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Modified 2,4-difluoro-5-chloro-pyrimidine
dyes and their application in ink-jet
printing on wool fabrics
M Clark,* K Yang and D M Lewis
Department of Colour Science, University of Leeds, Leeds LS2 9AL, UK
Email: m.clark@leeds.ac.uk
184 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190
14784408, 2009, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1111/j.1478-4408.2009.00195.x by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [30/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Clark et al. Ink-jet printing on wool fabrics
anion can be detected by FT-IR because it shows a strong The carbon atom in position 2 is more electrophilic and
peak at 2067 cm)1); (vi) the precipitated dye was dried in accessible to nucleophilic substitution than is the carbon
a vacuum desiccator at ambient temperature. atom in position 4, partly because of the two adjacent,
electron-withdrawing nitrogen atoms. When the fluorine
Ink-jet printing procedure in position 2 is substituted, the reactivity of the system
The textile ink-jet printing requires the following decreases, so it is difficult for the fluorine in position 4 to
processes: fabric pretreatment, ink-jet printing, fixation be substituted.
and washing off. Capillary electrophoresis showed that, with increasing
reaction time, the area of the separated peak
Wool pretreatment corresponding to the parent FCP dye decreased, while the
The wool fabrics were scoured using a solution component peak attributed to the modified dye increased.
containing 1 g ⁄ dm)3 Sandozin NIE and 2 g ⁄ dm)3 sodium CE was therefore used to monitor the progress of the
bicarbonate at 50 C for 15 min, rinsed with cold water modified dye synthesis.
and then air-dried before being padded with the
pretreatment solution. Analytical techniques
Scoured wool fabric was padded at 100% wet pick-up on Capillary electrophoresis
a Werner Mathis (Switzerland) HVF padder with the Capillary electrophoresis (CE) is a technique which can be
pretreatment solution containing 20 g ⁄ dm)3 sodium used to identify the components in a solution according
metabisulphite, 20 g ⁄ dm)3 thickener carboxymethyl to their different mobilities; mobility in the electric field
cellulose, 300 g ⁄ dm)3 urea and 5 g ⁄ dm)3 Alcopol O 60 depends on component size ⁄ mass-to-charge ratio.
(Huntsman, UK) and then dried at 60 C. The CE equipment (Dionex, USA) used in this study has
a fused silica capillary with an internal diameter of 50 lm
Ink-jet printing and a length of 47 cm from injection point to detector. The
The ink-jet printing was carried out on an HP Apollo P- voltage power applied was 20 kV and the buffer employed
1200 desktop printer at 600 dpi using the ink formulated was 10 mM potassium dihydrogen phosphate at pH 9.0
according to the recipe: 100 g ⁄ dm)3 Drimarene K dye, adjusted using 1 M sodium hydroxide.
300 g ⁄ dm)3 N-methylmorpholine N-oxide, 20 g ⁄ dm)3 2- When high voltage is applied, the cations migrate to the
pyrrolidone and 25 g ⁄ dm)3 propan-2-ol [9]. cathode and carry the bulk solution, a phenomenon termed
The ink was made up to 1 dm3 with distilled water and electroosmotic flow (EOF). In the case of positively charged
buffered to pH 7.0 using phosphoric acid. The dyes used components, their electrophoretic mobility is in the same
in this study were of commercial grade dye and were not direction as the EOF, so they arrive at the detector quickly;
purified unless otherwise indicated. in the case of negatively charged components, their
electrophoretic mobility lies in the opposite direction to
Fixation the EOF, hence their arrival at the detector is retarded.
The printed fabric was batched at 25 C under moist Neutral components are not affected by the electric field
conditions, which were provided by interleaving with a and so they arrive at the detector with the EOF front [10].
moist cotton fabric padded with distilled water at a wet
pick-up of 100%. Ultraviolet–visible spectrometer
The ultraviolet–visible (UV–vis) absorbance of the dye in
Washing off aqueous solution was measured using a Perkin Elmer
The printed, batched wool fabric was washed with cold Lambda 40 UV–vis Spectrometer (UK) in order to
water until no colour could be removed; hot washing was calculate dye concentration in the various wash-off
carried out on a Roaches Pyrotec-S temperature dyeing solutions and thus to determine fixation (degree of dye–
machine (Roaches, UK) with a solution containing fibre covalent bonding). Two identical printed fabrics
2 g ⁄ dm)3 Sandozin NIE and 5 g ⁄ dm)3 sodium bicarbonate with a size of 20 · 8 cm at 600 dpi were used to calculate
(NaHCO3) at 60 C for 15 min, after which the fabric was the per cent fixation: one was washed off immediately
rinsed again in running tap water for 10 min. after printing to obtain the total amount of the dye
printed on the fabric and the solution was diluted to
Modification of the Drimarene K dye 500 cm)3; the other one was used for batching followed
Drimarene K contains the 2, 4-difluoro-5-chloropyrimidine by washing to obtain the amount of the dye washed off
reactive group which is able to react with 4-hydroxy- after the fixation process and the washing solution was
benzensulphonic acid sodium salt by a nucleophilic diluted to the same volume of 500 cm)3. The absorbance
substitution reaction mechanism (Scheme 1). of the printed dye solution A0 and absorbance of the
H H
D N N F D N N O SO3Na
N + HO SO3Na N
Cl Cl
F F
Scheme 1
ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190 185
14784408, 2009, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1111/j.1478-4408.2009.00195.x by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [30/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Clark et al. Ink-jet printing on wool fabrics
wash-off solution A at the wavelength of maximum cysteine thiol groups in the wool by breaking some of the
absorption kmax were used to obtain the per cent fixation disulphide bonds crosslinking the wool structure; also, it
(%F) according to Eqn 1. is an effective reducing agent which can be used to bleach
the wool and thus reduce any fabric yellowness [16].
% F ¼ ðA0 AÞ=A0 100 ð1Þ
O O H2O O O
NaO S S Na O S H + HO S + 2Na
O O O O
Scheme 2
NH NH NH NH
HC CH2 S S CH2 CH + NaHSO3 HC CH2 SH + HC CH2 SSO3Na
CO CO CO CO
Cystine Cysteine
Scheme 3
H H
D N N F D N N S Wool
+ HS Wool
N N
Cl Cl
F F
Cysteine
Scheme 4
186 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190
14784408, 2009, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1111/j.1478-4408.2009.00195.x by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [30/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Clark et al. Ink-jet printing on wool fabrics
100 Ink stability of the FCP dye-based ink and the HBSA
Blue
Red
modified dye-based ink
80 Yellow The inks for both the parent and modified dyes were
formulated according to the ink recipe stated above. As
Yield, %
(a)
2.42x10–3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
(b)
1.36x10–3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
(c)
1.65x10–3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
(d)
1.58x10–3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
Figure 2 CE electropherogram of dyes: (a) commercial dye Drimarene Brilliant Red K-4BL; and Drimarene Red K-4BL ⁄ HBSA after
(b) 30-min reaction; (c) 60-min reaction; (d) 120-min reaction
ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190 187
14784408, 2009, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1111/j.1478-4408.2009.00195.x by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [30/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Clark et al. Ink-jet printing on wool fabrics
(a)
2.10x10–3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
(b)
2.31x10–3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
Figure 3 CE electropherogram of (a) fresh modified dye-based ink and (b) after 1 year of storage
(a)
1.98x10-3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
(b)
2.07x10-3
AU
0
0 2.0 4.0 6.0 8.0 10.0 12.0 14.0
Minutes
Figure 4 CE electropherogram of (a) fresh parent dye-based ink and (b) parent dye-based ink after 1 year of storage
100
Dye–fibre covalent bonding efficiency of the modified Blue
Red
dyes following ink-jet printing on wool substrate
80 Yellow
The fixation values (% fixation) obtained following wool
fabric printing with the three modified dyes and batching
Fixation , %
188 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190
14784408, 2009, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1111/j.1478-4408.2009.00195.x by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [30/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Clark et al. Ink-jet printing on wool fabrics
60
solution decreases, as do the reactive sites on the wool
40 fibres; therefore, the per cent fixation values level off to a
constant value.
20
Colour fastness tests
0 Washing fastness test was carried out according to the
2 4 6 8
Time, hours Woolmark test method 250; the results are shown in
Table 1. The change in shade was small, resulting in a grade
Figure 6 Per cent fixation values for the parent dyes vs batching of 4–5 to 5; there was no staining on the adjacent fabrics,
time except a light staining from the yellow dye on the cotton.
The excellent washing fastness is because of the strong
covalent bonding between the dye and the wool fibre.
Rubbing fastness test was carried our according to the
Table 1 Washing fastness of the modified Drimarene K dyesa
Woolmark test method 165 and the results are shown in
Table 2. The dry rubbing fastness can obtain the maximum
Staining
of 5 for all the modified dyes while the wet fastness varies
Change from 4–5 to 5. The good rubbing fastness is also due to the
Modified dye in shade CA C N P A W
strong covalent bonding of the dye on the wool fibre.
Light fastness was carried out according to the
Red K-4BL 5 5 5 5 5 5 5
Woolmark test method 5, using a QSun 1000 Xenon test
Yellow K-2R 4–5 5 4–5 5 5 5 5
Blue K-BL 4–5 5 5 5 5 5 5 chamber with irradiance of 0.65 W/m2 at a temperature of
45C. The prints for the Modified Drimarene K dyes were
a CA, cellulose acetate; C, cotton; N, nylon 6, 6; P, polyester; A, acrylic; tested to Blue Wool reference nos 5 and 6. As seen from
W, wool Table 3a,b, all of the dyes used in this work can pass
grade 5; moreover, the yellow dye can pass grade 6.
In general, the parent dye-based inks were either the
same grade or 0.5 grade lower when compared with the
Table 2 Rubbing fastness of the modified Drimarene K dyes
modified dye ink prints for all the fastness tests.
Warp Weft
Conclusions
The modification of Drimarene K dyes by reaction with 4-
Modified dye Dry Wet Dry Wet
hydroxybenzensulphonic acid sodium salt is an effective
method to improve their ink-jet printing ink stability. The
Red K-4BL 5 4–5 5 4–5
Yellow K-2R 5 4–5 5 4–5 modified dye-based inks show excellent solubility and
Blue K-BL 5 5 5 5 stability during storage for up to 1 year. Because of the
bisulphite present from the fabric preparation, a high
Table 3 Light fastness of the modified Drimarene K dyes under Blue Wool standard no. 5 (a) and no. 6 (b)
Modified dye Greyscale rating contrast 4 Greyscale rating contrast 3 Mean Action
(a)
Red K-4BL 4+ 3+ 5+ Pass
Yellow K-2R 4+ 3+ 5+ Pass
Blue K-BL 3–4 3 5 Pass
Modified dye Greyscale rating contrast 4 Greyscale rating contrast 3 Mean Action
(b)
Red K-4BL 3–4) 2–3) 6) Fail
Yellow K-2R 3–4 2–3 6 Pass
Blue K-BL 3–4) 2–3) 6) Fail
ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190 189
14784408, 2009, 3, Downloaded from https://onlinelibrary.wiley.com/doi/10.1111/j.1478-4408.2009.00195.x by Egyptian National Sti. Network (Enstinet), Wiley Online Library on [30/10/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Clark et al. Ink-jet printing on wool fabrics
degree of fixation was obtained for the printed samples 5. L Nicoll, in Digital Printing of Textile, Ed. H Ujiie
after 2 h batching at 25 C; this is a big advantage, as the (Cambridge: Woodhead Publishing Limited, 2006) 201.
6. J Provost, M Frenche, U Hees, M Kluge and J Weisre, in
new process allows ink-jet printing of wool to be carried Textile Ink Jet Printing, Eds T L Dawson and B Glover
out without the need for steaming. The printed samples (Bradford: SDC, 2004) 57.
show good colour fastness to washing, rubbing and light. 7. FR1283172 (ICI; 1962).
8. H A Riehen, H F Bottmingen and H M Riehen, CH464396
(Geigy; 1968).
Acknowledgements 9. D M Lewis and P J Broadbent, Proc. SDC Col. Conf., Belfast,
This work was carried out through a PhD scholarship UK (2006).
10. K D Altria, Capillary Electrophoresis Guidebook: Principles,
awarded under the China Australia Wool Innovation Operation, and Applications (USA: Humana Press, 1995).
Network (CAWIN) project. Funding for this project was 11. Woolmark Test Method 5: Colour Fastness to Light (Australia:
provided by Australian wool producers and the Australian Woolmark, 2000).
Government through Australian Wool Innovation Limited. 12. Woolmark Test Method 250: Colour Fastness to Hand
Washing (Australia: Woolmark, 2002).
13. Woolmark Test Method 165: Colour Fastness to Rubbing
References (Australia: Woolmark, 2002).
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190 ª 2009 The Authors. Journal compilation ª 2009 Society of Dyers and Colourists, Color. Technol., 125, 184–190