Dyes and Pigments 68 (2006) 109e117

www.elsevier.com/locate/dyepig

Dyeing of nylon with reactive dyes. Part 1. The effect of changes

in dye structure on the dyeing of nylon with reactive dyes
A. Soleimani-Gorgani, J.A. Taylor*
Textiles and Paper, School of Materials, University of Manchester, PO Box 88, Sackville Street,
Manchester M60 1QD, UK
Received 13 January 2005; accepted 25 January 2005
Available online 25 March 2005

Abstract

The dyeing behaviour of seven red commercial cellulosic reactive dyes, all based on the same chromophore and possessing one or
more reactive group, and one to three chromophore units, were evaluated on nylon. Fixation levels appeared to be independent of
the number of either reactive groups or chromophore units. Also, the degree of sulphonation, per se, appeared to have little effect on
fixation, whereas the type of reactive group was important. The major determinant of dye fixation appeared to be associated with the
shape of the molecule and the type, not the number, of reactive groups.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Reactive dyes; Nylon; Molecular size; Fixation efficiency

1. Introduction the mid-fifties Rattee and Stephen [2e5] showed that

dyes containing a dichlorotriazinyl reactive group are
The presence of terminal amino end groups in nylon capable of reacting with cellulosic fibres, in the presence
fibres imparts substantivity towards anionic dyes, of alkali, to form covalent dye to fibre bonds. Sub-
specifically acid dyes, direct dyes and reactive dyes. sequently, research into the chemistry and the applica-
Acid dyes are commonly used on nylon, with 1:2 pre- tion of reactive dyes focused overwhelmingly on
metallised acid dyes generally being used when reason- cellulosic fibres [6,7]. In contrast, considerably less
able levels of wet fastness [1] are required. However, attention has centred on reactive dyes for polyamide
even these dyeings can cause some staining of adjacent fibres. Thus, compared with the vast number of reactive
fabrics during laundering. Whilst an after-treatment of dyes for cellulose [8], relatively few reactive dyes have
the dyed nylon can result in somewhat improved wet- been introduced specifically for polyamide fibres. It is
fastness, repeated washing can still result in loss of known that some reactive dyes, which were developed
colour and there remains much scope for improvement. for cellulosic fibres, can be covalently fixed at the boil, to
Reactive dyes for cellulose resemble acid dyes in their nylon at slightly acidic pH. Under these conditions,
basic structure, but additionally possess one or more covalent bonds form between the dye and the amino
fibre reactive group, their name being derived from their groups of nylon, without the need for an alkaline
ability to react chemically with groups on the fibre. In fixation step [9,10]. Of the reactive dyes which have been
developed specifically for application to nylon the
Stanalan [11] and Eriofast [12] ranges are probably the
* Corresponding author. Tel.: C44 161 200 4112; fax: C44 161 955
best known. Eriofast dyes are metal-free, sulphonated
8150. reactive dyes, developed for application to nylon in
E-mail address: [email protected] (J.A. Taylor). order to achieve outstanding wet fastness properties.

0143-7208/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.dyepig.2005.01.014
110 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117

Water soluble dyes possessing electrophilic reactive were dyed at a liquor ratio of 20:1, using stainless steel
groups such as chlorodifluoropyrimidines [13], bromoa- dyepots, each of 200 cm3 capacity. The dyeing method
crylamides [14], chlorotriazines and vinylsulphones used is depicted in Fig. 1. At the end of the dyeing, the
[15,16], as well as some disperse types [17] have been dyed fabric was removed and rinsed in cold tap water
evaluated on nylon. for 5 min. An initial series of dyeings was carried out at
As a first step towards the design of novel reactive dyes 1% dye o.m.f to determine the effect of pH on dyeing.
for nylon, and before embarking on a synthetic pro- Five different pH values were selected, pH values of, 2,
gramme, an attempt was made to identify the structural 4, 6, and 8 were obtained by using McIlvaine buffers, as
features associated with good reactive dyeing perfor- shown in Table 2 [18], pH 10 was achieved by adding
mance on nylon. Therefore the effect, on dyeing sodium hydroxide to disodium hydrogen phosphate. No
properties, of changes in dye structure, including molec- additional electrolyte, levelling agent or alkali was used.
ular size, number of reactive groups, type of reactive Subsequent dyeings were carried out on 5 g pieces of
groups and also the degree of sulphonation were fabric, at eight depths of shade (0.05%, 0.1%, 0.2%,
evaluated. 0.5%, 0.8%, 1%, 1.5% and 2% o.m.f), at pH 4.

2. Experimental 3.1. Colour strength (K/S ) on fabric

2.1. Materials Reflectance measurements on the dry dyed fabrics

were carried out using a Datacolor Spectraflash 600
Scoured, modified nylon 6.6 ‘‘Tactel Coloursafe’’ specrophotometer under a D65 lamp. The average of
fabric was supplied by Du Pont (UK). Table 1 shows the three reflectance measurements, taken at different
commercial dyes selected. All were based on essentially positions on the dyed fabric, was used.
the same chromophore. All Procion dyes were obtained
from DyStar, Kayacelon React CN-3B was supplied by
Nippon Kayaku and Drimarene Red P-4B was obtained 3.2. Dye exhaustion
from Clariant.
HyperChem version 7.5 was used for molecular The extent of dye exhaustion was determined
modelling and three-dimensional analysis of molecules. spectrophotometrically. The absorbance of each dye-
HyperChem is available from Lightwave Scientific, UK. bath solution before and after the dyeing process was
measured using 1 cm quartz cells housed in a Philips PU
8720 UV/visible scanning spectrophotometer at the lmax
3. Dyeing of each dye. The percentage dyebath exhaustion (%E )
was calculated using Eq. (1), where A0 and A1 are the
Dyeings were carried out using a Roaches dyeing absorbance of the dyebath before and after dyeing,
machine (Mathis Labomat BFA 12): 5 g pieces of fabric respectively.

Table 1
Commercial dyes used for dyeing, Tactel Coloursafe
A0
A1
No. Dye No. of Reactive No. of %EZ !100 ð1Þ
A0
solubilising group reactive
sulphonate type groups
groups
D1 Procion Red 4 MCT 1 100 98oC
P-8B
Temperature (oC)

D2 Procion Red 3 MCT 1 80

H-EXL
D3 Drimarene 3 MCT 1
Red P-4B 60
D4 Procion 8 MCT 2
40oC
Red H-E7B 40
D5 Procion 6 MCT 2
Red H-E3B 30oC
D6 Kayacelon 6 3-carboxypyridinium 2 20
0 20 40 60 80 100 120 140 160 180
React Red triazinyl Time (min)
CN-3B
D7 Procion 9 MCT 3 Dye and Buffer
Rubine XLC
Fig. 1. Dyeing profile used.
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117 111

Table 2 Table 3
Composition of McIlvaine buffers in a total volume of 80 cm3 (K/S )1, (K/S )2, %E and %T of dyes at the different pH values
pH 0.2 M 0.1 M Citric Dye pH
Na2HPO4 (cm3) acid (cm3) 2 4 6 8 10
2 1.6 78.4 Drimarene Red P-4B (K/S )1 11 8.8 4.1 1.3 0.2
4 30.9 49.1 (K/S )2 6.2 4.4 2.5 1.2 e
6 50.6 29.4
%E 99 96 44 17 2
8 77.8 2.2 %T 56 48 26 14 e
Procion Red H-EXL (K/S )1 10.2 11.3 8.5 1.8 0.2
(K/S )2 6 9.49 5.6 1.5 e
3.3. Dye fixation %E 93 100 78 15 5
%T 55 84 51 12.5 e
Only a proportion of the total dye present on the
Procion Red H-E3B (K/S )1 9.9 8.9 5.2 0.6 0.2
substrate reacts to form covalent linkages, whilst the (K/S )2 7.8 8.25 4.4 0.5 e
remaining dye is attached by ionic bonds and by van der %E 100 89 55 8 2
Waals forces. Therefore, in order to determine the %T 78 82.5 46 7 e
degree of dye fixation, the following procedure was Kayacelon React Red (K/S )1 1.3 2.7 0.6 0.12 0.07
used. CN-3B (K/S )2 1.2 2.4 0.5 e e
A sample (1 g) of dyed fabric was immersed in %E 11.5 26 5 0.2 0.1
150 cm3 of 20% aqueous pyridine solution, the temper- %T 10 22 4.1 e e
ature was raised rapidly to boiling and treatment Procion Rubine XLC (K/S )1 14.4 7.6 5 0.1 0.01
continued under reflux until no further dye was removed (K/S )2 4.5 4.75 2.8 e e
%E 90 48 30 0.63 0.1
from the fibre, this took approximately 3 h. The stripped
%T 28 30 17 e e
dyeing was thoroughly rinsed in tap water and allowed
to dry in the open air. The extent of dye fixation was
determined spectrophotometrically. The percentage anionic dyes for (cationic) nylon. The pH can therefore
fixation of the dye which exhausted, %F, was de- play an important role in determining the exhaustion
termined by a method used by several earlier workers and final fixation of reactive dyes on nylon. Therefore,
[13e15] using Eq. (2) where (K/S )1 and (K/S )2 represent before commencing a study of the influence of the dye
the colour strength of the dyeing before and after chemistry on the dyeing of the modified nylon 6.6
stripping of any unfixed colour with aqueous pyridine. ‘‘Tactel Coloursafe’’, it was necessary to determine the
This method assumes, at least at the concentration of optimum application pH. Dyeings were applied at
dyes employed, that (K/S ) values are proportional to several pH values. Buffers of pH 2, 4, 6, 8 and 10 were
concentration of dye on fibre. The overall percentage made up as described above and the dyes applied over
fixation, %T, was evaluated from Eq. (3) 60 min at 98  C.
As the results in Table 3 indicate the fixation of each
ðK=SÞ2
%FZ !100 ð2Þ of the five dyes, at 1% dye o.m.f, is highest in the pH
ðK=SÞ1 range 2e4. The lowest total fixation for all the five dyes
was achieved at pH 10. At high pH the nylon is
%F!%E essentially anionic (Fig. 2). Under these conditions, the
%TZ ð3Þ concentration of nyloneNH2, the active nucleophilic
100
species, which reacts with the electrophilic group(s) of
the dye, is maximised. Since essentially no fixation takes
3.4. Determination of effective agent content dyes place at this pH, it is reasonable to surmise that this
(high concentration of non-protonated nucleophilic
The effective agent content of the dyes were de- amino groups) would be more than counteracted by
termined by titration against titanium (III) chloride [19]. the net electrostatic repulsion between highly anionic
dye and anionic fibre. This is similar to the situation
obtaining in reactive dyes for cellulose, where the
electrostatic repulsion between anionic dye and negative
4. Results and discussion

4.1. Effect of pH on dyeing performance

H+ H+ +
The ability of the amino groups in nylon to protonate NH2-PA-COO
- HOOC-PA-NH2 HOOC-PA-NH3
at low pH effectively reduces the concentration of
nucleophilic free amine and increases the affinity of Fig. 2.
112 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117

Table 4
(K/S )1, (K/S )2, %E and %T of dyes at pH 4
Dye 0.05 0.1 0.2 0.5 0.8 1 1.5 2
Procion Red P-8B (D1) (K/S )1 0.58 1.1 1.98 5.1 7.6 9.8 14.7 19.1
(K/S )2 0.55 1.02 1.83 4.64 6.38 7.9 10.7 11.26
%E 100 100 100 100 100 100 100 100
%T 94 93 92 91 84 81 73 59
Drimarene Red P-4B (D2) (K/S )1 0.49 0.95 1.86 4.5 7.1 8.83 12.67 15.5
(K/S )2 0.46 0.85 1.38 3.06 4.13 4.43 5.16 5.28
%E 100 100 100 100 97 96 90 79
%T 94 89 74 68 56 48 37 27
Procion Red H-EXL (D3) (K/S )1 0.73 1.19 2.27 5.9 9.3 11.3 16.9 21.6
(K/S )2 0.7 1.14 2.1 5.13 7.9 9.49 12.33 14.39
%E 100 100 100 100 100 100 100 100
%T 96 95 92.5 87 85 84 73 66
Procion Red H-E7B (D4) (K/S )1 0.57 1.12 1.64 3.94 4.9 5.9 7.1
(K/S )2 0.56 0.99 1.6 3.4 4.5 5.15 6
%E 100 100 75 71 56 52 40
%T 98 88 73 61 51 45 34
Procion Red H-E3B (D5) (K/S )1 0.52 1 1.96 4.31 6.85 8.9 12.38 14.7
(K/S )2 0.5 0.96 1.86 4.17 6.71 8.25 11.9 13.4
%E 100 100 100 97 90 89 83.5 73
%T 96 96 94.8 93.8 88 82.5 80 66.5
Kayacelon React (K/S )1 0.41 0.69 1.19 2.2 2.56 2.75 3.51 3.82
Red CN-3B (D6) (K/S )2 0.4 0.63 1.07 1.77 2.08 2.4 2.9 3.35
%E 77.5 65 56 45 30 26 22 18
%T 75 59 50.3 36 24 22 18 15.7
Procion Rubine XLC (D7) (K/S )1 0.85 1.67 2.39 5 6.5 7.6 8.9 9.7
(K/S )2 0.62 0.9 1.6 3.2 4.26 4.75 5.4 5.7
%E 100 100 73.5 60 50 48 36 28
%T 72.9 54 50 39 32 30 22 16.4

fibre is reduced by addition of an electrolyte, such as As all the dyes used in this study carry sulphonate
common salt. groups, the observed increase in initial dye uptake (K/S
The protonation of the terminal amino end groups is value) that accompanied a decrease in pH of application
an equilibrium process (Fig. 2). can be attributed to a corresponding increase in ioneion
In the presence of water, and depending on the pH attractive interaction operating between the anionic
within the fibre, the amino and carboxylic acid groups sulphonate groups of the dye and the cationic pro-
will be ionised to a greater or lesser extent. After the tonated amino end groups of the nylon. Additionally,
fibre is immersed in water the actual concentrations of anionic carboxylate groups attached to the fibre will
the four possible fibre species [PA-NH2, PA-NHC 3 , PA- become protonated, thus reducing the electrostatic
COOH, and PA-COO
, (PA- stands for the polyamide repulsion between the nylon and anionic dye. Conse-
fibre backbone)] will depend on the original concentra- quently, pH is one of the key parameters influencing the
tion of the available amino, and carboxylic acid groups, level of exhaustion, and therefore final fixation, of
as well as the pH. reactive dyes to nylon.
Table 3 shows the colour strength (K/S value) and
total fixation (%T ) of 1% dye o.m.f for the dyes applied
Table 5
at different pH values. (K/S )2 and %T were not
Effective agent contents of dyes
determined in cases where exhaustion was extremely low.
Dye Molecular Mol. Strength
When the pH is very low the concentration of NH2
weight (MW) In (MI) (%)
reduces even further and little fixation is observed.
Procion Red P-8B 992 1824 54
Additionally if the temperature is too high at low pH,
Drimarene Red P-4B 851 1291 66
Procion Red H-EXL 890 1580 56 polyamide hydrolysis is possible.
Procion Red H-E7B 1645 3715 44 Generally the optimum pH for dyeing ‘‘Tactel
Procion Red H-E3B 1341 2407 56 Coloursafe’’ with the anionic reactive dyes examined
Kayacelon React Red 1560 4638 34 was found to be around pH 4, at which pH reasonable
Procion Rubine XLC 2341 3347 70
to good dye exhaustion and fixation were achieved.
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117 113

o Procion Red P-8B (mono-functional)

T > 60 C
R1-N=N-R2 + 4TiCl3 + 4HCl R1NH2 + R2NH2 + 4TiCl4 Procion Red H-E7B (bi-functional)
Procion Rubine XL+(tri-functional)
12
Fig. 3.
10
8

(K/S)2
However, the optimum pH for dyeing varied slightly
6
from dye to dye.
4
2
4.2. Build-up properties of dyes
0
0 5 10 15 20
Having established that the optimum pH for dyeing is Eq x 10-3 of dye / kg fabric
4, the build-up properties of the dyes were examined
Fig. 5. (K/S )2 (fixed dye) values of dyes of mono-, bi- and tri-
using the dyeing application conditions shown in Fig. 1. functional dyes.
Table 4 lists the colour strength values (K/S ) for each
of the dyes, at pH 4, at a series of different
concentrations of applied dye. (K/S )1 refers to the linkages producing the corresponding amines as shown
observed colour strength before extraction with pyri- in Fig. 3.
dine, (K/S )2 refers to the colour strength after removal The Mol. In (MI) represents the quantity of isolated
of any non-covalent bond by aqueous pyridine extrac- dye (which contains water and electrolyte), in grams,
tion. which contains 1 mol of ‘‘pure’’ dye. This was de-
termined from Eq. (4).
4.3. Effect of varying the molecular size and the Mass!Hf!10; 000
number of reactive groups MIZ ð4Þ
Tf!Vol
In order to make interpretation of results easier, and where
more meaningful, the effective agent content of each of
the dyes was determined, by titration against titanium
Mass Z the mass (g) of the impure dye.
(III) chloride (Table 5). This allowed a direct compar-
Hf Z the hydrogen factor which is the number of
ison of equimolar quantities of dye on fabric. Addition-
‘‘hydrogens’’ required to reduce the azo or the nitro
ally, because some of the dyes were di- or trimeric, the
group, and is 4 and 6, respectively.
concentration of dye applied to fabric was always
Tf Z the titration factor which represents the
assessed using milli equivalents of dye. Thus complica-
strength (Tf % 1) of the titanous chloride solution
tions arising from different effective agent contents and
and is determined by titration against a standard dye
levels of functionality (mono-, di- or trimeric) were
of a known MI (Procion Orange MX).
obviated.
Vol Z the volume (ml) of the titanous chloride
The strength of the dyes were determined by titration
solution required to reduce all the amount of the
with titanium (III) chloride [19e21] which causes
dye solution.
reduction of the azo group with consequent discharge
of colour. Results are shown in Table 5. Nowadays, the
Because titanous chloride is readily oxidized by
titrimetric estimation of azo dyes with titanous chloride
atmospheric oxygen, it was kept in a closed vessel under
is widely used to determine the purity of azo dyes.
an inert atmosphere. The titration factor was determined
Under acidic conditions, titanous chloride reduces azo

120
Procion Red P-8B (mono-functional) Procion Red P-8B (mono-functional)
25 100 Procion Red H-E7B (bi-functional)
Procion Red H-E7B (bi-functional)
80 Procion Rubine XL+(tri-functional)
20 Procion Rubine XL+(tri-functional)
%T

60
(K/S)1

15
40
10
20
5
0
0 5 10 15 20
0
0 5 10 15 20 Eq x 10-3 of dye / kg fabric
Eq x 10-3 of dye / kg fabric
Fig. 6. %Fixation (%T ) values of dyes of mono-, bi- and tri-functional
Fig. 4. (K/S )1 values of mono-, bi- and tri-functional dyes. dyes.
114 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117

Dye X
X
H Procion Red H-E3B Cl
N N Dye
N N
N N Kayacelon React Red
Dye N N +
N -
H
X
CN-3B
COO

SO3Na H N
H O
Dye = N SO3Na
N

NaO3S

Fig. 7.

each time the titanium chloride is used. The discharge of at least in pale to medium depths of shade, the
dye colour indicated the end-point of the titration. Once KebulkaeMunk linear relationship of (K/S ) with dye
the MI of the dye had been determined, its purity or, concentration [dye] was approximately valid. In con-
effective agent (EA) strength was determined (Eq. (5)). trast, the bi-functional dye, Procion Red H-E7B, and
the tri-functional derivative, Procion Rubine XLC,
Molecular weight exhausted completely only at very pale depths of shade,
EAZ !100% ð5Þ
MI and thereafter exhaustion tailed off markedly. This
In order to gain some insight into the influence of the might be associated with the larger size of the latter two
number of reactive groups on the dyeing of modified dyes or their molecular shape. In the case of all of the
nylon three dyes, Procion Red P-8B (monochlorotri- dyes the (K/S )2 values at the palest depths of shade,
azinyl), Procion Red H-E7B (bis-monochlorotriazinyl) were very marginally less than the (K/S )1 values,
and Procion Rubine XLC (trisemonochlorotriazinyl), indicating high fixation of exhausted dye. At heavier
were compared. All are based upon a similar chromo- depths the (K/S )2 values deviated more markedly from
phore, being derived from a sulphonated 2-aminonaph- (K/S )1 indicating reducing levels of fixation (Figs. 4e6).
thalene, (diazo component) and H-acid, (coupling As the molecular size increases the level of fixation
compound). reduces, especially at heavier concentrations of applied
The initial exhaustion of the dyes varied markedly. dye. This is, in some ways, unexpected, since one
Procion Red P-8B exhibited essentially complete ex- equivalent of fixed colour of the mono-functional dye
haustion at all depths of applied dye (Table 5). This Procion Red P-8B, might be expected to occupy twice of
resulted in an almost linear increase in (K/S )1 with many reactive sites on the fabric as the bi-functional
increasing concentration of dye applied, suggesting that, Procion Red H-E7B, and three times as many as the tri-
functional Procion Rubine XLC. This in turn suggests

(K/S)1 Procion Red H-E3B

(K/S)2 Procion Red H-E3B
(K/S)1 Kayacelon React Red CN-3B
16
16 (K/S)2 Kayacelon React Red CN-3B
14
14
12 12
10
(K/S)1

10
(K/S)2

8 8
6 6
4 4
2 2
0 0
0 2 4 6 8 10 12 14 16 18 0 2 4 6 8 10 12 14 16 18
Eq x 10-3 of dye / kg fabric Eq x 10-3 of dye / kg fabric
Fig. 8. Comparison of initial exhaustion, (K/S )1, of Procion Red Fig. 9. Final exhaustion, (K/S )2, of Procion Red H-E3B and
H-E3B with that of Kayacelon React Red CN-3B. Kayacelon React Red CN-3B.
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117 115

Procion Red H-E3B 25

120
Kayacelon React Red CN-3B
100 20

80 15

(K/S)1
%T

60
10
40 Procion Red H-EXL
5 Procion Red P-8B
20 Drimarene Red P-4B
0
0 0 2 4 6 8 10 12 14
0 2 4 6 8 10 12 14 16 18
Eq x10-3 of dye/kg fabric
Eq x 10-3 of dye / kg fabric
Fig. 12. Comparison of the initial exhaustion, (K/S )1, value of Procion
Fig. 10. Fixation of Procion Red H-E3B and Kayacelon React Red Red H-EXL with those of Procion Red P-8B and Drimarene Red
CN-3B. P-4B.

that the formal availability of nucleophilic amino 4.5. Effect of changes in the ‘‘second leg’’ component
groups, per se, on the nylon is not the sole determinant attached to the triazine ring
of dye fixation.
In order to determine the influence of the number of
sulphonic groups and the shape of the dye molecule on
dyeing properties, three monofunctional monochloro-
4.4. Effect of changing the reactive group triazinyl cellulosic reactive dyes, Procion Red H-EXL,
Procion Red P-8B and Drimarene Red P-4B (Fig. 11),
Procion Red H-E3B and Kayacelon React Red CN-3B were compared (Figs. 12e14). All were derived from
differ only in the nature of the reactive group, the former 2-amino-naphthalene-1-sulphonic acid as diazo com-
possessing two mono-chlorotriazine units and the latter pound and H-acid as coupling compound, but the
two (3-carboxypyridinium) triazine units (Fig. 7). Indeed, ‘‘second leg’’ substituent attached to the monochloro-
Kayacelon React Red CN-3B dye is made by quaternisa- triazinyl reactive group was varied.
tion of nicotinic acid with Procion Red H-E3B. The All three dyes possess a single monochlorotriazinyl
properties of these two dyes on nylon are compared in reactive group. The two Procion dyes, Procion Red H-
Figs. 8e10. The initial exhaustion, as measured by (K/S )1 EXL and Procion Red P-8B differ in the levels of
varies markedly (Fig. 8). This might appear surprising, sulphonation but behave very similarly in terms of initial
since both have exactly the same chromophore and exhaustion and fixation, suggesting that the degree of
linking group, even the same net negative charge, sulphonation may not always be an important de-
assuming that the net negative charge associated with terminant of dye fixation and build-up. Procion Red
the 3-carboxypyridinium reactive group is zero. P-8B possesses four sulphonic acid groups and one

Dye R X Y
Dye
X Procion Red P-8B H 2-COONa 5-SO3 Na
N N
Procion Red H-EXL H 4-COONa H
Cl N N Y
R
Drimarene Red P-4B C2H5 H H

SO3Na

H H
N O N

Dye= N

NaO3S SO3Na

Fig. 11.
116 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117

16 Procion Red H-EXL

Procion Red H-EXL 120
14 Procion Red P-8B
Procion Red P-8B
100
12 Drimarene Red P-4B Drimarene Red P-4B

10 80
(K/S)2

%T
8 60
6
40
4
20
2
0 0
0 2 4 6 8 10 12 14 0 2 4 6 8 10 12 14
Eq x 10-3 of dye / kg fabric Eq x10-3 of dye /kg fabric

Fig. 13. Comparison of the final exhaustion, (K/S )2, value of Procion Fig. 14. Comparison of the, total fixation, (%T ) value of Procion Red
Red H-EXL with those of Procion Red P-8B and Drimarene Red H-EXL with those of Procion Red P-8B and Drimarene Red P-4B.
P-4B.

4.6. Wash fastness properties of dyes

carboxylic acid group whereas Procion Red H-EXL
The wash fastness properties of dyes were assessed
possesses one less sulphonic acid group. Drimarene Red
using the ISO 105CO6/C2S at 60  C wash fastness test
P-4B, like Procion Red H-EXL, is a trisulphonated dye
protocol [22]. The change in shade and the degree of
but initial exhaustion and fixation are both far inferior
cross staining were assessed visually using grey scales
to the other two dyes, suggesting that, at least in this
and the results are presented in Table 6.
case, the shape of the molecule may be more important
Wash fastness of each dye fixed to nylon 6.6 fabric
in determining dyeing properties on modified nylon 6.6.
was very good, at every depth of shade employed.
The introduction of an N-alkylarylamine as a ‘‘second
leg’’ component is a well known route to highly soluble,
low substantive dyes for printing of cellulosic substrates,
this high solubility is generally believed to be attribut- 5. Conclusions
able to the molecule being non-planar, the plane of the
‘‘second leg’’ being at a large dihedral angle to the rest of  In dyeing of Tactel Coloursafe with anionic reactive
the molecule. dyes, the optimum pH of application is 4. At this
This concept was further investigated when the three- pH, the rate of hydrolysis of the electrophlic reactive
dimensional (auto optimisation) structures were com- groups, by water, will be much lower than the rate of
puted using HyperChem, version 7.5 software. These hydrolysis of cellulose reactive dyes, by hydroxide,
three-dimensional images suggested that in Procion Red at high pH.
P-8B and Procion Red H-EXL the arylamine sub-  As the number of reactive groups increases, the
stituent and triazine rings were closer to being coplanar colour yield and fixation decreases.
than in Drimarene Red P-4B, where the triazine and  The chlorotriazine reactive group is more fixation
arylamine substituents ring deviate much more mark- efficient on nylon than the 3-carboxypyridinium
edly from coplanarity. This deviation from coplanarity triazine reactive groups.
of the molecule allows less interaction of dye with fibre  The degree of dye sulphonation is not always an
surface and this is probably responsible for lowering of important determinant of dye fixation and build-up
dye uptake, and hence, exhaustion and fixation of on nylon. The shape and size of the molecules is more
Drimarene Red P-4B. important in determining dyeing properties on nylon.

Table 6
Wash fastness results of dyes in the ISO 105CO6/C2S
Dye Staining
Secondary cellulose Bleached Un-merc. Nylon 6.6 Polyester Acrylic Wool
acetate cotton
Procion Red P-8B 4/5 4/5 4/5 4/5 4/5 4/5
Procion Red H-EXL 4/5 4/5 4/5 4/5 4/5 4/5
Drimarene Red P-4B 4/5 4/5 4/5 4/5 4/5 4/5
Procion Red H-E7B 4/5 4/5 4/5 4/5 4/5 4/5
Procion Red H-E3B 4/5 4/5 4/5 4/5 4/5 4/5
Procion Rubine XLC 4/5 4/5 4/5 4/5 4/5 4/5
 A. Soleimani-Gorgani, J.A. Taylor / Dyes and Pigments 68 (2006) 109e117 117

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