quaternary salts
Dye SubstrateCationicagenta
Wash fastness
Lightfastness
Changein colour Staining
CI AcidRed 127
Cotton CMAC 4–5 3 4–5CEAC 4 3 4–5CPAC 3 2–3 4–5CP5AC 3 2–3 4–5CDTAC 1–2 2 4–5
Nylon 4–5 2–3 4Wool 4–5 2–3 4
a CMAC, 3-chloro-2-hydroxypropyltrimethyl ammonium chloride;CEAC, 3-chloro-2-hydroxypropyltriethyl ammonium chloride;CPAC, 3-chloro-2-hydroxypropyltripropyl ammonium chloride;CP5AC, 3-chloro-2-hydroxypropyltripentyl ammonium chloride;CDTAC, 3-chloro-2-hydroxypropyldimethyltetradecyl ammonium chloride
Sharif et al. Role of quaternary ammonium salts
ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17 11
The dyeing behaviour of cotton, cationised with
3-chloro-2-hydroxypropyltrimethyl ammonium chloride
(8; Fisher Scientific), with direct dyes was investigated.
Findings revealed that cationised cotton could be dyed
without salt and required less rinsing to remove unfixed
dye than cotton dyed by conventional methods [51].
Dyeing of this cationised cotton with fibre-reactive dyes
showed deeper shades. Moreover, nonlinear colour
behaviour occurred with cationised cotton at lower
concentrations than with unmodified cotton, suggesting
that predicting shades on cationised cotton requires
caution [52]. Significant differences in dyeing rates and
dye uptake of acid dyes on this cationic cotton were
observed over untreated cotton. Fastness to laundering
and light was greatly improved for cationic cotton over
untreated cotton, but remained somewhat lower than the
values for nylon [53].
The printing properties of cationised cotton that had
been pretreated with compound 6 were found to be
very effective in reducing fixation (steaming) times and
washing off processes, and in increasing colour yield
and wet fastness properties for a number of reactive
[54] and direct dyes [55]. Printing on cationic cotton
with acid dyes could be carried out at neutral pH
because of the presence of cationic charges on the fibres
at all pH values, avoiding the need for a pH regulator
in the print paste and for neutralisation during washing.
This technique did not need an intensive washing
procedure, and thus appeared to be a more
environmentally friendly printing process [56]. The
effect of cationisation on the quality of ink-jet printing
on cotton fabrics was also investigated. Ink-jet printing
with reactive dyes or reactive inks on cationised cotton
was found to have good potential as a cost-effective and
more environmentally friendly printing method using
less dye, less thickener and less alkali without
relinquishing outline sharpness [57,58].
Epoxy and halohydroxy propyl derivatives of
diallylamine (9 and 10) have also been reported in this
regard. Cotton pretreated with these agents showed
improved fastness properties for a number of direct dyes
(Table 4) [59].
Table 3 Fastness properties of direct reactive, and acid dyes with nylon, conventional cotton and cationised cotton
Dye Cotton fabric K/S
Colour fastness
Light fastnessbChange in colour Staininga
Conventional cotton and cationised cottonCI Direct Blue 78 Untreated 8.67 2 2–5 5
Cationic 13.99 4–5 4 5CI Direct Blue 86 Untreated 8.76 1 2–5 5
Cationic 44.74 5 4–5 5CI Direct Red 80 Untreated 14.16 2 2 3–5
Cationic 20.11 4–5 5 4–5CI Direct Yellow 106 Untreated 10.29 3 3–5 5
Cationic 14.46 5 5 5CI Reactive Blue 21 Untreated 15.08 4–5 5 5
Cationic 53.34 4 5 4–5CI Reactive Blue 203 Untreated 16.37 4–5 4–5 5
Cationic 24.24 4–5 4–5 4–5CI Reactive Red 239 Untreated 8.24 5 4–5 4–5
Cationic 12.40 5 4–5 4–5CI Reactive Orange 107 Untreated 6.91 4–5 5 5
Cationic 18.24 4 5 4–5Nylon and cationised cottonCI Acid Black 172 Nylon 4–5 4–5 5
Cationic cotton 2–5 4–5 5CI Acid Blue 221 Nylon 4–5 4–5 5
Cationic cotton 3–5 4–5 4–5CI Acid Red 260 Nylon 5 4–5 5
Cationic cotton 3–5 3–5 5CI Acid Yellow 79 Nylon 4–5 4–5 5
Cationic cotton 4–5 4–5 5
a Staining of nylon fabric during laundering, and staining on cottonb 20 h
Cl
OH
NMe
Me Me
8
Cl
ON
CH3
CH2
CH2
Cl
OH
N
CH3
CH2
CH2
OSO3CH3 OSO3C2H5 SO3C6H4CH3=
9 10
X
X
X
Sharif et al. Role of quaternary ammonium salts
12 ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17
Mono- and bis-reactive haloheterocyclic derivatives
Mono- and bis-reactive haloheterocyclic compounds
having monochlorotriazine as the reactive group have
also been used for the cationisation of cellulose. Although
these treatments enhanced the uptake of dye, there are
practical drawbacks to all these treatments, including hue
changes, poor penetration into the fibre [29] and light
fastness limitations [26].
Monofunctional cationic agents of monochlorotriazine
type (11) were evaluated on cotton yarn in the
production of differential dyeing effects. Yarn pretreated
with these cationic agents show better uptake of acid and
direct dyes than does untreated yarn [60]. The
stoichiometry of interaction of both acid and direct dyes
with cotton modified with a reactive cationic agent (12)
was examined. The results showed that the presence of
the cationic sites enhanced the amount of dye taken up
by diffuse adsorption [61]. Recent developments revealed
that cotton fabrics pretreated with mono- and bis-reactive
cationic agents (13 and 14) showed fairly high degrees of
exhaustion and fixation of direct dyes under neutral
conditions in the absence of salt. Improved fastness was
also achieved for this modified fibre when compared
with untreated samples. Results also indicated that
cotton pretreated with the bis-reactive cationic agent
showed higher degrees of dye exhaustion and fixation
relative to cotton pretreated with mono-reactive agent
(Table 5) [30].
Reactive cationic agents, phenylmonochlorotriazinyl
and epoxypropyl, were used for cotton pretreatment using
a pad–dry–curing technique. The dyeability of cationised
cotton fabrics using CI Acid Red 1 was found to be
dependent on the cationic agent concentration and the
appropriate mixture used [62]. More complex
multifunctional structures (15) have also been evaluated
by exhaust applications and these gave effective
enhancement of dye uptake [63].
Polymeric quaternary ammonium saltsMany cationic polymers have been applied to cellulose
with a view to enhance the uptake of anionic dyes and
it is considerably more difficult in these instances
Table 4 Fastness properties of direct dyes on untreated andtreated cotton fabrics
DyeCationicagenta
Cottonfabric
ISO C2S wash fastness
Changein colour
Stainingon cotton
CI Direct Red 80 I Without 4 2With 5 3–4
CI Direct Blue 71 I Without 4 2With 5 5
CI Direct Violet 66 I Without 4–5 4With 5 5
CI Direct Green 26 I Without 4–5 3–4With 5 5
a I, N-(3-chloro-2-hydroxypropyl)-N-methyl-N,N-diallyl ammoniump-toluenesulphonate
NH
N
N
N
Cl
NH
NEt
Et
R
11X
N
N
N
Cl
NH
NH
N
Et
Et
12
Cl
NH
N
N
N
Cl
NH
NEt
Et
Et
13I
N
NN
NN
N
NHHN
Cl Cl
HN
N EtEtEt
HN
NEt EtEt
14
II
Table 5 Fastness properties of direct dyes on untreated (C) andpretreated cotton fabrics with mono- (C-1) and bis-reactive (C-2)cationic agents
DyeCottonfabricb F (%)
Wash fastnessa
Lightfastness
Changein colour SC SW
CI DirectYellow 50
C 3–4 3–4 3 4–5C-1 32 4 4 4 5C-2 75 4–5 4–5 4–5 4–5
CI DirectOrange 61
C 3 3–4 3 3–4 4–5C-1 45 4 4 4 4–5C-2 83 4–5 4–5 4–5 4–5
CI DirectBlue 71
C 1 3 2 1–2 4C-1 28 4 4 3–4 4C-2 68 4 4 4 2
CI DirectGreen 26
C 2 3–4 3 3 4C-1 29 4–5 4–5 4–5 3–4C-2 58 4–5 4–5 4–5 2
a SC, staining on cotton; SW, staining on woolb C-1, cotton cationised with monochlorotriazine mono-reactive cationicagent; C-2, cotton cationised with bischlorotriazine bis-reactive cationicagent
N
NN
NN
N
NHHN
Cl Cl
HN
N MeMeMe
HN
N MeMeMe 15
CI CI
Sharif et al. Role of quaternary ammonium salts
ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17 13
to interpret the precise mechanism of the interactions
involved, apart from the obvious participation of
electrostatic forces between the dye anions and the basic
groups (often quaternary nitrogen atoms) in the polymer.
Polyamide-epichlorohydrin resin (Hercosett 125;
Hercules Powder Corpn), having azetidinium cation
(16) as the reactive group, was applied to cotton with a
view to producing a modified fibre suitable for the
absorption and fixation of reactive dyes at neutral pH in
the absence of salt. Selected highly reactive dyes gave
good colour yield and fixation but lower fixation values
were obtained when dyes of low reactivity were applied
to the pretreated cotton [64]. It was thought that better
fixation of both high and low reactivity dyes might be
achieved by introducing more highly nucleophilic sites
into the cotton. Incorporation of thiourea and
ethylenediamine into the polymer during the application
process has beneficial effects on the results obtained.
Thiourea addition inhibits the crosslinking of the resin,
leaving more nucleophilic NH groups as sites for dye
reaction [65]. Ethylenediamine promotes crosslinking of
the resin but itself provides extra NH groups as dye
reactive sites [66].
Derivatives of poly-epichlorohydrin, instead of
epichlorohydrin were prepared and used as new cationic
agents. Poly-epichlorohydrin dimethylamine derivative
(17) was applied to cotton under alkaline conditions by
the exhaustion method. Pretreatment of cotton with this
agent not only reduced the amount of salt needed, but
also increased the exhaustion efficiency and perspiration
fastness of direct dyes (BAY; Table 6) [2].
A commercial cationic fixing agent, Solfix E (modified
quaternary polyamine derivative; Ciba) was used to
pretreat cotton prior to dyeing with six commercial direct
dyes in the presence of electrolyte. Pretreatment
enhanced the colour strength but wash fastness was
similar to their untreated counterparts [67]. Pretreated
fabrics also gave improved printability with pigment and
anionic dyes. The prints obtained on cationised cotton
showed better overall fastness properties than prints
obtained on untreated cotton [68]. Three commercial
cationic fixing agents, namely Matexil FC-PN (a phenol
formaldehyde ammonium chloride condensate, ICI),
Matexil FC-ER (poly diallyldimethyl ammonium chloride;
18, ICI) and Solfix E (Ciba), originally marketed as
aftertreating agents for direct dyes, were used as
pretreatments for cotton modification. Pretreatment was
found to increase the colour strength of the dyeings when
dyeing had been carried out without electrolyte.
However, when electrolyte was used, the pretreated
samples exhibited generally lower colour strength than
the standard dyeings. The wash fastness of the dyeings
almost remained unaffected by pretreatment while light
fastness was slightly lowered [69]. The study of the effect
of different pretreatment agents on the uptake of 1:2
metal complex acid dyes by samples of cotton/polyamide
fabrics showed excellent dye uptake by the pretreated
samples compared with the untreated samples. The
pretreatment using Matexil FC-ER (18, ICI) or a
development cationic fixing agent gave the most uniform
results [70]. Homopolymer or copolymers of alkyl
diallylamine with epichlorohydrin have also been
reported to improve the wet fastness properties of anionic
dyes on textile fibres [1].
Aftertreatment of the dyeings produced on cellulosic
fibres, pretreated with fixing agent 18 and Fixogene CXF
(copolymer of dimethylamine and epichlorohydrin; 19,
ICI), with cationic polymers enhanced the light and wash
fastness of acid (Table 7) [71] and reactive dyes [72]. The
subsequent application of syntan (synthetic tanning
agent) to the aftertreated dyeings enhanced the
effectiveness of commercial cationic fixing agents 18 and
Fixogene CXF, in improving the wash fastness of three
commercial direct dyes (Ciba-Geigy) on cotton but the
effect of syntan was both dye and fixing agent specific
(Table 8) [4]. It has also been examined that wash
fastness was noticeably better when these fixing agents
were applied under alkaline conditions (Table 9) [73].
A new fibre modification technique based on a cationic
acrylic copolymer (polymer pL) has been established.
Pretreatment of cotton with this polymer increased both
the substantivity and reactivity of the fibre towards
reactive dyes, even under neutral or acidic conditions [74].
Recently, poly(vinylamine chloride) has been investigated
Table 6 Fastness properties of direct dyes on untreated andtreated (poly-epichlorohydrin dimethylamine) cotton
DyeCottonfabric K/S
Wash fastness
Lightfastness
Changein colour
Stainingon cotton
CI DirectBlue 78
Untreated 14.02 3–5 3 4Treated 14.26 3 3 3–5
CI DirectOrange 39
Untreated 11.58 3–5 3–5 4Treated 11.90 3 3 3–5
CI DirectBlue 86
Untreated 6.06 3–5 4–5 4Treated 11.74 2–5 4–5 3–5
NOH
16
CI
O
NH
MeMe
n
17
CI
NMe Me
n
18
CI
N(CH3)2OH
n
19
CI
Sharif et al. Role of quaternary ammonium salts
14 ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17
as a pretreatment for the salt-free dyeing of cotton with
reactive dyes. Dye fixation was found to be much higher
than by conventional dyeing without pretreatment, even in
the presence of a large amount of salt. Dyed cotton
pretreated with poly(vinylamine chloride) showed
excellent wash fastness and good rub fastness [75].
ConclusionDifferent quaternary ammonium salts have been applied
to the cellulosic fibres either as pretreatment or
aftertreatment to improve the fastness properties of
anionic dyes on cellulosic fibres. These treatments
Table 8 Fastness properties of direct dyes on cotton aftertreated with cationic fixing agents/syntan
Dye Aftertreatmentsb
K/S Wash fastnessa
Before wash After wash S C V
CI Direct Red 89 Nil 14.84 11.13 4 1 1–24% M FC-ER 14.21 12.75 4–5 2–3 34% M FC-ER/2% F AXF 13.77 13.34 4–5 2–3 34% F CXF 14.74 12.72 4–5 1–2 24% F CXF/2% F AXF 14.45 13.26 4–5 2 2–3
CI Direct Yellow 106 Nil 10.98 8.01 3 1 1–24% M FC-ER 10.49 9.94 4 2–3 34% M FC-ER/2% F AXF 10.31 10.11 4 3 3–44% F CXF 10.36 8.81 4 1–2 24% F CXF/2% F AXF 10.65 8.73 4 1–2 2
CI Direct Blue 85 Nil 17.06 12.42 3 1 1–24% M FC-ER 17.06 16.94 4–5 2–3 34% M FC-ER/2% F AXF 16.81 16.14 4–5 2–3 34% F CXF 16.08 15.79 4–5 1–2 24% F CXF/2% F AXF 16.81 15.96 4–5 2 2
a S, change in shade; C, staining of adjacent cotton; V, staining of adjacent viscoseb M, Matexil; F, Fixogene
Table 7 Fastness properties of acid dyes on cotton
Cottonsample
Pretreatmenta Aftertreatmentb Wash fastness
LightfastnessMaterial % Material %
Shadechange
Staining
C W N K/S
CI Acid Green 1061C 0.91.1 PT1 2 3 4–5 5.60 671.2 PT1 2 AT1 2 3–4 5 5.781.2 PT1 2 AT2 2 3–4 5 5.801.4 PT1 2 AT3 2 4 5 5.731.5 PT2 2 2 4–5 6.051.6 PT2 2 AT1 2 3–4 5 6.011.7 PT2 2 AT2 2 2–3 5 6.061.8 PT2 2 AT3 2 4–5 5 5.97
CI Acid Red 3152C.1 1.962.1.1 PTI 2 3 2–3 4 3 9.89 52.1.2 PTI 2 AT1 2 3–4 3 4–5 3–42.1.3 PTI 2 AT3 2 4 3 4–5 42.1.4 PT2 2 2–3 2–3 3–4 3 10.932.1.5 PT2 2 AT1 2 3–4 3 4 3–42.1.6 PT2 2 AT3 2 4 3–4 4–5 4
CI Acid Yellow 2352C.2 2.172.2.1 PT1 2 3 4–5 3–4 4 7.23 672.2.2 PT1 2 AT1 2 3–4 4–5 4 4–52.2.3 PT1 2 AT3 2 3–4 5 4–5 4–52.2.4 PT2 2 2 4–5 3 4 6.542.2.5 PT2 2 AT1 2 3–4 4–5 4 4–52.2.6 PT2 2 AT3 2 4 5 4–5 4–5
a PT1, Matexil FC-ER; PT2, Fixogene CXFb AT1, Matexil FC-ER; AT2, Fixogene CXF; AT3, copolymer of diallyldimethylammonium and diallyl-2-hydroxy-3-chloropropyl ammonium chloride
Sharif et al. Role of quaternary ammonium salts
ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17 15
enhanced the exhaustion, fixation and wet fastness
properties of anionic dyes on cellulose fibres.
References1. B Danner and J Heller, US5908474 (Clariant; 1999).2. T S Wu and K M Chen, J.S.D.C., 108 (1992) 388.3. M Kamel, M M Kamel, B M Youssef and G M Shokry,
J.S.D.C., 114 (1998) 101.4. S M Burkinshaw and G W Collins, J.S.D.C., 114 (1998) 12.5. A Carpmael, GB383634 (1932).6. G Cuvelier and D Wattiez, US3778225 (Institute Textile de
France; 1973).7. G E John, A P Henry and S W Clarence, GB437273 (ICI;
1935).8. A Carpmael, GB460961 (IG Farbenindustrie AG; 1937).9. R T Patton, J D Kitchens and D M Hall, US5006125 (Dow
Chemical; 1991).10. R Gipp, O Berenstecher and H Renziehausen, US4035145
(Bayer; 1977).11. E Beyerbach, J.S.D.C., 6 (1890) 119; J.S.D.C., 6 (1890) 98.12. I D Rattee, J.S.D.C., 101 (1985) 46.13. G H Hurst, J.S.D.C., 4 (1888) 14.14. R Gill, J.S.D.C., 71 (1955) 380.15. C C Wilcock and C P Tattersfield, J.S.D.C., 59 (1943) 119.16. A F Gortvai, US2973239 (United Merchants & Mfg; 1961).17. W Knobel, B Kissling and T Robinson, DE3105897 (Sandoz;
1982).18. S Valenti, C Muller, J Heller, B Kissling and T Robinson,
US4764585 (Sandoz; 1988).19. C C Cook, Rev. Prog. Color., 12 (1982) 73.20. M Hewson, J.S.D.C., 110 (1994) 140.21. Y Yang and E F Carman, Am. Dyestuff Rep., 85 (1996) 39.22. H T Lokhande and R S Kabra, Am. Dyestuff Rep., 87 (1998)
40.23. N Sekar, Colourage, 46 (1999) 29.24. GB1445317 (Bayer AG; 1976); J.S.D.C., 93 (1977) 66.25. M Kamel, M Kamel and M A El-Kashouti, Am. Dyestuff
Rep., 60 (March 1971) 33; (April 1971) 44.26. D M Lewis and X P Lei, Text. Chem. Colorist, 21 (1989) 23.27. D M Lewis and X P Lei, J.S.D.C., 107 (1991) 102.28. X P Lei and D M Lewis, Dyes Pigm., 16 (1991) 273.29. G E Evans, J Shore and C V Stead, J.S.D.C., 100 (1984) 304.30. Y A Youssef, J.S.D.C., 116 (2000) 316.
31. P J Hauser and S G Helfrich, US5667533 (Virkler; 1997).32. D M Hall, T M Leonard and C D Cofield, US5330541
(American Emulsions; 1994).33. P J Hauser and A H Tabba, Color. Technol., 117 (2001) 282.34. J Yao and D M Lewis, J.S.D.C., 116 (2000) 198.35. H Wang and D M Lewis, Color. Technol., 118 (2002) 159.36. S Zhang, W Ma, B Ju, N Dang, M Zhang, S Wu and J Yong,
Color. Technol., 121 (2005) 183.37. B M Youssef, M M Kamel and G M Shokry, Tinctoria, 94
(1997) 61.38. M M Kamel, B M Youssef and G M Shokry, Am. Dyestuff
Rep., 88 (1999) 28.39. B M Youssef, M M Kamel and E Allam, Am. Dyestuff Rep.,
87 (1998) 18.40. G Y Guo and Y L Chen, Am. Dyestuff Rep., 83 (1994) 58.41. J D McClure and P H Williams, GB1056587 (1967).42. R E Klem and J B Doughty, US4066673 (Westvaco Corp.,
1978).43. D L Roerden and L P Childers, US6123738 (Dow Chemical;
2000).44. H J H Van Der Mass, US4450295 (Zaltbommel Chem. Fab.;
1984).45. J L Deavenport and B I Lopez, US5463127 (Dow Chemical;
1995).46. M Rupin, Text. Chem. Colorist, 8 (1976) 139.47. H S Seong and S W Ko, J.S.D.C., 114 (1998) 124.48. D F Herbert, F A Barkhuysen and N J J Van Rensburg,
SAWTRI Tech. Rep., 524 (1983) 14.49. D F Herbert, F A Barkhuysen and N J J Van Rensburg,
SAWTRI Tech. Rep., 523 (1983) 24.50. P J Hauser and A H Tabba, AATCC Rev., 2 (2002) 36.51. S L Draper, K R Beck and C B Smith, AATCC Rev., 2 (2002)
24.52. K M Cannon and P J Hauser, AATCC Rev., 3 (2003) 21.53. S L Draper, K R Beck and C B Smith, AATCC Rev., 3 (2003)
51.54. M Kanik and P J Hauser, Color. Technol., 118 (2002) 300.55. M Kanik and P J Hauser, Text. Res. J., 74 (2004) 43.56. P J Hauser, AATCC Rev., 3 (2003) 25.57. M Kanik, P J Hauser and C L Parrillo, AATCC Rev., 4 (2004)
22.58. M Kanik and P J Hauser, Color. Technol., 119 (2003) 230.59. R Toepfl, US5147411 (Ciba; 1992).60. J A Clipson and G A F Roberts, J.S.D.C., 105 (1989) 158.
Table 9 Fastness properties of direct dyeings aftertreated with Fixogene CXF and Matexil FC-ER under neutral and alkaline conditions
Dye pH Cationic agent K/S
Colour fastness
Shade change
Staininga
C V
CI Direct Red 89 Nil 14.84 4 1 1–27 4% Fixogene CXF 14.74 4–5 1–2 2
11 4% Fixogene CXF 14.64 4–5 2 2–3Nil 14.84 4 1 1–2
7 4% Matexil FC-ER 14.21 4–5 2–3 311 4% Matexil FC-ER 13.18 4–5 3 3
CI Direct Yellow 106 Nil 10.98 3 1 1–27 4% Fixogene CXF 10.36 4 1–2 2
11 4% Fixogene CXF 10.57 4 2–3 3Nil 10.98 3 1 1–2
7 4% Matexil FC-ER 10.49 4 2–3 311 4% Matexil FC-ER 10.57 4 3–4 4
CI Direct Blue 85 Nil 17.06 3 1 1–27 4% Fixogene CXF 16.08 4–5 1–2 2
11 4% Fixogene CXF 16.68 4–5 2 3Nil 17.06 3 1 1–2
7 4% Matexil FC-ER 17.06 4–5 2–3 311 4% Matexil FC-ER 17.40 4–5 3 4
a C, cotton; V, viscose
Sharif et al. Role of quaternary ammonium salts
16 ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17
61. J A Clipson and G A F Roberts, J.S.D.C., 110 (1994) 69.62. R M El-Shishtawy, Y A Youssef, N S E Ahmed and A A
Monsa, Color. Technol., 120 (2004) 195.63. C V Stead, G E Evans and J Shore, GB2119367 (ICI;
1983).64. S M Burkinshaw, X P Lei and D M Lewis, J.S.D.C., 105
(1989) 391.65. S M Burkinshaw, X P Lei, D M Lewis, J R Easton, B Parton
and D A S Phillips, J.S.D.C., 106 (1990) 307.66. X P Lei and D M Lewis, J.S.D.C., 106 (1990) 352.67. B C Koo and S M Burkinshaw, Adv. Col. Sci. Technol., 1
(1998) 76.68. R M El-Shishtawy and S H Nassar, Color. Technol., 118
(2002) 115.
69. S M Burkinshaw and A Gotsopoulos, Dyes Pigm., 42 (1999)179.
70. R S Blackburn, S M Burkinshaw and R Gordon, Text. Chem.Colorist Am. Dyestuff Rep., 32 (2000) 44.
71. S M Burkinshaw, R Gordon and G W Collins, US6200354(ICI; 2001).
72. S M Burkinshaw, R Gordon and G W Collins,US2001054209 (2001).
73. R S Blackburn, S M Burkinshaw and G W Collins, J.S.D.C.,114 (1998) 317.
74. Y Cai, M T Pailthorpe and S K David, Text. Res. J., 69(1999) 440.
75. W Ma, S Zhang, B Tang and J Yang, Color. Technol., 121(2005) 193.
Sharif et al. Role of quaternary ammonium salts
ª 2007 The Authors. Journal compilation ª 2007 Society of Dyers and Colourists, Color. Technol., 123, 8–17 17