Journal of TextilesVolume 2013 (2013), Article ID 320510, 6 pageshttp://dx.doi.org/10.1155/2013/320510

Research Article

Exploratory Investigation of Chitosan as Mordant for Eco-Friendly Antibacterial Printing of Cotton with Natural Dyes

M. D. Teli, Javed Sheikh, and Pragati Shastrakar

Department of Fibers and Textile Processing Technology, Institute of Chemical Technology, Mumbai 400019, India

Received 27 May 2013; Accepted 7 August 2013

Academic Editor: Gajanan S. Bhat

Copyright © 2013 M. D. Teli et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

Although a lot of antibacterial finishes are available for cotton, the user safety and durability of the finish are always the important issues. Some of the natural dyes are known to possess antibacterial properties; however, most of them are nonsubstantive. Hence, they are used in conjunction with eco-friendly natural mordants. Although metallic mordants are effective, they are environmentally pollutants, hence not desirable. In the current work, the novel natural mordant like chitosan with different concentrations (10% and 20% of weight of fiber) was applied on cotton and fabric was printed with natural dyes such as catechu, turmeric, and marigold using screen printing method. All the three dyes were used in powder form in print paste with different concentrations (1%, 5%, and 10%) and guar gum was used as thickener. The printed samples using chitosan as a mordant showed the equivalent color values to that of prints obtained using alum as a mordant. The printed fabric showed excellent antibacterial activity against both gram-positive and gram-negative bacteria. The method may be considered suitable for eco-friendly printing and antibacterial finishing of textile materials.

1. Introduction

Textiles, especially those made of natural fibers, are an excellent medium for the growth of microorganisms when the basic requirements for their growth such as nutrients, moisture, oxygen, and appropriate temperature are present. The large surface area and ability to retain moisture of textiles also assist the growth of microorganisms on the fabric [1]. The growth of microorganisms on textiles inflicts a range of unwanted effects not only on the textile itself but also on the wearer. These effects include the generation of unpleasant odor, stains, discoloration in the fabric, a reduction in the tensile strength of the fabric, and an increased likelihood of contamination [2]. In the last few decades, with the increase in new antimicrobial fiber technologies and the growing awareness about cleaner surroundings and healthy lifestyle, a range of textile products based on synthetic antimicrobial agents, such as triclosan, metal and their salts, organometallics, phenols, and quaternary ammonium compounds, have been developed and quite a few are also available commercially [3]. Even though the excellent antimicrobials are available, their user ecology is always a question. Some of the natural dyes are reported to possess antimicrobial properties.

Synthetic dyes are here to remain as one can tailor make them depending upon the required hue, substantivity, and fiber. The development of synthetic dyes at the beginning of the twentieth century led to a more complete level of quality and more reproducible techniques of application. As a result, a distinct lowering in the dyestuff costs per kg of dyed goods was achieved [4]. Also, a full gamut of color is available for application on various types of fibers.

However, during the last few decades, the use of synthetic dyes is gradually receding due to an increased environmental awareness and harmful effects, of either toxic degraded products or their nonbiodegradable nature. In addition to previously mentioned, some serious health hazards like allergenicity and, carcinogenicity are associated with some of the synthetic dyes based on azo chromophores. As a result, a ban has been imposed all over the world including European Economic Community (EEC), Germany, USA, and India on the use of some synthetic dyes (e.g., azodyes) which finally triggered active research and development to revive world heritage and traditional wisdom of employing safer natural dyes [5]. Consumers nowadays are becoming more and more concerned about environmental issues and hence are demanding for natural product incorporating natural ingredient. Due to increasing awareness of environmental issues and pollution controls, natural dyes are gaining importance as they are obtained from renewable resources and they present no health hazards and some of them sometimes act as a health care product [6]. Hence, it is important to understand that, although natural colors cannot substitute use of synthetic dyes completely, there is definitely increasing market for such complete eco-friendly dyed or printed materials.

Natural dyes with a few expectations are nonsubstantive and hence must be used in conjunction with mordants. Mordant is a chemical, which can fix itself on the fiber and also combines with the dyestuff. The challenge before the natural dyers in application of natural color is the necessity to us metallic mordants which themselves are pollutant and harmful. Due to the environmental hazard caused by metallic mordant while dyeing of textile fabric, dyers are always looking for safe natural mordant for natural dyes. In this paper, this issue of screening a natural mordant for printing is explored.

The main objective of printing is to produce colored patterns with sharp boundaries on textile materials without any dye spreading beyond the boundaries of the motif of design [7]. Although a lot of research has been reported in the area of printing and natural dyeing of textiles, the research in the area of natural dye printing is reported to a limited extent. Also application of natural dye prints as antibacterial finish has also remained unexplored. The applications of chitosan for different applications in textiles are reported [8–24], but the application of such functional biopolymer as a mordant in natural dyeing has been quite rare in the literature. In the current work, chitosan extracted from waste shrimp shells [24] was utilized as a mordant for simultaneous natural dye printing and antibacterial finishing of cotton in comparison with commonly used metal mordants. The efficacy of chitosan as ecofriendly mordant and antibacterial finish has been studied. The antibacterial activity against both gram-positive and gram-negative bacteria has also been screened.

2. Materials and Methods

2.1. Materials

Chitosan (mol. wt. 124999.8, degree of deacetylation, 89.06%, nitrogen content, 7.1%) was extracted from waste shrimp shells [24] and used for the study. Ready for dyeing (RFD) Cotton fabric (Plain weave, EPI-69, PPI-88, GSM-122.95) was purchased from the market. Catechu, turmeric, and marigold were purchased from the market. All other chemicals used were of laboratory grade.

2.2. Methods

2.2.1. Preparation of Mordant

Stock solutions of alum and CuSO₄ were made by dissolving in double distilled water. Chitosan was dissolved in aqueous acetic acid (20 grams per liter, gpl). Chitosan powder was added to acetic acid solution followed by warming at 60°C for 2 h with continuous stirring using mechanical stirrer.

2.2.2. Preparation of Dye for Printing

All the dyes used were first converted to powder form. For this purpose, catechu, turmeric, and marigold were first dried in an oven at 50° for 24 h and later grinded in mixer grinder. The powder so obtained was filtered through the 60 mesh nylon fabric. The fine powder of natural dye was used for printing.

2.2.3. Mordanting of Cotton Fabric

Mordanting of cotton was carried out with different mordants at two different concentrations on the weight of fabric (alum; 10% and 20%, copper sulphate; 1% and 2%, and chitosan; 10% and 20%) at 90°C for 60 mins with material to liquor ratio as 1 : 30. The mordanted fabric was squeezed and dried in open width form at 100°C for 5 mins and then used for printing.

2.2.4. Printing

The stock paste of guar gum was prepared using 2% of guar gum powder. The guar gum powder was sprinkled slowly in water with continuous stirring in order to prevent lump formation. The paste was stirred continuously at 90°C for 1 h.

The print paste was prepared in different dye concentrations (1%, 5%, and 10%) on the basis of print paste. For preparation of 1% of print paste, 1 gm of dye powder was first pasted with small quantity of water followed by addition of 99 gm of guar gum stock paste. The print paste was continuously stirred for 30 mins. The mordanted cotton fabrics were then printed with two strokes of squeeze, steamed at 102°C for 10 mins. The samples were washed with water and then dried in air.

2.3. Analysis of Printed Fabrics

2.3.1. Color Value by Reflectance Method

The printed samples were evaluated for the depth of color by reflectance method using 10-degree observer. The absorbance of the dyed samples was measured on Spectraflash SF 300 (Datacolor International, USA) equipped with reflectance accessories. The values were determined using expression where is the reflectance at complete opacity, is the absorption coefficient, is the Scattering coefficient

Dyed fabrics were simultaneously evaluated in terms of CIELAB color space (, and ) values using the Rayscan Spectrascan 5100+. In general, the higher the value, the higher the depth of the color on the fabric. corresponding to the brightness (100 = white, 0 = black), to the red-green coordinate (+ve = red, −ve = green), and to the yellow-blue coordinate (+ve = yellow, −ve = blue). As a whole, a combination of all these parameters enables one to understand the tonal variations.

2.3.2. Washing Fastness

Evaluation of color fastness to washing was carried out using ISO II methods [25]. A solution containing 5 gpl soap solution was used as the washing liquor. The cotton samples were treated for 45 min at 50°C using material to liquor ratio of 1 : 50 in rota machine. After rinsing and drying, the change in color of the sample and staining on the undyed samples was evaluated on the respective standard scales (rating 1 : 5; where 1: poor; 2: fair; 3: good; 4: very good and 5: excellent).

2.3.3. Light Fastness

Printed cotton fabric was tested for color fastness to light according to ISO 105/B02 [26]. The light fastness was determined using artificial illumination with Xenon arc light source, Q-Sun Xenon Testing Chamber with black standard temperature of 65°C with relative humidity of the air in the testing chamber as 40% and daylight filter, wavelength,  nm. The cotton samples were compared with the standard scale of blue wool reading (ratings, 1 : 8; where 1: poor; 2: fair; 3:moderate; 4: good; 5: better; 6: very good; 7: best and 8: excellent).The color fastness to light was measured using test method.

2.3.4. Determination of Antibacterial Activities of Printed Fabrics

The antibacterial activity of the printed fabrics was estimated by AATCC Test Method  100-2004 [27].

3. Results and Discussion

3.1. Color Values of Natural Dye Printed Cotton

The efficacy of chitosan as mordant was screened in comparison with metal mordants and the results are summarized in Tables 1, 2, and 3.

Table 1: Effect of mordants and catechu concentration on color strength of cotton.

Mordant (%)
Catechu
Colour value
CIE colour coordinates
Washing fastness
Light fastness

(%)

Change
Staining

Alum

    10
1
0.2514
81.626
4.566
8.739
5
5
6

    10
5
0.6024
83.211
4.991
11.255
5
4-5
7

    10
10
1.0746
83.757
5.434
12.167
4-5
4-5
7

    20
1
0.299
82.104
3.562
8.851
4-5
4-5
6

    20
5
0.5852
83.216
5.055
11.454
4-5
4
7

    20
10
1.1067
83.842
5.752
12.448
4
4
7

Chitosan

    10
1
0.3363
79.477
4.235
9.042
5
5
6

    10
5
0.5287
78.845
6.323
8.972
5
5
6

    10
10
1.0201
79.248
7.689
10.13
4-5
4-5
7

    20
1
0.4182
78.529
4.718
7.628
4-5
4-5
7

    20
5
0.8044
79.117
7.286
9.349
4-5
4-5
7

    20
10
1.3245
79.183
8.214
9.867
4-5
4
7

Copper sulphate

    1
1
0.7087
72.994
6.824
14.267
4-5
5
7

    1
5
1.6571
71.891
9.586
13.176
4-5
4-5
7

    1
10
3.0619
73.111
9.882
14.614
4-5
4
7

    2
1
0.6359
72.575
6.913
13.488
4
4-5
7

    2
5
3.7264
73.109
10.569
14.928
4
4
7

    2
10
3.7948
72.734
10.114
14.604
4-5
4
8

Table 2: Effect of mordants and turmeric concentration on color strength of cotton.

Mordant (%)
Turmeric (%)
Colour value
CIE colour coordinates
Washing fastness
Light fastness

Change
Staining

Alum

    10
1
0.8084
84.007

33.849
4-5
4-5
3

    10
5
4.3847
89.655
2.389
43.257
4-5
4
3

    10
10
5.9102
90.404
1.295
44.146
4
4
3

    20
1
0.937
84.934
4.716
35.625
4
3-4
3

    20
5
3.7634
90.364
3.028
44.609
4-5
3-4
3

    20
10
7.9375
91.327
3.129
45.076
4
4
4

Chitosan

    10
1
1.1319
83.174
5.348
39.866
5
4-5
3

    10
5
2.4573
84.203
1.755
42.078
4-5
4-5
4

    10
10
6.3261
86.902
1.418
45.928
4-5
4
4

    20
1
1.1838
81.587
3.784
37.307
4
4
3

    20
5
2.4426
84.3
0.586
42.285
4
3-4
3

    20
10
6.6156
87.28
1.097
46.202
4
4
4

Copper sulphate

    1
1
0.6626
81.256
3.234
27.299
4-5
4
5

    1
5
2.6011
87.844
3.495
37.35
4-5
4
5

    1
10
5.0764
89.695
4.177
39.489
4-5
3-4
5

    2
1
0.7542
82.015
3.598
28.505
4
3-4
5

    2
5
4.0985
88.032
2.253
37.751
3-4
3-4
5

    2
10
7.3138
89.973

40.382
4
3-4
6

Table 3: Effect of mordants and marigold concentration on color strength of cotton.

Mordant (%)
Marigold (%)
Colour value
CIE colour coordinates
Washing fastness
Light fastness

Change
Staining

Alum

    10
1
1.1593
81.411
2.234
32.553
5
4-5
6

    10
5
3.6119
85.186

36.621
4-5
4
6

    10
10
6.2023
86.014
1.086
37.852
4-5
3-4
7

    20
1
1.1186
80.382

31.881
4-5
3-4
6

    20
5
4.3349
85.02
0.058
37.712
4
3-4
7

    20
10
7.2649
86.29
0.494
38.388
4-5
4
7

Chitosan

    10
1
1.3023
72.346
1.266
21.601
5
5
7

    10
5
2.2313
76.981
0.533
24.224
5
4-5
7

    10
10
3.4716
78.828
2.247
28.088
4-5
4-5
7

    20
1
1.5061
74.502
0.916
23.481
5
4-5
7

    20
5
3.5484
78.269
2.107
26.801
4-5
4-5
7

    20
10
4.561
78.963
3.354
28.089
4-5
4
7

Copper sulphate

    1
1
1.0403
74.96
2.073
22.475
5
5
7

    1
5
3.0923
78.166
1.362
26.119
5
5
7

    1
10
7.7622
81.004
0.148
29
4-5
4-5
7

    2
1
1.4072
75.411
1.78
23.091
4
4
7

    2
5
4.9077
79.504
1.514
28.381
4-5
4
7

    2
10
12.4811
82.349
0.323
30.92
4
4
7

The initial attempt was to explore the role of chitosan as a mordant for the localised coloration (printing) with natural dyes in the study. For this purpose, the cotton fabric was printed with all the three dyes with and without mordants. The prints were very light in shade and the color bled heavily after washing where mordants were absent. However, in case of chitosan, like other metal mordants, the color values obtained were higher and the prints were washed fast and this trend was valid for all the three dyes studied. The observations confirmed the role of chitosan as a mordant in natural dye printing. The role of chitosan as a mordant may be attributed to the presence of amino groups which get protonated and offer the sites for attachment of the dye which is mainly anionic in nature. The mechanism of dye attachment to the fiber is similar to that in case of metal mordants.

The mordant concentrations used were 10 and 20% for alum and chitosan and 1% and 2% for CuSO₄. The results in Tables 1–3 indicate the dye specific trends of color values. In case of catechu as a dye, CuSO₄ showed the highest color values among the mordants. However, the color values for chitosan and alum mordants were comparable. In case of turmeric, alum mordant showed highest color values while in case of marigold CuSO₄ showed highest color values. The varying combinations of mordant and dye resulted in different shades and tones of dyed cotton fabric. In case of all the dyes and mordant combinations, keeping the dye concentration constant, the increasing mordant concentrations resulted in increasing color values. The same trend was valid when dye concentration was varied keeping mordant concentration constant.

The fastness properties of the printed cotton fabrics were studied and the results are presented in Tables 1–3 which indicate the comparative fastness properties in the case of all the mordants. The only dyed samples showed much inferior fastness properties which were improved with mordanting (irrespective of the type) which indicate the positive role of mordant in holding the dye on fabric. The improvements in fastness properties with mordant concentration clearly indicate the positive role of mordants in case of natural dyes. The washing fastnesses obtained varied in the range of good to excellent grades. Light fastness was found to be improving with improving values. CuSO₄ showing very high light fastness as well as high degree of antibacterial activity which may be attributed to its positive contribution in improving the stability of dye-metal complex to light as well as its known toxic nature.

3.2. Antibacterial Activity of Printed Cotton Fabric

The quantitative antibacterial assessment was made using AATCC-100(2004) test method and the results are presented in Table 4.

Table 4: Effect of mordant and dye combinations on antibacterial properties.

Mordant
Mordant conc. (%)
Dye
Dye conc.
Bacterial reduction (%)

(% of print paste)
S. aureus
E. coli

Alum
20
Catechu
10
98.25
97.50

Chitosan
20
10
99.75
99.80

CuSO₄
2
10
100
100

Alum
20
Turmeric
10
98.25
97.00

Chitosan
20
10
99.25
99.10

CuSO₄
2
10
100
100

Alum
20
Marigold
10
99.50
99.00

Chitosan
20
10
99.90
99.75

CuSO₄
2
10
100
100

Represents average value of 3 determinations.

The results for mordanted and printed fabrics indicate the excellent antibacterial activity for all the mordants. The cotton fabric showed no antibacterial activity against both S. aureus and E. coli.

As far as antibacterial activity is concerned, the chitosan mordanted samples showed comparative antibacterial activity with that of CuSO₄ and higher activity than that of alum in case of all the dyes studied. Chitosan is known for antibacterial activity against broad spectrum bacteria and mechanism of antibacterial activity was explained by researchers [12, 28]. The chitosan hence can be claimed as eco-friendly mordant cum antibacterial finishing agent for cotton.

4. Conclusion

The concept of printing of cotton fabric with natural dyes in fine powder form was successfully carried out using chitosan as an eco-friendly mordant. The color values varied with the dye mordant combination; however, the chitosan mordant showed good color values. The excellent antibacterial activity was displayed by the printed samples. The printed cotton also displayed excellent fastness properties. The role of chitosan as a mordant in natural dye printing has been confirmed through this study. The proof of demonstration of concept sample can open door for further research to develop antibacterial printed cotton using natural dyes.

Conflict of Interests

The authors do not have any stake in Data color international or AATCC and their names appear in the paper purely in coincidental and academic nature. Their reference is made to indicate a standard equipment and test method were made use of in this work and in no way it advocates these brands.

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