© December 2015| IJIRT | Volume 2 Issue 7 | ISSN: 2349-6002

Dyeing of cotton using reactive dyes without Salt

V.Ilango
Head of the department, Department of Textile Technology (MMF), SSM Polytechnic College,
Komarapalayam

Abstract - In this study 3-chloro-2-hydroxypropyl the fiber. Many studies devoted to improving the
trimethyl ammonium chloride was used as a cationic dyeability of cotton fibers have used quaternary
agent to cationize cotton fabric by a pad-batch process. cationic agents having various reactive groups (e.g.
The cationized cotton samples were dyed with different
epoxy and chlorotriazine) [2-4]. The most common
reactive dyes containing various reactive groups. The
approach is via reaction of various types of fiber-
dyeability of the cationized cotton samples with reactive
dyes without salt was significantly improved due to an reactive substituted amino compounds [5-12]. By
increase in the ionic attraction between the dye and introducing amino groups, the cellulose fiber will be
cationized cotton. The results showed that the wash and cationized giving high substantivity for anionic dyes
dry rubbing fastness of the cationized cotton dyed with due to columbic attraction between the positive charge
different reactive dyes are similar to those of the on the fiber and the negative charge on the anionic
untreated cotton. However, the light fastness of some of dyes. This cationized cotton could be dye able with
the cationized fabric samples was improved. reactive dyes under neutral or mild acidic conditions
in the absence of electrolyte in the dye bath. It is also
Index Terms - Salt, Reactive dye, Cotton, Cationization,
known that cotton treated with modified poly
Fastness, Pre-treatment
carboxylic acid can be dyed with different anionic
dyes such as acid, direct and reactive dyes under
INTRODUCTION
specific dyeing conditions [13].
Catinization of cotton with UV curable monomers
Cellulose fibers when they come in contact with water
produced a large increase in dye-ability with anionic
produce slightly negative charge due to the ionization
dyes. This is due to the introduction of dye/fiber ionic
of hydroxyl groups, whereas most of the dye classes
interaction [14]. Hebeish et al. [15] and Eleftheriadis
suitable for cotton are anionic (such as reactive and
et al. [16] reported that quarternization of 2-vinyl
direct dyes) in solution. The slightly negative charge
pyridine grafted to cotton with epichlorohydrin or an
on the fibers results in repulsion of anionic dyestuffs
alkyl bromide could enhance the exhaustion values of
and thus the exhaustion of the bath is limited.
reactive and/or direct dyes towards the limited value
Therefore, in dyeing of cotton with anionic dyes, a
of 95-100 %. Wang and Lewis synthesized a new fiber
large amount of electrolyte, such as Glauber’s salt or
reactive quaternary compound containing an
sodium chloride is required in order to reduce the
acrylamide residue. This can be applied to cotton
charge repulsion between the negatively charged
fabrics via pad-dry-cure under alkaline conditions.
cotton and the anionic dyes. However, normally not all
The treated cotton can be dyed with reactive dyes
the dye in the dye bath is exhausted, thus causing
without additives such as salt or alkali. Reactive dyes
environmental problems due to the discharge of
can be exhausted almost entirely onto the treated
effluent that is colored as well as having a high salt
cellulose fiber [17]. In this study various reactive dyes
concentration. Chemical modification of cotton in
with three different reactive groups including
order to improve its dyeability without the large
monochloro triazine, dichloro triazine and vinyl
amount of salt has been considered for a long time.
sulphone were applied onto the cationized cotton
Pre-treating the cellulose fibers with reactive cationic
fabrics. The cationic agent used for modification was
agent could diminish or eliminate the amount of
2,3- epoxypropyl trimethylammonium chloride
electrolyte required [1]. Chemical modification of
(EPTMAC). This compound will react with cotton
cotton is generally performed by reaction with the
under alkaline conditions to form a cationized cotton
functional groups (hydroxyl groups) already present in

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 © December 2015| IJIRT | Volume 2 Issue 7 | ISSN: 2349-6002

fiber. The dyeability and fastness properties of the reactive dyeing with monochlorotriazine reactive
cationized cotton with different reactive dyes were groups, 1 % o.w.f. dye was added to a room
investigated. temperature dye-bath. The fabric sample was then
added and the bath was heated to 80o C at a rate of
EXPERIMENTAL MATERIALS 1.5o C/min. Before approaching to 80 o C, sodium
sulphate (40 g/l) was added in two portions at 55 o C
Plain weave cotton fabric (desized, scoured and and 65 o C. After holding the temperature at 80 o C for
bleached) was used for this work. Cationizing agent, 10 min, 3 g/l of sodium carbonate was also added. The
3-chloro-2-hydroxypropyltrimethylammonium bath was held at 80 o C for 50 min, cooled to 60 o C
chloride (Fluka) is commercially available as a 65 % at a rate of 2.5 o C/min and then discarded. Dyeing of
solution in water and was used as received. Sodium untreated cotton with vinyl sulphone and
hydroxide, sodium carbonate, acetic acid and sodium dichlorotriazine reactive dyes was performed at 60 o
sulphate were all of laboratory reagent grade (Merck). C. The fabric sample and 1 % o.w.f. dye were added
Tinegal W (Ciba) was used as detergent. The reactive to a 60 o C dyebath and after 20 min 40 g/l of sodium
dyes used with different reactive groups including sulphate added, and 10 min later 3 g/l of sodium
monochlorotriazine, dichlorotriazine and carbonate was also added. The bath was then held at
vinysulphone are listed in Table 1. All reactive dyes 60 o C for 60 min and discarded. The dyed samples
were from Ciba representative in Iran. were rinsed with 50 o C water and divided into two
Table 1. Different reactive dyes used equal portions. One portion was soaped in a solution
containing Tinegal W (1 g/l) and sodium carbonate (1
g/l) at the boil for 15 min at 40:1 liquor to goods ratio.
The fabric was rinsed once with 50 o C water, and once
with cold water. The other portion was left unsoaped.
The procedure for dyeing cationized cotton with
reactive dyes was the same as that for the untreated
cotton (as outlined above), except dyeing cationic
cotton was performed in the absence of salt.

Dye Exhaustion and Fixation

Pre-treatment of Cotton The dye uptake by the cotton was determined using a
The solution consisting of 35 g/l of 3-chloro-2- UVvisible light spectrophotometer and the dye-bath
hydroxypropyltrimethylammonium chloride absorbance was measured at the wavelength of
(CHPTMAC) (65 % w/w) and 15 g/l of sodium maximum dye absorption (λmax). The percentage of
hydroxide was applied to the well-prepared cotton dye-bath exhaustion (E) was calculated using Eq. (1)
fabric. The wet pick up was 100 %. To minimize the [17]
hydrolysis of reactant, the alkali was added to the bath
just before application. The padded fabric was put in
plastic bag to prevent chemical migration and water where A0 and A are the absorbance of the dye solution
evaporation. The fabric was stored at room at the maximum wavelength before and after the
temperature for 24 hr, and then rinsed several times process, respectively. The use of reflectance values
with water and finally neutralized with a dilute acetic (R) to determine the concentration of dye in the fabric
acid (1 g/l). The final fabric pH was 7.6. is well established [18] and the relationship between R
and K/S is shown in Eq. (2).
Dyeing of Treated and Untreated Cotton
Laboratory dyeing with the reactive dyes was carried
out in Ahiba Texomat laboratory dyeing machine with The color strength of the dyed fabrics was expressed
liquor to fabric ratio of 40:1. Dyeing of untreated as K/S values obtained for the unsoaped and soaped
cotton with reactive dyes was performed according to fabrics. The fixation of adsorbed dye (F) was
the procedure offered by the manufacturer. For calculated using Eq. (3) and the total fixation of the

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 © December 2015| IJIRT | Volume 2 Issue 7 | ISSN: 2349-6002

original applied dye (T) was calculated using Eq. (4) the large amounts of electrolyte that is normally
[17]. needed to drive the dyes from the water onto the cotton
fiber. In this paper we used the nitrogen content
determination for proving cationization. The nitrogen
content of the untreated cotton was about zero but the
nitrogen content of the cationized cotton was about
0.06 %. This can prove the cationization of the sample
where the subscripts 1 and 2 indicate values obtained
by a quaternary ammonium salt
before and after soaping respectively. Fastness The
dyed samples were tested according to ISO standard
DYEING RESULTS
methods. The specific tests used were ISO 105
C01:1989, color fastness to washing; ISO 105-
Reactive dyes with various reactive groups were
X12:1993, color fastness to rubbing. Color change was
examined to assess their suitability for use on the
rated according to the appropriate gray scale. A light
treated cotton. The results showed that all of the dyes
fastness test was carried out using the ISO 105
employed gave an excellent exhaustion with 1 %
B02:1994, standard method and the degree of fading
o.w.f. and most of them showed a high fixation with
was assessed by SDC blue wool scales. Nitrogen
good levelness. Also, the reactive dyes were applied to
Content The percentage of nitrogen content of sample
untreated cotton according to the manufacturer
was determined by Micro Kejeldahl method [19].
recommendations. The results for three different
Results and Discussion Reaction of CHPTMAC with
dyeing methods are listed in Table 2. It can be seen
Cellulose 2,3-epoxypropyltrimethylammonium
that the exhaustion, fixation and color strength values
chloride (CHPTMAC) was prepared in situ by the
for the most dyes on the treated cotton is higher than
reaction of 3-chloro-2-
those on the untreated cotton. With exception of
hydroxypropyltrimethylammonium chloride with
Cibacron Brilliant Blue BR-P, all the dyes were
alkali as shown in
exhausted very well by the treated cotton. The fixation
values varied from dye to dye. In these dyeing
systems, the strong attraction between the cationic dye
sites on the modified cotton and the anionic dyes
existed which led to obtain a very high exhaustion
rates without addition of electrolytes to the dye-bath.
The color strength of most of the dyeing on the treated
cotton was often twice and in some cases up to four
times of untreated cotton. However, these high color
strength values might be partially attributed to surface
dyeing or ring dyeing. The wash fastness of the
cationized dyed cotton was similar to that of the
untreated dyed fabrics and the cross staining results
were good (see Table 3). The excellent light fastness
of the reported dyeing on cationic cotton is particularly
striking, since cationic pretreatments, as a general rule,
are known to impair light fastness. The cationic
Scheme 1.
pretreatment used here is nonpolymeric in nature and
EPTMAC will react with alcohols under alkaline
can be expected to penetrate the cotton fiber prior to
conditions to form ethers (Scheme 2) and will thus
fixation. This uniform modification of the fiber
produce a modified fiber when it reacts with cotton as
evidently allows for enhanced color yields and wash
shown in Scheme 3. As a result, cotton will have
fastness without adverse effect on the light fastness.
cationic dye sites covalently bound to the polymer
The rubbing fastness of both sets of samples was good.
chains. These dye sites will strongly attract anionic
The observation of the dyed samples also showed a
reactive dyes, enabling the use of these dyes without
good level of uniformity.

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Table 2. Results of reactive dyes on EPTMAC treated and untreated cotton fabrics

Table 3. Fastness of untreated and cationized cotton fabrics dyed with reactive dyes

Figure 2. Effect of electrolyte concentration on

Figure 1. Build-up properties of Cibacron Red HF for
exhaustion of Cibacron Red HF for treated cotton
treated and untreated cotton fabrics.
fabrics.

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INFLUENCE OF ELECTROLYTE IN DYEBATH

The effect of salt on the dyeing of the quarternized

cotton is shown in Figure 2. In the dye concentrations
applied to the fabrics well below the saturation limit of
the treated fibers, the degree of exhaustion decreased
with increasing salt concentration. For 2 % o.w.f.
Cibacron Red HF, the treated cotton gave 60 %
exhaustion of anionic dye in the absence of electrolyte,
but the exhaustion droped to 45 % after adding 20 g/l
of sodium sulphate. This unfavorable effect was
because of the sulphate anions which have a
significant affinity for qurternized cellulose and they
were able to compete with dye anions for the
quaternary sites in the modified fibers with increase in
salt concentration, as nearly all the quaternary sites are
occupied and the fiber became neutrally or even
negatively charged. In this way dye adsorption was the
same as the untreated cotton.

CONCLUSION

The cotton fabric treated with EPTMAC provides

cationic sites which can be dyed with reactive dyes
without electrolytes to give excellent results. Reactive
dyes can be exhausted almost entirely onto the treated
cellulose fibers. Dyeing on the treated cotton gave
better color strength than the comparable dyeing on
untreated cotton by the conventional method. The
color fastness of these dyeing is equal or superior to
that of some dyes on untreated cotton. The results on
the different reactive groups indicated that the type of
reactive groups of reactive dyes had no influences on
the dyeing properties of the cationized cotton fabrics.

REFERENCES

[1] D. P. Chattopadhyay, Indian J. Fibre Text. Res.,

26, 108 (2001)
[2] T. S. Wu and K. M. Chen, J. Soc. Dyers
Colourists,109, 153 (1993).
[3] X. P. Lei and D. M. Lewis, J. Soc. Dyers
Colourists, 106, 352 (1990).
[4] A. I. Vogel, “Elementary Practical Organic
Chemistry”, 2nd ed., Longman, London, 1975.
[5] J. Jang, S. W. Ko, and C. M. Carr, Color.
Technol., 117, 139 (2001)
[6] M. Rupin, Text. Chem. Colorist., 8, 139 (1976).

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