You are on page 1of 6

Coloration in the next century

David M Lewis

INTRODUCTION
Thinking about the year 2000 AD and beyond,
environmental requirements and related legislation will
be the major driving force for innovation in both the dye
manufacturing and dye application industries. Many
textile companies are taking a stand against using dyes or
dyeing systems containing heavy metals, and a
particularly affected area is that of polyamide fibres. In the
case of wool and nylon, 1:2 metal-complex dyes are valued
for their excellent wet and light fastness. If their usage is
voluntarily restricted, replacement dyes for wool could
come from the available reactive dye ranges, and in the
case of nylon and s i k from the further development of
reactive disperse dyes. In the early 1970s ICI had such a
range (the kocinyls), but their reactivity was low under
neutral application conditions.
It is most unlikely that cotton will lose its position as the
worlds premier fibre, in terms of volume, and thus
research efforts must be redoubled to improve the
environmental impact of dyes for cellulosic fibres and the
respective dyeing processes. Current dyeing processes for
these fibres are, to varying degrees, environmentally
suspect; undoubtedly one of the major problems, colour
in effluent, comes from the application of reactive and
sulphur dyes. A further problem arises from the use of
high electrolyte concentrations, especially in reactive
dyeing. It is therefore of paramount importance that
solutions to these problems are continually sought. In this
context, profitable research directions include novel (nonhydrolysing) reactive systems, crosslinkable dyes and fibre
modification. The latter approach may be more attractive
for the recently launched solvent-spun cellulosic fibres
(so-called IyoceU fibres), since there exists the possibility
for additives to be included in the solvent phase or in the
aqueous precipitation baths where the fibres are in an
extremely accessible state.
Microfibres have gained some popularity in specific
outlets. For the next generation of microfibre textiles to be
successful, there is a need to process blends of nylon and
polyester microfibres to develop novel fabrics.
Unfortunately, non-reactive disperse dyes give poor wetfastness properties on the nylon component and a
reappraisal of reactive disperse dyes again appears vital.
Much research effort has already gone into reactive
disperse dyes, especially for the cottodpolyester blend
market. A single dye for each fibre in these blends remains
a very important research target.
In terms of new chromophore research there may be
new pressures to move away from azo dyes, and should

this prove to be commercially important the pioneering


work on benzodifuranone disperse dyes will be
invaluable. Methods to apply such disperse dyes to
hydrophilic fibres could then be demanded.
The following four research and development themes
will continue to challenge the colour chemist and process
scientist and technologist well into the next century:
(a) Necessary responses to environmental pressures
@) Innovations in coloration demanded by new fibres
and fabrics
(c) Potential for new chromophores
(d) Improved and novel processes produced in response
to global economicpressures.

ENVIRONMENTAL PRESSURES
The pressures on the coloration industry, and for that
matter the whole chemical industry, from environmentalists are a disconcerting mix of good sense, passion
and in some cases downright nonsense. Out of this heady
brew various legislative requirements have emerged with
increasing regularity. In response the industry has been,
and is being, forced to become increasingly innovative in
order to develop new products and practices that are
more environmentally friendly than existing ones. In this
section some of the more important problem areas will be
highlighted and solutions suggested or reported.

Mordant and metal-complex dyes


The only important mordant dyes are the chrome dyes for
wool, almost universally applied by the afterchrome
process. Despite numerous predictions of the demise of
these dyes over the last 30 years, it is clear that they are still
important in the market place due to their extraordinary
fastness properties and economy, especially in full shades
of navy and black [l].Chromium in aqueous discharges is
increasingly seen as a severe environmental problem, and
draft regulations indicate that very little chrome in
dyehouse effluents will be tolerated, as little as 100 parts
per billion [2]. It could be argued that this is unrealistic. For
example, Hilden has argued that consumption of the
trivalent chromium cation of 10 mg per day in food is
normal, and necessary for good health, and the natural
content of Cr(rn) in soil is of the order of 200 mg per kg [3].
However, it is important to concede that the hexavalent
form of chromium, as present in bichromate salts, is highly
toxic, both to man and fish life, and steps should be taken
to eliminate it from the dyeing process. It is for this reason
that research programmes have been camed out, aimed at

REV.PROG.
COLORATION
VOLUME
29 1999 23

replacing the toxic bichromate used in current industrial


chrome dyeing procedures with fibre substantive Cr(rn)/
organic acid anionic complexes [MI.If this research is
successful it will allow the wool dyer to continue to use
this valuable class of dye without employing hazardous
bichromate salts. An additional advantage lies in the fact
that the oxidative damage to wool associated with the use
of bichromate salts wilI be greatly reduced.
Clearly other workers see the future demise of chrome
dyes for wool as an opportunity for reactive dyes [7].
Unfortunately, in deep shades of navy and black most
wool reactive dyes do not give sufficient covalent dyefibre fixation to allow the production of these shades in
equivalent fastness. Thus extensive alkaline clearing of
unfixed dye is necessary, which has the potential to
damage the fibre. It is important, therefore, to optimise the
reactive dyeing of wool in deep shades (>4% owf dye), by
researching the various processing parameters that
influence the overall degree of dye-fibre covalent
bonding. Total fixation efficiencies of greater than 95%
need to be targeted. The need for this research has been
greatly highhghted by Marks and Spencer, which recently
announced that it intended to sell textile articles dyed only
with heavy-metal-freedyes by the year 2OOO.
Metal-complex dyes, important for wool and nylon,
face pressures similar to those affecting chrome dyes.
Many large US mills have already banned their use and
consequently it is becoming difficult to obtain muted
shades of the required light fastness and levelness,
especially on nylon. Reactive dyes may offer a solution to
the wet-fastness problems but are unlikely to reach the
light-fastnessstandards so readily attained by dyeing with
metal-complex dyes. In this respect a re-examination of
vat dyes for use on nylon fibres may prove worthwhile.
Improved reactive dyeing systems for cellulosic fibres
Hobbs has observed that dyeing cellulosic fibres with
reactive dyes is a major contributor to the problem of
coloured effluents [S]. A further important problem is the
requirement, when dyeing cellulosic fibres with anionic
reactive dyes, to use large amounts of electrolyte (common
salt or Glauber's salt) to suppress the negative charge at
the fibre surface.
These problems have focussed the research and
development activities of a number of research groups,
including those in university and dye manufacturing
laboratories. As a result of these activities DyStar has
launched the Remazol EF (environmentally friendly)
range of high substantivity multifunctional reactive dyes,
and more recently Ciba has introduced the Cibacron LS
(low salt) range. These are just two examples of the
changes that are occuning in reactive dye technology in
response to environmental pressures. All dye manufacturers are tending to offer multifunctional reactive dyes
as a means of securing the highest possible fixation
efficiencies, thus reducing the problem of colour in
effluent.
An alternative approach to improving the reactive

24 REV.PROG.COLORATION
VOLUME29 1999

dyeing of cellulosic fibres has been developed [9,10]. This


research has been aimed incorporating nucleophilic
amino residues in the fibre in place of the less reactive
hydroxyl groups. Such modified fibres could be dyed at
pH 7 with most reactive dyes, in the absence of salt, giving
high colour yields with very high fixation.
A further way of thinking about this problem is to turn
the problem on its head by making the fibre reactive and
the dye nucleophilic [ll].
Such procedures will only find commercial success if
the products are cheap and of low toxicity, and if methods
of applying the fibre-mo-g
agent can be developed
that fit readily into current dyehouse practice. However,
chemical companies are already selling reactive aminating
compounds to achieve the above objectives. In the USA
the commercial development of the Virkler No-Salt
system is worthy of note. The major problem in ensuring
fibre modification is successful in mill practice is the lack of
substantivityof the m m g agents, which restricts their
application to padding processes. A recent publication has
indicated that a fibre-substantive, cellulose-cationisation
agent is now available as Tscamin ECE (Vutz-Inotex)[12].
Dyeing in nonaqueous systems
Bearing in mind the increasing costs of using and
disposing of water, a particular research goal has been to
develop nonaqueous dyeing systems. Such systems
would produce an effluent that would not be discharged
into the aqueous environment. Solvent recovery would be
necessary and this would result in a dry solid waste.
However, most of the organic solvent systems evaluated
for solvent dyeing were based on chlorinated hydrocarbons, especially perchloroethylene (131, which are now
subject to controls. Equally, solvent recovery can never be
100%efficient, thus giving rise to air pollution problems.
A great deal of interest was thus reawakened with the
ITMA 1991 demonstration by Joseph Jasper, Ciba and the
research group at the German North West Textile Research
Institute in Krefeld, which revealed a new method of
dyeing from an environmentallysafe solvent,'supercritical
carbon dioxide. In this cooperative research, Joseph Jasper
GmbH & Co. was the machine builder and Ciba the
manufacturer of suitable disperse dyes [14]. The first
laboratory pilot-scale studies were initiated at the Krefeld
Institute [15,16).
As a solvent, supercritical carbon dioxide shows ideal
properties in that it is cheap, recycleable and extremely
safe. The carbon dioxide that is used in such processes is
obtained as a by-product from fermentation and ammonia
synthesis, and does not therefore add to the greenhouse
effect. The disadvantage of processing in supercritical
fluids is the high pressure involved, which requires special
vessel engineering.
Before discussing the dyeing process it would be useful
to give a brief description of the properties of supercritical
fluids. In order to understand how gases and liquids are
affected by changes in pressure and temperature it is
useful to study a typical phase diagram. Figure 1illustrates

100
._ _

It is doubtful whether such technology can make a full


breakthrough unless it could be applied to cellulosic fibres.
Thus Saus ef al. evaluated different carbodiimide and resin
pretreatments designed to make the cellulosic fibre more
hydrophobic, and hence dyeable with disperse dyes, in
the supercritical carbon dioxide system [18]. Clearly there
are possibilities to develop this area, but a feasible system
will probably require cellulose modification and disperse
dyeing in the Same system.

80

Colour in effluent and water recycling


Although dyes are in the main of very low toxicity to fish
life [19], increasingly the dyeing industry is under severe
pressure to reduce colour discharge. It has been estimated
that some 450 OOO tonnes of organic dyes are synthesised
world wide, and of this production 9000 tonnes are
wasted in manufacture and 41 O00 tonnes wasted in
application.In the UK the Environment Agency is actively
pursuing the setting of standards to control colour
pollution of river water.
The wool and acrylic dyer tends to be in a happier
situation than the dyer of other fibres since high
exhaustion (over 90%)is normal when applying anionic
dyes to wool and cationic dyes to acrylics. Table 1
summarises the extent to which dyes are lost in dyebath
exhaust and wash liquors according to data collected by
Laing [a].
The biggest problems relate to the dyeing of
cotton with reactive and sulphur dyes. It is likely therefore
that the dyeing industry will move to total reuse of its
water by a process of capital investment in a number of
readily available technologies, the most important of
which include the following:
(a) Membrane filtration [21]
(b) Dye removal by 'clay' based absorbents [22]
(c) Chemical decolorisation, e.g. ozonation [a].

Liquid

t
a

tI I<;-k
-yint

point

lmO
0.1

/I

-80

-40

Vapour
I

40

Temp., OC

Figure 1 Phase diagram for carbon dioxide

the phase relationships of carbon dioxide, indicating


regions in which it exists as solid, liquid or gas. The curves
represent interfaces between phases, while at the triple
point (at around 60 "C and 0.5 MPa pressure) all three
phases may coexist. Above the triple point, an increase in
temperature drives liquid into the vapour phase, whilst an
increase in pressure drives vapour back into liquid. This
situation pertains until the critical point is reached; at this
point if the gas is heated above its critical temperature it
cannot be liquified, however high the applied pressure. In
the case of carbon dioxide, the critical point is at 31 "C and
a pressure of 7.3 MPa.
Above their critical temperature, gases retain the free
mobility of the gaseous state but, with increasingpressure,
density will increase towards that of a liquid. Such a
highly compressed gas is termed a superaitical fluid and
this medium combines the valuable properties of both
liquid and gas. Solvating power is proportional to density
whilst viscosity remains comparable to a normal gas. The
'fluid thus has remarkable penetration properties. Key to
the dyeing process is the fact that solvating power is
increased with increasing density. Thus increasing
pressure has a great effect on increasing the amount of
disperse dye dissolved in supercritical carbon dioxide.
Two machines are currently available from Joseph
Jasper and Uhde for dyeing polyester yarn in package
form [17]. A typical dyeing procedure may be summarised:
(a) Set up the bath with goods and a charge of pure
disperse dye
(b) Run in superaitical carbon dioxide
(c) Raise the temperature and pressure to 130 "C and 30

MPa
(d) Gradually reduce the pressure in order to reduce the
solubility of the disperse dye in the supercritical fluid
(e) Recover the carbon dioxide.

In the above procedure, which lasts about 3045 min, the


dveinn levelness is controlled bv the pressure reduction
program; virtually 100%dye uptake miy be obtained and
the need for reduction clearing is eliminated. Currently it
is claimed that the system is suitable for dyeing polyester,
aramid and polypropylene fibres, special dialkylaminoanthraquinone dyes being necessary for the latter.
*

Of these techniques membrane filtration is widely used


already by dye manufacturers to separate dyes in high
purity from reaction streams.
Total recycling of water is clearly an achievable goal but
a harder objective is the recovery and reuse of unused
dye. Undoubtedly with the application of colour

Table 1 Extent to which dyes are lost in


exhaust and wash liquors
Dye
class
Direct
_.
Acid
Basic
Metalcomplex
Sulphur
Reactive
Disperse
Vat
~

Amount of dye charged


lost in effluent (%)
5-20
- __

7-20
2- 3
2- 5
30-40

2040
1-20

5-20

REV.PROG.
COLORATION
VOLUME
29 1999 25

chemistry and chemical engineering principles even this


latter objective is likely to be normal practice within ten
years. It should be noted that in the case of indigo, systems
are already commercially available to recover and reuse
dye (suppliers in the USA include Romicon and DorrOliver).

Absorbable organohalogen legislation


Special attention is also likely to be required when
discharging compounds containing absorbable organohalogens (so-called AOX). The concept of AOX has arisen
from a German drinking water directive @LN 38 409 414,
1987). Consent limits as low as 2 m@ are awaited.
Products used by the dyer and printer that fall into this
category are the insectproofing agents applied to wool in
dyeing, some types of carriers for dyeing polyester with
disperse dyes, certain chromophores themselves and
some classes of reactive dyes. This type of foreseeable
legislation will therefore direct the colour chemist to
develop new systems that will reduce these discharges to
the allowable limits. These implications are indeed farreaching. For example, in the case of dyeing cellulosic
fibres with reactive dyes, the demand for achieving
virtually 100%dye uptake and covalent bonding is urgent.
Research is therefore required to develop innovative
reactive systems or fibre pretreatments that solve the
problem of existing reactive dyes. Many reactive dyes fall
into the AOX category and unless efforts are directed at
replacing halogen groups with other leaving groups it will
be necessary to develop aftertreatments that effectively
liberate any halogen from unfixed dye. Interestingly
organofluorine compounds do not fit into the AOX
classification since the fluoride ion liberated in the test
protocol as soluble silver fluoride is not detected. Dye
makers are thus likely to concentrate on vinylsulphone
and fluoroheterocycle-containingreactive dyes.
Shrinkproofing wool by chlorine treatments is widely
practised but can lead to AOX levels of 1 @, which can
appear in effluents from subsequent dyeing processes.
Alternative processes to replace chlorine are currently
being researched, the most promising being those based
on permonosulphuricacid.

NEW FIBRES AND FABRICS


Many fibre manufacturing companies are looking again at
environmentally friendlier ways of spinning regenerated
cellulose. Currently the method of dissolving cellulose in
N-methylmorpholine oxide and spinning into a suitable
aqueous coagulating bath is gaining momentum. The
market leader is Courtaulds (now Acordis) with Tencel.
This new cellulose fibre offers the dyer and fibre producer
unique opportunities; available information indicates that
Tencel is more readily dyed than cotton but suffers from
fibrillation. This effect can be used to advantage in the
development of 'peach-skin' fabrics. The generic name for
these fibres is lyocell and the market is being developed by
Acordis and Lenzing. Antifibrillation treatments to

26 REV.PROG.COLORATION
VOLUME
29 1999

produce clear surface fabrics have been produced, based


on the use of reactive crosslinking agents.
It is also a realistic expectation that the Tencel fibre can
be treated with fibre-modifying agents, possibly in the
'never-dried state, to improve subsequent dyeability,
possibly producing fibres that are dyeable without salt,
even in deep shades.
Microfibres have become established as the purely
synthetic fibre route to high-comfort fabrics. The second
wave of these fabrics is likely to be a polyesterhylon
mixture but the available technology to enable these fibres
to be dyed or printed to a sufficiently high standard of wet
fastness is of questionable quality. The major problem is
that currently available disperse dyes will not reserve
nylon and the subsequent dyeing has inadequate wet
fastness. Thus the development of reactive disperse dyes
is an important issue. An excellent review of work in this
field up until 1980 has been published in Japan [XI.The
disperse reactive dye concept was mentioned earlier but
with a different emphasis, that of replacing metal-complex
dyes for nylon. Since the demand is coming from two
different directions, its importance is enhanced.
Introducing minor chemical changes will lead to new
polyester fibres. For example, Shell has recently introduced a new polyester polymer, coded PES 3GT In this
polymer the usual ethylene glycol is replaced by butylene
glycol (1,3dihydroxypropane). Fibres melt-spun from the
polymer prepared by condensing butylene glycol with
terephthalic acid show the following differences
compared with normal ethylene glycolherephthalic acid
polyester:
(a) Improved recovery from deformation (similar to
nylon fibres)
(b) Dyeability with disperse dyes at 100 "C (and hence
greater compatibilitywith spandex fibres)
(c) Reduced wet-fastness properties but still acceptable
for carpets and most apparel requirements
(d) Biodegradability.
Dupont in collaboration with Genencor International has
researched biotechnological synthetic routes to the 3GT
butylene glycol monomer, by the bacterial fermentation of
corn starch. This single-step approach will greatly
cheapen the cost of the monomer and is seen to be a more
environmentallyfriendly option for producing at least one
of the components of an important synthetic fibre.
The biotechnology theme is also being developed by
scientists in the US Army Research Centre and at
Dupont, to develop spider silk in industrial quantities
[=I. The Florida golden orb spider produces a particular
dragline fibre of a remarkable balance of strength,
toughness and stiffness, resulting in the dissipation, as
heat, of 70% of the energy of impact from flying prey
hitting the web. This protein fibre is therefore being
bioengineered using standard gene expression techniques. Apparel fabrics and high-performance technical
textiles of the future could thus be protein-based and
dyed in the manner of silk or wool.

THE POTENTIAL FOR NEW


CHROMOPHORES

NOVEL AND IMPROVEDPROCESSES

New chromophore development has had notable


successes recently. Benzodifuranone chromophores for
brilliant red disperse dyes have been pioneered by Zeneca
Colours (now BASF) but are unlikely to find application as
the basis of water-soluble dyes for cotton and wool, since
the lactone ring in the chromophore is readily hydrolysed
[%I. In fact this latter aspect is utilised to advantage when
applying this type of disperse dye to polyester, since the
dyeings produced are readily alkali cleared, because the
chromophore is discharged by alkali to a colourless
compound. Undoubtedly it would be possible to develop
yellows and blues based on benzo- or naphthodifuranone chemistry and it is interesting to speculate that
should azo dyes be limited by legislation, then the
industry has the potential to develop a new class of
chromophore based only on carbon, hydrogen and
oxygen. The structure of the benzodifuranone
chromophore is exemplified in Figure 2.
The brilliant red diphenyldiketopyrrolopyrrole was
developed by Iqbal at Ciba and has resulted in widespread
usage. The pigmentary properties of this chromophoreare
first class and has earned it the nickname 'phthalocyanine
red [27,28].The structure is shown in Figure 3. This fairly
recent discovery and the bringing to market of these
brilliant red chromophores must surely indicate that
innovations in colour chemistry are still possible, and that
future research may unlock new treasures. There is clearly
a need to develop unmetallised turquoise blue chromophores of lower molecular size than copper phthalocyanine. Equally, intense, non-azo blues of the brilliance
normally achieved with anthraquinone chemistry would
be a market winner.

Electron beam (EB) dye fixation


Ciba has evaluated a series of dyes that contain polymerisable vinyl groups; these are available in test
quantities as Cibacron EB dyes and are suitable for printing [29]. Following printing with a paste containing a dye
monomer and a specially selected cationic monomer,
fixation is achieved by electron beam irradiation. This
promotes copolymerisation and network formation with
other polyvinyl monomers added to the original print
paste. The target of 100% dye utilisation is approached
and minimal washing-off is required.
Bubble-jetprinting
Bubble-jet printing is now an exciting reality. Recently
Canon has launched a new machine for the textile
industry that prints fabric at 1 d m i n to a maximum width
of 1.65 m. The cost of the machine is about E300 O00 and
inks are available for cotton, silk, viscose, nylon, wool and
polyester. Fixation is carried out by normal steaming or
Thermosol techniques. Bubble-jet printing is capable of
taking images from a computer screen and directly transposing them to the fabric. Huge advantages in eliminating
screen production, screen washing and time savings in
changing design are immediately apparent. Print quality
is excellent, the detail level claimed being 0.08mm (screen
printing typically 0.2 mm) and overlap precision 0.04 nun
(screen printing about 0.3 mm). In terms of ink-drop
delivery, a resolution of 360 dots per inch is claimed.
A universal dye for all fibres

Figure 2 Typical benzodifuranone dye

It would clearly be a great advantage for the industry to be


able to dye all fibres with the same type of dye and some
research has been ongoing in this area using disperse
dyes. If cottordpolyesteror wooVpolyesterblends are to be
dyed with disperse dyes then it is important that the
natural fibre components are modified with a suitable
auxiliary, which covalently incorporates a disperse dye
site. It has been found that suitable fibre reactive
auxiliaries can be prepared that may be included in
disperse dyebaths to selectively m o w the natural fibres
[30-32]. In the case of sulphatoethylsulphonederivatives,
Lewis and WDI claimed a type of water-soluble arylating
agent (Figure4) "1.

Figure 3 Diphenyldiketopyrrolopyrolle (DPP)

Figure 4 Typical structure of water-soluble arylating agent [30]

REV.PROG.
COLORATION
VOLUME
29 1999 27

If the above compound were included in a wool


dyebath containing commercially available disperse dye
and the dyebath set at pH 6.5, then the wool could be
satisfactorily dyed with the disperse dye on raising to the
boil and boiling for an hour. At this pH the sulphatoethylsulphone derivative is absorbed as a colourless acid
dye, while at high temperatures p-elimination to the
vinylsulphone derivative occurs and the agent then reacts
with the fibre to covalently incorporate additional aryl
groups. The presence of these additional aryl groups
enhance disperse dye substantivity by providing sites that
interact with aryl residues in the disperse dye.
Hydrophobic and K-K interactions are especially relevant
in this context [33].

CONCLUSIONS
In the early decades of the third millenium, innovation
and developments in colour chemistry and dyeing will
allow the colorist to meet ever-increasing environmental
restrictions, to produce novel effects and also to reduce
processing costs. Total recycling of dyehouse water is an
inexorable trend and the technology is already available to
achieve this. Novel chromophores are a real possibility.
Reactive disperse dyes appear to be necessary to achieve
progress with dyeing microfibre blends of polyester and
nylon, as well as to satisfy demands for improved wet
fastness on nylon without the problem of barre.
New fibres will be developed. Biotechnology will play
an innovative role both in providing feedstock for
polyester fibres and by allowing the chemical industry to
produce in commercial quantities, through gene
expression, some of nature's wonder fibres.

REFERENCES
1.
2.
3.
4.
5.

PA Duffield in Wwl dyeing, Ed. D M Lewis (Bradford:S I X , 1992).

off I. Eur. Comm., C351(31 Dec 1985) (COM (85)733 final).

J Hilden, Proc.IFATCC Symposium,Wien (1996) 183.


DMLewisandGYan,I.S.D.C.,110(1994)281.
D M Lewis and G Yan, Proc. Int. Wool Res. Conf., Biella, Vol. 3
(1995)39.

6. J Xing and M J Pailthorpe, Text. Res. I., 63 (1995) 70.

7. R Bauhofer and K Hanneman, Proc. Int. Wool Res. Conf., BieUa,


Vol. 1 (1995)%.

28 REV.PROC.COLORATION
VOLUME
29 1999

8. S J Hobbs, UK dye production and use in the textile industry, Dept. of


Environment, Environmental Industry Category Document
(1988).
9. DMLewisandX-PLei,I.S.D.C.,107(1991)102.
10. D M Lewis, I.S.D.C.,109 (1993) 359.
11. D M Lewis and X-P Lei, AATCC Internat. Conf. and Exhib.,
Atlanta, Book of Papers (1992)259.
12. D Dvorsky, Proc. IFATCC Conf., Wien (1995)204.
13. B Milicevic, Text. Res. I., 39 (1%9) 677.
14. D Werthemann, W Schlenker and U Beines, Textil Praxis, 46 (1991)
932.
15. W Saus, D Knittel and E Schollmeyer,Text. Res. I., 63 (1993)135.
16. E SchoUmeyer, D Knittel, H-J Buschmann, G M Schneider and K
Ibulakis, German P 3 906 72A A l .
17. E Bach, E Cleve and E Schollmeyer, Proc. Int. Symp. Text. Dyeing
and Finishing, Wakayama (1998) 116.
18. W Saw, S Hoger, D Knittel and E SchoUmeyer, Textilveredlung, 28
(1993)38.
19. I Holme in Chemistry and technology of organic dyes, Ed. J Griffiths
(London: SCI, 1964) 111.
20. I G Laing, Rat. Prog. Col., 21 (1991) 56.
21. J Elliott in Environmental chemistry of dyes and pigments, Ed. A Reife
and H S Freeman (New York J Wdey, 1996).
22. K R F Cockett, S D C lecture (1995).
23. M Matsui in Environmental chemistry of dyes and pigments, Ed. A
Reife and H S Freeman (New York: J Wdey, 1996) 43.
24. T Niwa, K Himeno and T Hihara, Senshoku Kogyo, 30 (1995) 496.
25. D L Kaplan, P M Fossey, P M CunnitT, C Mello, S Arcidiacono, K
McGrath, K Senecal, J Prince and D L Vezie, Proc.Int. Symp. Fibre
Sci. and Technol., Yokohama (1994) 157.
26. C W Greenhalgh, J L Carey and D F Newton, Dyes and Pipienfs, 1
(1980)103.
27. A Iqbal, Lecture, Colorchem %, Spinderlov Myln, Czech Republic.
28. A Iqbal, L Cassar and Ciba-Geigy, USP 4 415 685 (1983).
29. K Fritzsche, Lecture, Schloss-Elmau Conf. (1994).
30. D M Lewis and WDI, USP 4 563 189 (1986).
31. P A Broadbent, X-P Lei and D M Lewis in Cellulosics: mafcrinls for
selective separations and other technologies (Chichester: Ellis
Horwood, 1993) 297.
32. P A Broadbent and D M Lewis, Proc. IFATCC Conf., Wien (1996)
107.
33. D M Lewis, Int. I. Cosmetic Sci., 18 (1996) 123.

You might also like