Also welcomed were Honorary Secretaries from most of

the Regions and Student Sections, some members of the

staff of Perkin House, ably led by the Chief Executive and
General Secretary, Dr M Tordoff, and representatives from
sister societies, including: M r J L Turner and M r C B Abnett
(a Past Prime Warden and Assistant Clerk respectively of
the Worshipful Company of Dyers), M r D J Holborow (Master of the Worshipful Company of Feltmakers), M r D H Tuck
(President of the Society of Leather Technologists and
Chemists), M r W Sondhelm (Vice-president of the Textile
Institute), M r G Gordon (President o f the Guild of Technical
Dyers) and M r K McLaren (Chairman of the Colour Group).
The Society was also pleased to welcome several leading
figures from the worlds of education, research, dye manufacturing and textile manufacturing amongst its guests.
Mr Parkinson said that in such a gathering of almost 400
people time did not permit the mention o f all the guests by
name. (Oh, please do, shouted someone entering a little
overzealously into the spirit of the occasion.) But to all the
Societys guests, those who had travelled from overseas or
from distant parts of the UK and those who had travelled
from the Manchester area, was bidden a hearty welcome.
Members of the Society were asked to drink a toast to The
Guests.
In response Sir William Downward, Lord Lieutenant of
Greater Manchester, said that he was relieved to see that so
many people had turned up. He concluded that Society
members were either enthusiastic, generous o r rich peo-

ple. Whichever it was, he was grateful for the splendid

dinner he had enjoyed.
A few people, he said, were disappointed that he had not
come in his official uniform, which was based, he thought,
o n that worn by men o n duty outside the major picture
palaces. Uniforms such as this took some getting used to,
and Sir William described i n detail h o w t o get in and out of a
car whilst encumbered with a ceremonial sword and spurs,
without any lasting self-inflicted injury.
Greater Manchester, he said, was a relatively new
county; some parts of it had even formerly belonged to
Yorkshire. However, a change from white rose to red had
not been universally unpopular. One old lady who had
become a Greater Mancunian without moving had expressed a preference for her new county because the winters were warmer.
Nevertheless, rivalry between the two sides of the Pennines was strong, and curiously exclusive of outsiders. He
told the (possibly) apocryphal tale of the visiting Southerner at an Old Trafford Roses match w ho was clapping the
batting enthusiastically and interjecting an occasional Well
played sir! in cultured Home Counties tones. Eventually a
disgruntled local turned and silenced the unfortunate
intruder with a curt Shurrup! Its nowt tdo wi thee.
In thanking members of the Society for their hospitality,
Sir William wished the Society well for its Centenary and
expressed the wish for continuing good relations between
it and the industry it served.

The Structure and Properties of Disperse

Dyes in Polyester Coloration
J F Dawson
Yorkshire Chemicals plc
Kirkstall Road
LeedsLS3 1LL
Presented to the Societys 1eicester Student Section on
the 29 October 1980, to a joint meeting of the Societys
West Riding Region and Leeds Student Section on 25
February 1982 and to the Societys Scottish Region on 2
March 1982.

John Dawson was educatedat Prince Henrys GrammarSchool, Otley, and

the University of Leeds. He graduated from the Department of Colour
Chemistry and Dyeing in 7961 before taking up an appointment as a
research chemist with the then Yorkshire Dyeware & Chemical Co. Ltd,
working primarily on the synthesis of new disperse and cationic dyes. He
was appointed dye research manager in 1969and elected to the board in
1976. He is now technical director of Yorkshire Chemicals plc, and also a
member of the Societys Publications Committee.

INTRODUCTION
Going backto first principles, the Society defines a disperse
dye as a substantially water-insoluble dye having substantivity for one or more hydrophobic fibres, e.g. cellulose
acetate, and usually applied from a fine aqueous dispersion [I 1.
The mention of cellulose acetate should remind us that
this was the fibre that established disperse dyes as a class
and this part of the story is well described in the 13th John
Mercer Lecture entitled The Disperse Dyes - Their
Development and Application given by R K Fourness in
1956121. It is interesting t o note that at the time of this
lecture polyester fibres were still in their infancy- the first
sale of terylene filament yarn is said to have taken place on
4 October 1948 [3]. There were some problems initially with
the coloration of this new fibre [41, but the use of carriers at
the boil and the subsequent exploitation of hightemperature dyeing eventually overcame them. To quote
Fourness, without disperse dyes and the dispersion process certain man-made prodigies would have been stillborn or at best remained Peter Pans 121. Whilst this was
certainly true in the case of both cellulose acetate and
polyester fibres, there is n o doubt that the commercialisation of polyester fibres also proved to be a landmark for
disperse dyes and their manufacturers.
Information is available t o compare the world production
JSDC Volume 99 JulyIAugust 1983 183

of polyester and cellulose acetate fibres since the former

was launched [5], as shown in Figure 1.

Figure 1

- World fibre production (7950-1980)

Cellulose acetate production has remained comparatively static whilst polyester fibre production, which was
still relatively small at the time of the 13th John Mercer
Lecture in 1956, has since undergone a period of phenomenal growth. It is fair t o assume that this increase in fibre
production has been followed by a similar trend in dye
manufacture and use; hence the dye makers research work
has been primarily directed towards dyes for polyester
fibre. In any case, the dyes used for the coloration of cellulose acetate are in many cases well established and have
adequate properties for the fibres intended use, with the
possible exception of wet fastness.

APPLICATION TECHNIQUES AND FASTNESS PROPERTIES ON POLYESTER FIBRES

Application Techniques
Six different methods of applying disperse dyes have been
developed since the introduction of polyester fibres.
1. Batchwise dyeing at the boil in the presence of a carrier
is sometimes used for delicate fabrics, polyester/wool
blends, etc.
2. Batchwise dyeing at 120-135C in pressurised vessels
was initially used for dubbing and yarn. Compared with
carrier dyeing this technique gave better exhaustion and
often improved fastness to light (as there were no
residual carrier problems), rubbing and perspiration.
Fabrics were originally beam dyed, but jets are n o w
more commonly used.
3. Thermofixation techniques at 190-220C are used for
the continuous processing of certain types of fabric.
4. Transfer printing, usually at 210C for 30 s, is an important recent development.
5. Solvent dyeing techniques are available but are not
popular despite the development of special dye ranges
and appropriate application methods.
6. Printing and continuous dyeing processes are available
for polyester/cotton blends using specialist dyes and
application techniques such as the Dybln (DUP), Cellestren (BASF) and Dispersol PC (ICI) ranges.
Dyeing and Fastness Properties
Before considering specific examples of the relationships
between disperse dye structure, and dyeing behaviour and
fastness properties, some general points are worthy of
note.
1. The use of higher dyeing temperatures for polyester
fibres compared with those used for cellulose acetate
has made possible the use of dyes of higher molecular
weight, the so-called high-energy dyes. This has had the
184 JSDC Volume 99 July/August 1983

effect of opening up many more structural possibilities

for dye synthesis.
2. The uptake of disperse dyes by synthetic-polymer fibres
takes place by progressive adsorption of the small concentration of dye in solution always present in an aqueous dispersion. The substantivity of the dye, which
determines its tendency to partition in favour of the fibre
depends o n factors such as molecular size, geometry
and, in particular, the polarity of the molecule. It is quite
possible for a small variation in molecular structure to
produce a dye of greater substantivity for cellulose acetate than for polyester, and vice versa.
3. Many disperse dyes give slightly, or sometimes markedly, different hues on nylon and on cellulose acetate
fibres. This is no problem on polyester, a given dye
generally yielding similar hues on polyester and cellulose acetate.
4. The light fading of dyes involves a complex series of
processes, which are only understood i n general terms.
The way in which light fastness varies with the nature of
the substrate is even less easily explained. Consequently it is difficult to do other than draw u p a series of
empirical rules applicable to a range of structurally
related dyes o n a particular fibre. In general it can be said
that high light fastness is favoured by the following 161.
(a) Stable aromatic compounds with a minimum
number of double bonds or reactive substituents
available for chemical attack show improved light
fastness. It is worth noting that the 13-hydroxyethyl
group, which has been widely used i n disperse dyes
for cellulose acetate, generally gives rather poor
light fastness on polyester fibres.
(b) Many disperse dyes contain amino groups.
Improved light fastness is usually obtained if these
are substituted in such a way as t o reduce the basicity of the amino group.
(c) Other factors, such as intramolecular dipole forces
or hydrogen bonding between adjacent or per;
atoms or groups, can also give rise t o improved light
fastness.
5. Fastness t o washing is usually less o f a problem o n
polyester than o n acetate fibres, which is not surprising
if we bear in mind the easy on/easy off principle. A
problem peculiar t o polyester fibres is that migration of
the dyeto the fibre surface can take place during stentering, which gives poor wash fastness but only usually for
the first wash. The reasons for this are not yet fully
understood, especially in relation to dye structure.
6. The sublimation fastness of a dye is not particularly fibre
dependent. However, the use of higher application
temperatures and heat treatments for the pleating or
stabilisation of polyester fabrics have necessitated the
development of dyes of higher sublimation fastness.
7. Fastness t o burnt gas fumes is usually less of a problem
o n polyester fibres. Presumably the oxides of nitrogen
penetrate cellulose acetate fibres more easily because of
their relatively hydrophilic character.

CLASSIFICATION OF DISPERSE DYES ACCORDING TO

CHROMOPHORIC GROUPS
The following chromophores commonly occur in disperse
dyes:
1.
2.
3.
4.

Nitrodiphenylamine

Azo
Anthraquinone
Styryl or methine.

These will n o w be considered individually as regards

their use in conventional disperse dyes noting appropriate
points of interest relating t o application and fastness prop-

TABLE 1

erties. Dyes for speciality applications will be considered

later.

Improving Sublimation fastness of a Nitrophenylamine

Dye by Increasing Molecular Size

Nitrodiphenylamine Dyes
Numerically these are a small class of yellow disperse dyes.
They have survived because they are cheap and have good
light fastness despite being rather weak tinctorially. They
are manufactured by condensing an o-nitrochlorobenzene
derivative with an arylamine as shown in Figure 2. The
ortho nitro group is particularly important as it confers
stability by intramolecular bonding; this is one of the
reasons for the high light fastness of these dyes.

Sublimation fastness
(30 s at 180C)
Colour
Polyester
Serisol Fast Yellow PL
(C.I. Disperse Yellow 9)

change

stain

4-5

4-5

NO2
0 - N H 2

A
-

Serilene Golden Yellow T-FS

(C I . Disperse Yellow 70)
0,
O=N

figure 2 - Manufacture of nitrodiphenylarnine dyes

(R=NO,or S o p H , , which may besubstituted by Alk orAr;
A may be further substituted usually in the 4-position

properties, has enabled these dyes to challenge in the areas

traditionally held by anthraquinone dyes. Their main
advantage is an economic one, although initially this had t o
be balanced against problems of dye stability and difficulties i n covering barre effects. As the quality of fibre production has n o w improved, this is less of a problem. There are
three main groups of azo disperse dyes.

In some cases the older disperse dyes for cellulose acetate had a lower substantitivity for polyester, but slight
structural modifications improved this (Figure 3). The
upper dye shown in Figure 3 has better substantivity for
secondary cellulose acetate whilst the lower one is more
appropriate for polyester, which is more hydrophobic.
Serisol Fast Yellow GGL (C.I. Disperse Yellow 33)*
e

-N

o- 2

O2N

Dispersol Yellow C-T (ICI, C.I. Disperse Yellow 42)

figure 3 - Structural modification to improve substantivity

of a nitrodiphen ylamine disperse dye
The sublimation fastness of many of the original disperse
dyes was also inadequate for the more severe end uses o n
polyester, but this has been improved b y increasing the
molecular size. For example, an existing dye has been
diazotised and coupled t o a substituted phenol; this also
has the advantage of introducing an additional
chromophoric group (Table 1).

Azo Dyes
Numerically these f or m by far the largest chemical class,
accounting for more than half the total of disperse dyes.
They n o w cover virtually the whole of the spectrum from
greenish yellows through oranges, browns, reds, bright
pinks, rubines, violets, royal blues, navy blues, greens and
blacks if diazotised and developed products are considered. When the dyes then available were first applied t o
polyester fibres they had several defects:
1. The colour gamut was rather limited, particularly with
regard to hue and brightness
2. Some dyes had relatively l o w light fastness
3. Sublimation fastness was inadequate in many cases.
The extension of the colour gamut has also resulted i n
brighter colours and this, coupled with improved fastness
All the dyes mentioned in this paper are manufactured by Yorkshire Chemicals plc unless stated otherwise.

Aminoazobenzene Dyes
These are traditionally the most important dyes and the
majority are represented by the general formula shown in
Table 2. Commercially these cover the ranges from orange
to blue as shown.
The colour range described is probably not appreciably
different from that theoretically available for cellulose acetate. The most significant advance in recent years has been
the replacement of halogen atoms ortho to the azo linkage
with cyano groups using cuprous cyanide in dimethylformamide, which gives bright blue dyes [71, see Figure 4.
These dyes cannot be. prepared economically by direct
coupling because of the instability of this heavily substituted diazo component.
The structures described in Table 2 rely b y and large on
traditional diazo components, but the coupling components are specially designed to make the dyes more suitable for polyester fibres. The original coupling components
for disperse dyes on cellulose acetate were manufactured
b y reacting aniline or its derivatives with ethylene oxide
(see Figure 5). These coupling components are rather too
hydrophilic t o be ideal for polyester fibres and the
P-hydroxyethyl groups are responsible for the relatively
poor light fastness of the derived dyes on this fibre. The
more modern coupling components are typically manufactured by acylating the hydroxyl groups in the previously
described couplers, or by replacing the ethylene oxide with
acrylonitrile or methyl acrylate as shown in Figure 6.
The effect of this type of development o n the light fastness of disperse dyes,on polyester fibres has been
described I81 and is illustrated in Table 3.
As previously mentioned the presence of P-hydroxyethyl
groups in these dyes gives rise t o relatively poor light fastness. Their replacement by groups such as cyano and
acetoxy gives dyes of very good light fastness, and it
should be noted that these groups are electron deficient
and so should reduce the basicity of the tertiary amino
group. The sublimation fastness of some of the a20 dyes
already described does not meet the more critical requireJSDC Volume 99 July/August 1983 185

TABLE 2

Some Commercial Arninoazobenzene Dyes

Dye
Serilene Orange 2RL
(C.I. Disperse Orange 25)
Serilene Yellow Brown R-LS
(C.I. Disperse Orange 30)
Resolin Red RL
(BAY, C.I. Disperse Red 90)
Foron Blue SE-2R
(S, C.I. Disperse Blue 183)
Serilene Navy Blue ZGN-LS
(C.I. Disperse Blue 79)

~ _ _
Y

~-

___
R

~~

~-

~ _ _ _ _~ _ _ _ _ - ~ _ _ _
R2
R3
R
~-

~-

NO2

Et

C2H,CN

NO2

CI

CI

C,H,CN

C2H,0COMe

NO2

CN

C,H,CN

C,H,COOMe

NO2

CN

Br

NHCOEt

NO2

NO,

Br

OEt

NHCOMe

Et

Et

C,H,OCOMe

C,H,OCOMe
-

TABLE 3

Light Fastness of Some Aminoazobenzene Disperse Dyes

on Polyester
,CN

CN

F(IHC0Me

O z N q N . N 0 N H 4\CzH4RZ
R

Resolin Blue BBLS

(BAY, C.I. Disperse Blue 165)
~

Figure 4

- Manufacture

of C.I. Disperse Blue 765

CI
CI
CI
CI
CI
CI
CI
CI

H
H
CN
CN
CN
CN

H
H
H
H
H
H
H

OCOMe
OCOMe

R Z

Light fastness
on polyester

OH
H
OH
H

3
3-4

OCOMe

7
7

CN
H
OCOMe

6
6
6-7

ments of pad-Thermos01 dyeing and durable-press finishing. This has been solved b y introducing additional polar
groups or increasing the molecular size of the dye; Table 4
exemplifies the latter approach [91.

Figure 5 - Method of manufacture of original coupling

components for disperse dyes on cellulose acetate

C~HICN
@HC2H4CN

+ H,C:CHCOOMe

-+

\
NC2H4COOMe

Figure 6 -Method of manufacturing coupling components

for disperse dyes on polyester

Heterocyclic Dyes
The use of heterocyclic diazo and coupling components has
enabled the colour ranges t o be extended and has made the
production of brighter colours possible; therefore, as previously mentioned, some of the very bright dyes are n o w
challenging the traditional strongholds of the anthraquinone and styryl dyes. The high neat colour strengths of
many of these dyes coupled with their relative ease of
manufacture helps to offset the high cost of some of the
heterocyclic intermediates. A selection of disperse dyes for
polyester fibres using typical heterocyclic diazo and coupling components covering a wide colour gamut is shown in
Table 5. It can be seen that pyridone, thiazole, thiadiazole
and thiophene rings are present in the above dyes, which
all have acceptable fastness properties o n polyester fibres
for most end uses.
Disazo Dyes
Several disperse dyes of this type have proved useful for
the coloration of cellulose acetate. Most of these are
derived from simple, cheap intermediate:;, which helps to
offset the cost of the tw o diazotisations and couplings usually required. The dyes are mainly yellows and oranges and
occasionally reds. Many of the original dyes were useful for

TABLE 4
Improving Sublimation Fastness of an AminoazobenzeneDye by Increasing Molecular Size
0 2 N @ 4 : N e N / c 2 CH
2H,R42 R

Sublimation fastness
(30 s at 210C)
Dye
Serilene
Yellow Brown R-LS
_.
(C.I. Disperse Orange 30)
Serilene Yellow Brown G-LS
(C.I. Disperse Orange 62)

R Z

CI

CI

CN

CI

CI

CN

Colour
change

Polyester
stain

OCOMe

3-4

OCOPh

4-5

TABLE 5
Some Heterocyclic Disperse Dyes for Polyester
Sublimation fastness
(30 s at 180C)
Light
fastness

Colour
change

Polyester
stain

6-7

5-6

4-5

4-5

Greenish blue [14]

5-6

Bluish green [IS]

4-5

4-5

Dye
Bright greenish yellow [ l o ]

&::

N&N

HO
Et

Scarlet [ I 11

Bright bluish red 1121

,CH,Ph
EtS

Et

AcHN

Violet 1131

JSDC Volume 99 July/August 1983 187

TABLE 6

Some Disazo Disperse Dyes for Polyester

v'

R"

Sublimation fastness
(30 s at 180C)
~

Dye
Foron Yellow E-RGFL
(S, C.I. Disperse Yellow 23)
Golden yellow 1161
Orange 1171
Bright yellowish red I181

R'

R Z

R'

R4

Light
fastness

OH

NHAc

NO2

H
H

Me
Me

H
Me

H
Me

4-5
3-4

NHAc

OH
OH
,C,H,CN
N
'C,H,OCOMe

the coloration of polyester fibres, but did not always have

the requisite sublimation fastness. This was overcome
primarily by the introduction of more polar groups as
shown in Table 6.
It should also be noted that all the dyes in Table 6 have
good light fastness as they are relatively simple stable
molecules.

Polyester
stain

6 7

tl

!I

violet, blue and blue green colours. However, a major disadvantage w i th many of the anthraquinone dyes is the
number of intermediate stages or isomer separations
involved in their production, which often has necessitated

Serilene Red 2BL (C.I. Disperse Red 60)

Anthraquinone Dyes
Theoretically it is quite possible t o cover the whole spectrum with anthraquinone disperse dyes, but traditionally
they complemented the nitrodiphenylamine and azo dyes,
being particularly useful for the production o f bright red,

Dispersol Red A-28 (ICI, C.I. Disperse Red 15)

Colour
change

OH

Latyl Violet BN (DUP, C.I. Disperse Violet 27)

OH

OH

Foron Blue S-BGL (S, C.I. Disperse Blue 73)

Serisol Brilliant Violet 2R (C.I. Disperse Violet 1)

I
I

MH2

NH2

Serilene Brilliant Blue 2G (C.I. Disperse Blue 60)

Serisol Brilliant Blue BG (C.I. Disperse Blue 3)

Serisol Fast Blue Green BW (C.I. Disperse Blue 7)

W

HO

Resolin Green C-FGS (BAY, C.I. Disperse Green 5)

NHC,H,OH

1
Figure 7 - Original anthraquinone disperse dyes for cellulose acetate
188 JSDC Volume 99 July/August 1983

J
I

Figure 8 - Some anthraquinone disperse dyes

the use of dedicated plant of relatively high capital and

maintenance costs, making them somewhat expensive.
They have the advantage of brightness and molecular stability, which is not always achievable with azo dyes, but the
gap between the t w o classes is n o w closing rapidly.
The original disperse dyes for cellulose acetate were relatively small simple molecules often containing
P-hydroxyethyl groups (see Figure 7). If we compare these
structures with the previously described azo and nitrodiphenylamine dyes, we would expect that the molecules
of anthraquinone derivatives for polyester dyeing would be
slightly larger and more hydrophobic, and that
P-hydroxyethyl groups would be absent. This proves to be
so, as shown in Figure 8.
It is difficult t o produce rules covering light fastness, but
some general trends can be seen from Table 7.
The presence of one or more primary amino groups on
an anthraquinone ring results i n only moderate light fastness, lower than the hydroxyanthraquinone analogues. A
methylamino group is electron releasing, giving greater
basicity and therefore even lower light fastness. Anilino
and especially benzoylamino groups, however, are electron attracting and less basic, which favours higher light
fastness. Further improvements in light fastness can be
obtained by incorporating electron-attracting groups into
the P-positions of l,Cdiaminoanthraquinone, which also
reduces the basicity of the amino groups. A good example
of this is Serilene Brilliant Blue 2G (C.I. Disperse Blue 60),
which has a light fastness of 7 o n polyester fibres.

Sublimation fastness is also improved by the incorporation of polar groups or by increasing molecular size, as.
shown in the bright bluish-red dyes shown i n Table 8.

Styryl or Methine Dyes

This small class of dyes was particularly suitable for the
production of greenish-yellow colours on acetate fibres.
One of the original dyes is Celliton Fast Yellow7G (GAF, C.I.
Disperse Yellow 31),which is shown in Figure 9. Unfortunately this dye did not have much substantivity for polyester, was pH sensitive and was rather unstable in the
dyebath under typical application conditions, presumably
because of hydrolysis. Structures with a rather more hydrophobic character were produced by similar methods and
these had acceptable affinity for polyester, although the
early versions had poor sublimation fastness. An increase
in molecular size or the incorporation of polar groups overcame the problem. Table 9 illustrates how the use of the
bifunctional adipoyl chloride effectively doubles the
molecular size, C.I. Disperse Yellow 99 having the greater
sublimation fastness.
TABLE 9

Increasing Molecular Size in a Styryl Dye t o Improve Sublimation Fastness

Sublimation fastness
(30 s at 180C)

Dye
Serisol Brilliant Yellow 6GL
(C.I. Disperse Yellow 90)

TABLE 7

change

Polyester
stain

4-5

3 4

Colour

Light Fastness of Some Anthraquinone Disperse Dyes

ke

Terasil Brilliant Yellow 6G

(BAY, C.I. Disperse Yellow 99)
R

Light fastness of polyester

NHMe
NH,

NHPh
OH

4-5
5-6

NHCOPh

/-Y

CIC H\N+Cn:cfN

/
C4H9

\COOEt

I
TABLE 8

Figure 9 - Celliton Fast Yellow 7G (C.I. Disperse Yellow 3 I )

Improving Sublimation Fastness of Anthraquinone Dyes

on

Sublimation fastness
(30 s a t 180C)
Colour

change

Polyester
stain

SMe 1191
SO,NHC,H,OEt 120J

5
5
5

2-3
5
5

~~

DYES FOR SPECIAL APPLICATION TECHNIQUES

Transfer Printing
The commercialisation of this process led to a reversal of
some of the recent trends in disperse dye chemistry. The
ability to sublime rather than sublimation fastness became
the order of the day, and this and good light fastness are
n o w the main requirements. The typical three-dye combination of low energy disperse dyes originally used is
shown i n Table 10.
Occasionally the light fastness obtained by a transfer
printing process with this mixture was slightly inferior t o
more conventional dyeing techniques, presumably as a
result of lack of diffusion into the fibre leaving a proportion
of dye on the surface. In addition, it soon became clear that
JSDC Volume 99 July/August 1983 189

TABLE 10
Three-dye Combination of Low-energy Disperse Dyes
Light fastness
( 1:1 standard deDth)

Dve
Serilene Yellow 3GL
(C.I. Disperse Yellow 54)

6 7

Serilene Red 2BL

(C.I. Disperse Red 60)

OH

Dyes for PolyesterKotton Blends

Polyester/cotton blends have become very important
commercially and two main approaches irivolving the use
of special dyes have been introduced.
Dybln Process (DUP)
This process was pioneered by du Pont 1241.The fabric is
printed or padded with specially developed dyes from an
aqueous dispersion containing a selected polyethylene
glycol capable of maintaining the cellulosic fibres in a swollen condition during subsequent fixation a t 180-220C.
The selection of the disperse dye was of crucial importance as difficulties were encountered both in dyeing the
cellulosic fibres on tone and in obtaining adequate fastness
to skin fat. A typical commercial dye is shown in Figure 10
and its similarity to an azoic combination should be noted.
The Cellestren process (BASF)has been described [25]and
appears similar in concept. The success of this type of
process is likely to depend on the skill of the dye chemists in
synthesising appropriate dyes.

Dispersol Blue G
(ICI, C.I. Disperse Blue 14)
0

NHMe

NHMe

the blue component did not have satisfactory light fastness

for many end uses.
Consequently, the search for a blue dye with good light
fastness has received the most attention. It should be noted
that none of the previously mentioned dyes are of the azo
type and to date it has not been possible to produce an azo
blue of sufficient brightness coupled with an acceptable
transfer rate. Modifications have therefore been concentrated on anthraquinone dyes, building on the principles
already mentioned. The replacement of one of the
methylamino groups in Dispersol Blue G by an amino
group and the incorporation of an electron-attracting group
in the P-position improves the light fastness whilst maintaining acceptable colour and transfer properties. Thus
1-amino-2-cyano-4-ethylaminoanthraquinone [211 and
1-amino-2-cyano-4-anilinoanthraquinone[221 have light
fastness ratings of 4-5 and 5 respectively.
Solvent Dyeing
Interest in this method of application does not appear to be
increasing and, unless there is greater commercial exploitation than at present, little further work from the dye makers appears likely. There are two main application possibilities:
(a) Exhaustion processes from a solution or dispersion in
perchloroethylene using specially selected disperse
dyes at temperatures up to 130C; the dyeing rate is
said to be enhanced by the presence of small amounts
of water 1231 but the major problem appears to be the
selection of dyes having a high partition coefficient in
favour of the fibre.
(b) Padding processes for continuous dyeing systems
using disperse dye solutions in perchloroethylene followed by drying (typically 1 min at 80C) and then
fixation at 190-220C for 45 s; solubility in the solvent
is usually achieved by the use of long alkyl chains, a
typical example being the substitution of the phenolic
ring in l-amino-2-phenoxy-4-hydroxyanthraquinone
with a chain such as iso-octyl by the use of 4iso-octylphenol instead of phenol in the condensation
reaction.
190 JSDC Volume 99 JulyIAugust 1983

Figure 70 - Dybln Scarlet G (DUP, C.I. Disperse Red 220)

Special Dyes for Application in Conjunctioti with Reactive

Dyes
The most important advance appears to be the Dispersol
PC range (ICI), which may be applied in conjunction with all
types of reactive dye.
Conventional disperse dyes usually stain the cellulosic
portion of the blend to some degree and removal of this
stain can be problematical. The Dispersol PC dyes generally
contain two alkoxycarbonyl groups, a typical example
being shown in Figure 11 [26],which dyes polyester fibres
red. In the presence of hydroxyl ions the ialkoxycarbonyl
groups can be converted to the corresponding carboxylic
acids, which are water-soluble products and have little or
no substantivity for cellulose or polyester. These dyes are
particularly useful in printing, and if a little sodium hydroxide is added to the wash liquor staining of the white
unprinted areas is virtually eliminated.

Figure I 1

REFERENCES
1. J.S.D.C., 89 (1973) 414.
2. Fourness, J.S.D.C.. 72 (1956) 513.
3. ICI, 'The Launching of a New Synthetic Fibre - A Historical Survey',
(June 1954).
4. Waters, J.S.D.C.. 66 (1950) 609.
5. Textile Organon (1951-1977).
6. Schroeder and Boyd, Text. Research J., 27 (1957) 275.
7. BAY, BP 1125683 (1966).
8. Muller, Amer. Dyestuff Rep., 59 (Mar 1970) 37.
9. YCL, BP 1055399 (1964).
10. ICI, BP 1256093 (1968).

11.
12.
13.
14.
15.
16.
17.
18.

Martin Marietta, BP 1256434 (1968).

Eastman Kodak Co., BP 1275603 (1968).
CFM. BP 1123103 (1965).
BASF, BP 1112146 (1965).
ICI, BP 1394368 (1972).
YCL, BP 128804 (1969).
ICI, BP 1533121 (1975).
S, BP 1395791 (1971).

19.
20.
21.
22.
23.
24.
25.
26.

BAY, BP 952045 (1962).

BASF, BP 913902 (1961).
LBH, BP 1390864 (1972).
CGY, 6P 1334114 (1970).
Harris and Guion, Text. Research J., 42 (1972) 626.
Sklar, AATCC National Technical Conference Papers (1976) 380.
Miksovsky, J.S.D.C., 96 (1980) 347.
ICI, BP 1012238 (1963).

An Introduction to the Burning Behaviour of

Cellulosic Fibres
A R Horrocks
Department of Textile Studies
Bolton Institute of Higher Education
Deane Road
Bolton BL3 5AB

Presented to the Societys Huddersfield Region on 16

September 1982

The actions of heat and flame on cellulosic fibres are

compared with the physical and chemical behaviour of
other fibres. The combustion mechanism is discussed in
terms of concerted p yrolysis and oxidative stages, which
can be represented as an energy feedback system. The
action of different flame retardants are seen to interfere
with the system and thereby inhibit burning. The
condensed-phase synergistic mechanism of
phosphorus-nitrogen-containing retardants used for
cotton and viscose rayon are discussed in terms of char
enhancement whereas halogen-based retardants operate
in the vapour phase. The latter s ynergistically function in
the presence of antimon y (Ill)oxide and, although lacking
extreme durability, offer the advantage of conferring
flame retardance to adjacent fibrous and non-fibrous
materials. The effect of retardants on smoke and
combustion product toxicity is also considered.

INTRODUCTION
The importance of cotton during both classical and modern
times as a textile fibre of both versatility and economy has
enabled certain disadvantageous properties to be
accepted. The poor creasing character and dimensional
stability of cotton fabrics has been largely overcome by use
of resin formulations and preshrinkage treatments
developed during the present century. The very highly
flammable behaviour of cellulose-containing textiles has
been realised as a hazard rather than an inconvenience and
so perhaps this aspect received attention earlier than did
poor setting properties.
Both wood and cotton have been treated with flameretardant formulations, usually based on salts such as
alum, for very many years. During the nineteenth century,
as chemical science became established, more systematic
researches showed that a variety o f formulations, often
based on soluble inorganic salts, were effective retardants.
For instance, the use of boric acid/sodium borate mixtures
and sodium phosphates is well known. Unfortunately,

such simple treatments lack durability and so developments since the Second World War have emphasised the
need to find durable flame-retardant systems for cellulosic
fibres, in particular cotton and viscose rayon. Within
Europe and in especially the United Kingdom, commercial
retardants, such as Proban 210 (AW) and Pyrovatex CF
(CGY), have proved t o be extremely long-lasting treatments for cotton; these interact within the fibres polymeric
matrix and so do not adversely interfere with either the
technological or the aesthetic characteristics of cellulose
textiles.
Insoluble halogen derivatives (usually containing
chlorine or bromine) combined with the antimony (Ill)
oxide usually present within a polymeric binding matrix are
applied as coatings and so are more restrictive i n their use.
Unfortunately the chemical complexity of flame retarda nts can cause toxicolog ica I and physiological hazards
and in recent years certain formulations have been banned
from use, especially in the USA. Of particular note here is
tris or tris-(2,3-dibromopropyl)-phosphonate used in
some flame-retardant viscose rayon fibres until the
mid-1970s [I].
Most commercial flame-retardant systems fall into one of
the three main groups:
1. Inorganic salts, e.g. zinc chloride, borates, diammonium
phosphate
2. Organophosphorus compounds, e.g. Proban 210,
Pyrovatex CF
3. Halogen compounds often used i n conjunction with
antimony (111) oxide t o give a synergistic system.
It is interesting to note that the phenomenon of synergism, whereby tw o chemical species together provide an
effect greater than the sum of their individual actions, is
quite common in flame-retardant systems. Not only does
the halogen and antimony in 3 above interact in this manner, but the elements of phosphorus and nitrogen when
incorporated together in certain type 1 and 2 systems are
considered to suppress burning synergistically.
To understand h o w the above types of retardants function, it would be useful t o consider why fibres in general
and cellulose (cotton) i n particular are flammable. Once a
simple mechanism of flammability has been developed,
then the action of the various retardant systems may be
understood.

ACTION OF HEAT ON FIBROUS MATERIALS

The effect of heat on a fibre can produce a physical as well
as a chemical effect. Physical changes are shown primarily
b y thermoplastic fibres, which soften above a second-order
JSDC Volume 99 July/August 1983 191