Dyes and Pigments 45 (2000) 65±74

The dyeing of nylon 6,6 with sulphur dyes

Stephen M. Burkinshaw a,*, Samit N. Chevli a, David J. Marfell b
a
School of Textile Industries, The University, Leeds LS2 9JT, UK
b
Du Pont Nylon (UK), Brockworth, Gloucester GL3 4HP, UK

Received 12 November 1999; accepted 13 December 1999

Abstract
When nylon 6,6 was dyed with ®ve sulphur dyes using two reduction systems, dyeings on nylon 6,6 were of compar-
able depth of shade to dyeings produced on cotton. The dyeings on nylon 6,6 displayed very good fastness to repeated
washing and high resistance to oxygen bleach fading. The fastness of the dyeings to these agencies was enhanced by
means of an aftertreatment with a commercial cationic ®xing agent. Both the dry and wet rub fastness of the dyeings
was very good but the dyeings displayed poor fastness to light. # 2000 Elsevier Science Ltd. All rights reserved.
Keywords: Nylon 6,6; Sulphur dyes; Repeated wash fastness; UKTO test

1. Introduction treatments. However, the high level of wet fastness

displayed often is secured only by recourse to an
Nylon 6,6 can be dyed using many types of dye, aftertreatment with a synthetic tanning agent
namely: (syntan); in addition, the use of pre-metallised acid
dyes has attracted environmental interest in recent
. anionic, acid (including pre-metallised acid), years.
mordant, direct and reactive classes; It was against this background that a decision
. cationic, basic dyes used predominantly on was made to look at the feasibility of dyeing nylon
modi®ed (cationic dyeable) nylon 6,6; 6,6 with sulphur dyes in deep shades using an
. nonionic, disperse and vat classes. exhaust (immersion) dyeing method.
Sulphur dyes are one of the most popular dye
The merits and demerits of using these dye types classes for cellulosic ®bres and their blends, being
on nylon 6,6 have been well documented elsewhere widely used to produce inexpensive, medium to
[1±3]. It is widely held that only one of the dye heavy depths. It is considered that sulphur dyes
types, videlicet the pre-metallised acid dyes, can constitute the largest class of dye used in terms of
furnish deep shades on nylon 6,6 of good/very quantity consumed globally and that Sulphur
good fastness to light and to wet and washing Black 1, in all its forms (C.I. Sulphur Black 1, C.I.
Solubilised Sulphur Black 1 and C.I. Leuco Sul-
phur Black 1), is the most important black dye in
* Corresponding author. Tel.: +44-113-233-3722; fax: +44-
113-233-3704. the world [4]. Typically, sulphur dyes possess
E-mail address: [email protected] moderate to good fastness to light and wet treat-
(S.M. Burkinshaw). ments on cellulosic substrates but are less resistant
0143-7208/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0143-7208(00)00003-6
66 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74

to washing with detergent/perborate formulations Five sulphur dyes were chosen, arbitrarily; these
that are now common in domestic washing pow- are listed in Table 1. Leucad 71, a commercially
ders [4,5]. The so-called sulphur vat dyes or sul- available, aqueous solution of sodium sul®de
phurized vat dyes, which are either sulfur or vat and sodium sulfhydrate, was kindly supplied by
dyes that often are applied to cellulosic ®bres J Robinson Ltd. A commercial sample of the
using a di€erent reduction system to that of sul- cationic ®xing agent Sol®x E was obtained from
phur dyes, display higher wet fastness and greater Ciba-Geigy and a commercial sample of the
resistance to bleaching than traditional sulphur non-ionic surfactant Lanapex R was provided
dyes on cellulosic ®bres [4,5]. by Uniqema. All other chemicals used were
In the context of nylon 6,6, sulphur dyes are laboratory grade reagents obtained from Aldrich.
used on blend materials, notably nylon/cellulosic
blends [6±8] and recent patent literature suggests 2.2. Procedures
continuing commercial interest in the application
of sulphur and sulphur vat dyes to nylon blend Four dyeing methods were used (Table 2) which
substrates [9±13]. In contrast, there appears to are designated methods 1, 2, 3 and 4. In each case,
have been little, if any, reference in the open lit- a 10:1 liquor ratio was used and dyeing was car-
erature to the use of the dyes on 100% nylon 6,6 ried out in 300 cm3 capacity sealed, stainless steel
since the 1939 study of the dyeability of the ®bre dyepots, housed in a Roaches Pyrotec S infrared
which concluded that sulphur dyes had very little dyeing machine.
substantivity for nylon ®bre and would not hold
much commercial importance for the dyer [14]. 2.2.1. Method 1
This paper describes the dyeing of nylon 6,6 This was the standard method recommended by
with sulphur dyes in deep shades using an exhaust J Robinson Ltd for the application of the Sulphosol
(immersion) dyeing method and an investigation of range of C.I. Solubilised Sulphur dyes to cotton. In
the fastness properties of the dyeings. In addition, this method, pre-wetted samples of cotton were
the e€ects on dyeability of a traditional, commer- dyed using Leucad 71 as reducing agent (Fig. 1);
cial, sulphide-based reduction system and a non at the end of dyeing, the samples were oxidised
sulphide-based reduction system are discussed. using the procedure described below.

2.2.2. Method 2
2. Experimental Nylon 6,6 was dyed following the method
shown in Fig. 1 using Leucad 71 as reduction sys-
2.1. Materials tem (Fig. 1); at the end of dyeing, the samples were
oxidised using the procedure described below.
Scoured, knitted, nylon 6,6 fabric (78f68, 1.15
dtex per ®lament) was kindly supplied by Du Pont 2.2.3. Method 3
UK; scoured, woven, ¯uorescent brightener-free Nylon 6,6 was dyed following the method
cotton fabric was obtained from Whaleys. shown in Fig. 2 using glucose/NaOH as reduction

Table 1
Sulphur dyes used

Commerical name C.I. generic name Manufacturer

Sulphosol Yellow SR Solubilised Sulphur Yellow 23 J Robinson

Sulphosol Green SBCF 125% Solubilised Sulphur Green 2 J Robinson
Sulphosol Bordeaux SB Solubilised Sulphur Red 6 J Robinson
Hydrosol Blue R Solubilised Sulphur Blue 7 J Robinson
Immedial Indocarbon Black CL Sulphur Black 11 DyStar
 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74 67

Table 2
Dyeing methods

Method Fibre type Process Reducing

system

1 Cotton Dyeing only Leucad 71

2 Nylon 6,6 Dyeing only Leucad 71
3 Nylon 6,6 Dyeing only Glucose/NaOH
4 Nylon 6,6 Combined scouring Glucose/NaOH
and dyeing

Fig. 2. Method 3.

Fig. 1. Methods 1 and 2.

system; at the end of dyeing, the samples were

oxidised using the procedure described below.

2.2.4. Method 4
This combined scouring and dyeing method
(Fig. 3) utilised a non-ionic surfactant (Lanapex
R) and glucose/NaOH as reduction system. At the
Fig. 3. Method 4.
end of dyeing, the samples were oxidised using the
procedure described below.
steel dyepots housed in a Roaches Pyrotec S
2.2.5. Oxidation infrared dyeing machine following the method
At the end of dyeing, the samples were rinsed shown in Fig. 4. At the end of aftertreatment, the
for 5 min in cold water and then for 5 min in hot dyed samples were rinsed in running cold water
(60 C) water and then oxidised, using a liquor for 5 min and allowed to dry in the open air.
ratio of 50:1, at 60 C in a bath containing 2 glÿ1
35% H2O2 at pH 4.5, for 15 min. At the end of 2.2.7. Wash-fastness
oxidation, the samples were rinsed in running cold The dyed fabric was subjected to ®ve con-
water for 5 min and allowed to dry in the open air. secutive ISO CO6/C2 [15] wash tests; at the end of
each wash test, the washed sample was rinsed
2.2.6. Aftertreatment with cationic ®xing agent thoroughly in tap water but was not dried. A fresh
The oxidised, sulphur dyed samples of cotton sample of SDC multi®bre strip was used to assess
and nylon 6,6 were aftertreated with Sol®x E in an the extent of staining for each of the ®ve wash
attempt to improve the wash fastness of the dye- tests. The extent of the staining of the adjacent
ings. Aftertreatment was carried out using a liquor multi®bre strip samples was expressed in the
ratio of 20:1 in 300 cm3 capacity, sealed stainless appropriate staining grey scale whereas the change
68 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74

Fig. 4. Aftertreatment using commerical cationic ®xing agent.

in shade of the sample after washing was expressed

in
E CMC (2,1) units.

2.2.8. UKTO test

Dyeings were subjected to the UKTO [16] test at
60 C and the change in shade reported in
E Fig. 5. Colour yield achieved using dyeing methods 1±3.
CMC (2,1) units.

2.2.9. Rub fastness to that achieved on cotton, with the exception of

Sulphur dyed samples were subjected to the ISO the red dye used. The use of the sulphide-free, glu-
X12 test method (15). cose/NaOH reduction system (method 3) instead
of Leucad 71 proved to be advantageous in terms
2.2.10. Light fastness of the fk values of the yellow, green and red dyes.
The fastness of the dyeings to light was deter- Hence, the results shown in Fig. 5 clearly
mined using the ISO B02 method (15). demonstrate that the four sulphur dyes displayed
high substantivity towards nylon 6,6. This sub-
2.2.11. Colour measurement stantivity may be attributable to polar forces of
All measurements were carried out using an X- attraction such as dispersion forces, ion±dipole
rite spectrophotometer interfaced to a PC using forces, dipole±dipole interactions and hydrogen
D65 illumination, 10 standard observer with spec- bonding; while it is possible that ion±ion forces
ular component excluded and UV component could operate between the reduced form of the
included. Each fabric was folded once to give two dye, namely the anionic, thiolate derivative and
thickness and an average of four readings was protonated sites in the ®bre, such forces can be
taken each time. assumed to be negligible under the alkaline appli-
cation conditions used. This particular aspect of
the research work is receiving further attention.
3. Results and discussion Table 3 shows the colorimetric data obtained for
cotton which had been dyed using method 1 and
Fig. 5 shows the colour yield (fk values) achieved for nylon 6,6 fabric which had been dyed using
using dyeing methods 1±3. It is evident that in the method 2. Results are presented for the dyeings
case of cotton fabric which had been dyed using both before and after ®ve, consecutive, ISO CO6/
method 1 (the dye maker's recommended dyeing C2 wash tests. Evidently, there was a di€erence in
method that used the commercial, sodium sul®de/ shade obtained for the same dye on the two dif-
sodium sulfhydrate reduction system, Leucad 71), ferent types of substrate. The
E values quoted in
the colour strength achieved for the four dyes used Table 3 refer to the colour di€erence between a
varied from around 75 to 275 fk units. Fig. 5 also dyeing on a given substrate before and after ®ve
reveals that when the same, traditional, sul®de- consecutive ISO CO6/C2 wash tests; as such, the
based dyeing method for cotton was used to apply
E values provide a measure of the extent of dye
the dyes to nylon 6,6 fabric (method 2), the colour loss that occurred from the dyeing during repeated
strength of the nylon 6,6 dyeings was comparable wash testing. A comparison of the
E values
 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74 69

Table 3
Colorimetric data obtained for dyeing methods 1 (cotton) and 2 (nylon 6,6)

Dye Fibre Aftertreatment Washes L* a* b*
E

Yellow 23 Cotton Nil 0 61.2 12.7 55.0 6.5

Sol®x E 5 71.2 5.7 54.2
0 60.3 13.2 53.0 3.8
5 65.3 9.7 56.5
Nylon 6,6 Nil 0 68.5 10.0 59.4 3.6
5 73.4 5.7 60.7
Sol®x E 0 68.1 9.2 57.6 2.3
5 71.2 6.6 58.9
Green 2 Cotton Nil 0 27.4 ÿ15.7 ÿ6.5 5.8
5 34.2 ÿ18.0 ÿ10.9
0 27.1 ÿ15.9 ÿ7.4 2.5
5 28.4 ÿ16.5 ÿ10.4
Nylon 6,6 Nil 0 30.5 ÿ25.2 ÿ6.5 2.1
5 31.4 ÿ25.7 ÿ8.7
Sol®x E 0 30.5 ÿ24.8 ÿ6.7 1.7
5 30.8 ÿ25.1 ÿ8.5
Red 6 Cotton Nil 0 22.1 14.4 2.5 12.7
5 37.9 20.0 3.5
Sol®x E 0 22.6 15.8 3.7 7.3
5 31.1 19.3 6.7
Nylon 6,6 Nil 0 44.0 15.5 3.4 3.5
5 49.4 16.1 5.6
Sol®x E 0 45.2 16.1 5.3 1.5
5 47.6 15.7 6.0
Blue 7 Cotton Nil 0 18.6 2.9 ÿ12.4 7.9
5 22.2 7.6 ÿ20.2
Sol®x E 0 18.3 4.7 ÿ14.8 2.8
5 19.1 7.0 ÿ17.5
Nylon 6,6 Nil 0 16.5 2.1 ÿ17.3 2.9
5 15.9 4.5 ÿ19.7
Sol®x E 0 16.3 2.2 ÿ17.5 2.4
5 16.2 4.2 ÿ19.6

obtained for each of the dyes on the two di€erent Figs. 6 and 7 also show that the aftertreatment
substrates reveals that the extent of dye loss was of both the cotton and the nylon 6,6 dyeings with
markedly lower for the nylon 6,6 dyeings. In turn, the commercial cationic ®xing agent, Sol®x E,
this result implies that the fastness, to repeated enhanced the fastness of the dyeings to repeated
wash testing, of the nylon 6,6 dyeings was superior wash testing. Previous work [17±19] has shown
to that of the corresponding dyeing on cotton. that the fastness to detergent/perborate washing of
Fig. 6 shows graphically the fk values obtained the oxidised dyeings of C.I. Solubilised Sulphur,
for the cotton dyeings quoted in Table 3 and C.I. Leuco Sulphur and C.I. Sulphur dyes on cot-
Fig. 7 shows the fk values secured for the nylon 6,6 ton was markedly improved by the use of cationic
dyeings. The reduction in colour strength that ®xing agents that were applied using simple
occurred as a result of ®ve repeated ISO CO6/C2 exhaust or continuous aftertreatment procedures.
wash tests is apparent, especially in the case of the It was postulated [17±19] that this improved wash
cotton dyeings. fastness could be attributed to:
70 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74

. the formation of a large molecular size dye± to explain the enhancement of wash fastness
cationic agent of reduced aqueous solubility imparted by aftertreatment with the Sol®x E,
within the ®bre and/or; further work is clearly required to establish the
. the formation of a `layer' of the polymeric precise mechanism by which such enhanced wash
cationic ®xing agent at the periphery of the fastness is imparted.
dyed ®bre. When Figs. 6 and 7 are compared, it is obvious
that the nylon 6,6 dyeings underwent considerably
It was considered that such a mechanism would less reduction in colour strength during repeated
lower the rate at which the dye di€used out of the wash testing than the corresponding cotton dye-
dyed substrate during washing and thus improve ings. The grey scale ratings of the stained adjacent
wash fastness. However, while no direct evidence cotton and nylon 6,6 materials after wash testing
was obtained to support this mechanism, indirect (Table 4) clearly show that the extent of staining
evidence, in the form of ®ndings reported in other of the adjacent nylon 6,6 and cotton fabrics was
publications, was advanced [17±19]. Whilst it considerably lower in the case of the nylon 6,6
seems reasonable to propose that the above dyeings.
mechanism could be applied to the present work In Table 4, when the grey scale ratings for the
aftertreated dyeings are compared to those
secured for the non-aftertreated dyeings, it is clear

Table 4
Staining results obtained using dyeing method 1 (cotton) and
method 2 (nylon 6,6)a

Wash Dyed cotton Dyed nylon 6,6

Cotton Nylon 6,6 Cotton Nylon 6,6

Yellow 23
1 3 (3/4) 3/4 (3/4) 3/4 (4) 4 (4/5)
2 3 (3/4) 3/4 (4) 3/4 (4) 4 (4/5)
3 4 (3/4) 4 (4) 4 (4/5) 4 (5)
4 4 (4) 4 (4/5) 4 (4/5) 4/5 (5)
5 4 (4/5) 4/5 (4/5) 4/5 (4/5) 4/5 (5)
Green 2
Fig. 6. fk values for cotton dyed using method 1. 1 3 (3) 3 (3/4) 4 (4) 4 (4/5)
2 3 (3/4) 3 (3/4) 4 (4) 4/5 (4/5)
3 3 (3/4) 3/4 (3/4) 4 (4/5) 5 (5)
4 3 (3/4) 3/4 (4) 4 (4/5) 5 (5)
5 3/4 (4) 3/4 (4) 4/5 (5) 5 (5)
Red 6
1 2/3 (3/4) 5 (5) 5 (5) 5 (5)
2 2/3 (3/4) 5 (5) 4/5 (4/5) 5 (5)
3 3 (3/4) 5 (5) 4/5 (5) 5 (5)
4 3 (4) 5 (5) 5 (5) 5 (5)
5 3/4 (4) 5 (5) 5 (5) 5 (5)
Blue 7
1 2 (2/3) 5 (5) 4/5 (4/5) 5 (5)
2 2 (2/3) 5 (5) 4/5 (4/5) 5 (5)
3 2 (3) 5 (5) 5 (5) 5 (5)
4 3 (3) 5 (5) 5 (5) 5 (5)
5 3 (4) 5 (5) 5 (5) 5 (5)
a
Fig. 7. fk values for nylon 6,6 dyed using method 2. Figures in brackets refer to Sol®x E aftertreated samples.
 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74 71

that the cationic ®xing agent reduced the extent of

staining of the adjacent materials during repeated
wash testing.
Table 5 shows the colorimetric data obtained for
nylon 6,6 which had been dyed using method 3 in
which a glucose/NaOH reduction system was used
instead of the commercial Leucad 71 reduction
system previously employed in method 2; the cor-
responding fk values for the dyeings are displayed
in Fig. 8. The fk values in Fig. 8 and the
E values
in Table 5 reveal that the dyeings displayed good
fastness to repeated wash testing; this ®nding was
con®rmed by the very good/excellent grey scale
staining assignments presented in Table 6.
The fk values in Fig. 8 and the
E values in Fig. 8. Colour strength data obtained for dyeing method 3 on
Table 5 also show that aftertreatment with Sol®x nylon 6,6.
E enhanced the wash fastness of all four dyes used.
When the
E results presented in Table 5 are
compared with those displayed in Table 3 for the Table 6
nylon 6,6 dyeings, it can be concluded that gen- Staining results obtained for nylon 6,6 using dyeing method 3a
erally deeper dyeings were obtained using method Wash Staining of
3 and also, that these particular dyeings displayed
higher fastness to repeated wash testing. The rea- Cotton Nylon 6,6
sons for the increased depth of shade and superior Yellow 23
wash fastness of the dyeings on nylon 6,6 obtained 1 3/4 (4) 4 (4/5)
using the glucose/NaOH application method 2 3/4 (4) 4 (4/5)
(method 3) are currently being investigated; the 3 4 (4/5) 4 (5)
4 4 (4/5) 4/5 (5)
5 4/5 (5) 4/5 (5)

Table 5 Green 2
Colorimetic data obtained for nylon 6,6 using dyeing method 3 1 4 (4) 4/5 (4/5)
Dye Aftertreatment Washes L* a* b*
E 2 4 (4) 4/5 (4/5)
3 4 (4/5) 5 (5)
Yellow 23 Nil 0 67.1 10.3 59.4 3.4 4 4 (4/5) 5 (5)
5 72.6 7.3 63.2 5 4/5 (5) 5 (5)
Sol®x E 0 65.8 10.2 58.6 1.4
5 68.2 8.9 60.2 Red 6
1 4 (4) 5 (5)
Green 2 Nil 0 22.5 ÿ19.4 ÿ5.9 1.0
5 22.7 ÿ20.2 ÿ7.2 2 4/5 (4/5) 5 (5)
Sol®x E 0 23.2 ÿ19.6 ÿ5.8 0.9 3 4/5 (4/5) 5 (5)
5 23.0 ÿ19.0 ÿ6.9 4 4/5 (4/5) 5 (5)
5 4/5 (4/5) 5 (5)
Red 6 Nil 0 33.1 18.4 3.9 2.4
5 36.5 20.0 5.1 Blue 7
Sol®x E 0 34.8 18.7 5.3 1.0 1 4/5 (4/5) 5 (5)
5 36.1 19.8 5.7 2 4/5 (4/5) 5 (5)
Blue 7 Nil 0 16.5 2.2 ÿ16.0 2.6 3 4/5 (5) 5 (5)
5 16.4 4.1 ÿ18.7 4 4/5 (5) 5 (5)
Sol®x E 0 15.9 2.1 ÿ16.4 0.6 5 5 (5) 5 (5)
5 15.8 2.3 ÿ17.2
a
Figures in brackets refer to Sol®x E aftertreatted samples.
72 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74

higher dyeing temperature used in method 3 may protocol that was designed to identify coloured
be a contributory factor. cotton fabrics susceptible to oxygen bleach fading
The staining ratings displayed in Table 6 clearly through repeated washing with domestic deter-
show the high fastness of the nylon 6,6 dyeings gents. Consequently, sulphur dyeings on cellulosic
to repeated wash testing and also, that after- ®bres can be expected to show poor fastness to the
treatment with the cationic ®xing agent enhanced UKTO test method, as was demonstrated [16,20]
this fastness. for several sulphur dyes. According to the UKTO
As mentioned earlier, while sulphur dyes on methodology, when the colour di€erence [
E
cellulosic ®bres possess moderate to good fastness CMC (2,1)] between a dyed cotton sample before
to light and wet treatments, they are much less and after testing is <4 units, the sample is con-
resistant to washing with detergent/perborate for- sidered to be robust to oxygen bleach fading while
mulations that are now common in domestic a
E>4 units indicates bleach sensitivity.
washing powders. The recently introduced UKTO Table 7 shows the colorimetric data obtained for
test method [16,20] is a diagnostic single wash test cotton which had been dyed using the commercial

Table 7
Colorimetric data obtained for the UKTO wash test

Dye Fibre Aftertreatment Washes L* a* b*
E

Yellow 23 Cotton Nil 0 61.1 12.5 55.0 7.2

Sol®x E 1 72.8 5.8 58.9
0 60.8 12.8 52.9 4.0
1 67.2 9.6 56.4
Nylon 6,6 Nil 0 66.2 10.2 58.5 4.5
1 73.4 7.0 64.5 2.6
Sol®x E 0 61.6 10.5 54.1
1 66.4 8.9 56.9
Green 2 Cotton Nil 0 27.9 ÿ16.0 ÿ7.2 6.6
1 30.2 ÿ14.9 ÿ15.1
0 27.9 ÿ16.3 ÿ7.6 4.6
1 29.1 ÿ13.4 ÿ12.1
Nylon 6,6 Nil 0 22.3 ÿ19.4 ÿ5.9 2.7
1 22.6 ÿ17.4 ÿ8.7
Sol®x E 0 23.1 ÿ20.3 ÿ6.1 2.5
1 23.1 ÿ17.9 ÿ8.6
Red 6 Cotton Nil 0 22.0 14.2 2.9 15.5
1 41.6 19.3 3.6
Sol®x E 0 21.8 15.5 4.1 9.3
1 32.6 19.9 7.4
Nylon 6,6 Nil 0 34.5 18.8 5.0 1.4
1 37.0 18.8 4.9
Sol®x E 0 33.6 18.4 4.0 1.4
1 36.1 18.6 4.1
Blue 7 Cotton Nil 0 18.7 2.9 ÿ12.6 8.6
1 23.4 7.2 ÿ21.5
Sol®x E 0 18.3 4.7 ÿ14.7 3.2
1 20.2 6.3 ÿ18.2
Nylon 6,6 Nil 0 16.4 2.2 ÿ16.2 2.3
1 16.3 3.7 ÿ18.9
Sol®x E 0 15.4 2.7 ÿ15.8 1.3
1 15.6 3.6 ÿ17.2
 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74 73

Table 8 Thus, from the data presented in Table 7, it is

Rub fastness of sulphur dyes on nylon 6,6 clear that the four sulphur dyes showed very poor
Dye Wet Dry resistance to the UKTO test method on cotton but
very good bleach resistance on nylon 6.6. This
Yellow 23 5 5 di€erence in the behaviour of the dyes on the
Green 2 5 5
Red 6 5 5
two substrates may be attributed to the more
Blue 7 5 5 hydrophobic nature of the nylon 6.6 ®bre leading
to lower oxidative degradation of the sulphur
linkages in the dyes.
reduction system (method 1; Leucad 71) as well Table 8 shows the rub fastness of nylon 6,6
as nylon 6.6 fabric which had been dyed using which had been dyed with the sulphur dyes using
the glucose/NaOH reduction system (method 3). method 3 (glucose/NaOH), from which it is clear
Evidently, the
E values obtained for the non- that both the dry and wet rub fastness of the sul-
aftertreated cotton dyeings were very high show- phur dyeings was excellent. The light fastness of
ing the susceptibility of the dyeing to oxygen the dyes on nylon 6,6 when applied using method
bleach fading; however, aftertreatment with the 3 (Table 9) left much to be desired, the ratings
commercial cationic ®xing agent reduced the
E obtained being much lower than can be expected
values and so lowered the susceptibility of the for the dyes on cellulosic ®bres.
dyeings to oxygen fading. The
E values secured As the sulphur dyeing of nylon 6,6, shown in
for the non-aftertreated nylon 6.6 dyeings were very Figs 1±3 had been carried out under alkaline con-
much lower than those of the corresponding cotton ditions and, because the scouring of nylon 6,6 is
dyeings; aftertreatment with Sol®x E also improved also typically carried out under alkaline conditions,
the bleach resistance of the nylon 6.6 dyeings. it was decided to combine these two operations.

Table 9
Table 11
Light fastness of sulphur dyes on nylon 6,6
Colorimetric data obtained for a deep black shade on nylon 6,6
Dye Wet
Test Wash L* a* b* fK
E
Yellow 23 1±2
CO6/C2 0 12.7 1.0 ÿ1.5 554.7 0.9
Green 2 2
5 12.2 1.2 ÿ2.0 563.7
Red 7 2
Blue 7 3/4 UKTO 0 12.4 1.0 ÿ1.5 560.2 1.0
Black 11 >4 1 11.9 1.2 ÿ2.0 587.4

Table 10
Colorimetric data obtained using conventional dye after scour and combined scour and dye methods

Process L* a* b* C h fk

Yellow 23
Dyed after scouring 67.1 10.3 59.4 60.3 80.2 60.8
Combined scour and dye 65.8 10.2 58.6 69.5 80.1 65.6
Green 2
Dyed after scouring 22.5 ÿ19.4 ÿ5.9 20.3 196.9 314.7
Combined scour and dye 22.7 ÿ19.6 ÿ5.8 20.4 196.5 30.92
Blue 7
Dyed after scouring 16.5 2.2 ÿ16.0 16.2 277.8 348.8
Combined scour and dye 16.9 2.0 ÿ16.4 16.5 277.1 337.7
74 S.M. Burkinshaw et al. / Dyes and Pigments 45 (2000) 65±74

Table 10 shows the colorimetric data obtained for on nylon 6,6 showed excellent wet and rub fast-
nylon 6,6 samples which had been dyed using the ness but the light fastness of the dyeings was poor.
combined scouring and dyeing process (method 4) The study implies that sulphur dyes may provide
that used the glucose/NaOH reduction system as an alternative to metallised acid dyes in obtaining
well as the corresponding data secured when nylon economical, deep shades on nylon 6,6, especially
6,6 had been dyed after scouring using method 3 for outlets where high light fastness is not an issue.
(glucose/NaOH). Investigation of the results dis- E€orts are now being focussed to improve the
played in Table 10 shows that there was little dif- light fastness of the dyeings and to extend the dye
ference, between the two dyeing methods used, in colour gamut.
terms of both the colour and the colour strength
of the dyeings.
Perhaps the most important shade that could be References
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