RJTA Vol. 11 No.

3 2007

Modification of Cotton Fibers with Sericin Using Non-Formaldehyde Released Crosslinking Agents
Arunee Kongdee* and Nuchsirapak Chinthawan Department of Chemistry, Faculty of Science, Maejo University, Chiang Mai, Thailand, 50290

ABSTRACT
Cotton fibers were modified with silk sericin in a pad-dry-cure process in this investigation. By using glutaraldehyde and dimethyloldihydroxyethylene urea as crosslinking agents, sericin was successfully bound to cotton fibers as seen from IR absorption bands at 1515 and 1546 cm-1, and 1687 cm-1 which corresponded to NH and -C=O of sericin respectively, and the bands at 1747, 1789 and 1750 cm-1 indicated C=O of the regenerated functional groups. The examination of the modified fibers by Scanning electron microscope showed round fibers and deposited sericin on cotton fiber surfaces. The modification of cotton fibers with sericin using these crosslinking agents was clearly proved by dyeing with an acid dye. In samples treated with sericin, the increase in the color strength and b-values, and the decrease in L-values were the proof of the reaction between cellulose and sericin using glutaraldehyde and dimethyloldihydroxyethylene urea as crosslinking agents. With increasing sericin concentration in finishing solutions, further increases in the color strength and b-values and decrease in L-values were investigated. The presence of sericin in cotton fibers might improve its comfortablity with regard to the changed fiber surfaces. The modified cotton fibers from this investigation may be useful for the development of medical textiles, for instance, gauze and pad dressing as their high moisture absorbency and smooth surfaces. Keywords: Cotton fibers, sericin, glutaraldehyde, DMeDHEU, color strength, water retention

1.

Introduction

Sericin, also known as silk gum protein, is produced by silkworms. In raw silk, the major component is fibroin (approximately 70%), and approximately 30% of the component is sericin. Due to the many reactive groups such as hydroxyl, carbonyl and amino groups which are composed of sericin, sericin shows special reactivities and properties. The use of sericin in many applications such as cosmetics, membrane, food industries, support for immobilized enzyme and medical materials have been reported (Zhang, 2002). In textile, it has been used for the functionalization of natural and synthetic fibers in order to improve water absorbency and smooth surface (Yoshiharu et al., 2001; Tadashi et al.,
____________________ * Corresponding author. Tel.: 66 5387 3544; Fax: 66 5387 3548 E-mail address: arunee.k@mju.ac.th (Arunee Kongdee)

2001; Jin et al., 1993). Polyester fibers have been modified with sericin by crosslinking with glyceryl polyglycidyl ether and diethylene triamine (Yamada et al., 1993). Fibroin-mixedsericin wound dressing has been developed to accelerate healing; it has been peeled off without disturbing new formed skin (Tsubouchi, 1999). Sericin has been found to improve moisture regain and water retention, and reduce electrical resistivity of cotton fibers by using dimethyloldihydroxyethylene urea (DMDHEU) as crosslinking agents (Kongdee et al., 2005). In this investigation, cotton fibers were selected to keep moisture absorbency; they were modified with sericin for biomedical purposes. As DMEHEU is a formaldehyde-released crosslinking agent for cotton fibers which could cause irritation, in this present work, we attempt to substitute it by non-formaldehyde released crosslinking agents such as glutaraldehyde (GD) and N,N-dimethyl-4,5-dihydroxyethylene urea (DMeDHEU). GD has been used as crosslinking
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for numerous materials such as chitosan, poly(ethyleneglycol-g-acrylamide), gelatin, whey, dextran, pullutan, cassava starch and sodium carboxymethylcellulose (Lee & Rosenberg, 1999, Parra et al., 2004; Agnihotri & Aminabhavi, 2006; Rokhade et al., 2006) whereas DMeDHEU is a free-formaldehyde based resin for dry cure process that crosslinks through hydroxyl groups of cellulose. We present GD and DMeDHEU here as substitutions of DMDHEU which is commonly used for cotton fiber modification (Bajaj, 2002). Modified cotton fibers were analyzed by Fourier transform infra-red spectrophotometer. Scanning electron microscope and dyeing method were used to prove the fixation of sericin onto cotton fibers.

was used in order to analyze functional group in the washed samples over 500-4000 cm-1. Scanning electron microscopy (Jeol, JSM5410LV, Japan) was used to examine the surface morphology of the washed samples. The samples were sputter coated with gold. Fabric morphology was performed on images at 1000 magnifications. Dyeing samples with acid dye were used to prove the fixation of sericin on cotton fibers. Samples (840 cm2) were dyed in 0.2% Supranol Gleb 4GL in an acetic acid solution at a liquor ratio of 1:100 at 60C for 30 minutes. After air drying, the color strength, and L- and b-values, of samples were measured using DataColor 650 spectrophotometer (USA).

2.

Experimental

Materials Magnesium chloride (AjaxFinechem, Australia), 50% v/v glutaraldehyde (Fluka, Switzerland), DMeDHEU (Clariant, Thailand), acetic acid (Merck, Germany) and Supranol Gleb 4GL acid dye (DyStar, Germany) were used without further purification. Sericin powder was prepared from degummed solution by spray dry. Preparation of treated cotton fabrics Ten recipes of finishing solutions composed of glutaraldehyde, DMeDHEU and sericin were prepared according to Table 1, and concentration of sericin varied from 25 to 50, 75 and 100 g/L. One hundred percent cotton fabrics (3040 cm2) was padded through the finishing solutions in a laboratory padder. The samples were then dried in a laboratory dryer at 100C for 2 minutes and cured at 160C for 2 minutes. The samples were throughly washed in distilled water at 70C for 30 minutes. For 0 g/L sericin, the fabrics were padded through the finishing solutions without sericin added, and it was treated as control. Characterizations and analyses of treated cotton fabrics A Vector 22 FTIR spectrophotometer (Bruker, Germany) equipped with attenuated total reflectance (ATR, MIRacleTM, Pike Technology)

3.

Results and Discussion

By finishing process, 74.36-81.13% pick up was obtained. The percentage of add-on in the range of 0.05-5.96 % was received (see Table 1). Figure 1 shows the results of the percentage of add-on of samples finished with GD and DMeDHEU. The percentage of add-on of the samples sharply increases with increasing concentration of sericin up to 100 g/L sericin; the increased tendency of percentage of add-on shows that sericin can be used for the modification at higher concentration. FTIR-ATR spectra of samples finished with GD and DMeDHEU are shown in Figures 2 and 3 respectively. The spectrum of samples treated with GD only is identical to that of the untreated ones while that of the samples treated with the combination of GD and sericin is distinctly different. Absorption bands at 1515 and 1546 cm-1 correspond to NH bending of sericin. The band at 1747 cm-1 indicates C=O stretching from the esterification of hydroxyl group in sericin with aldehyde group in GD whereas C=O stretching of sericin appears at 1687 cm-1. Absorption bands appear at 1460 cm-1 which correspond to OH in plane bending in sericin. As the intensity of all bands increased with increased concentration of sericin in finishing solutions, it can be concluded that cotton fibers were modified with sericin using GD as a crosslinking agent.

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Table 1. Composition of finishing solution Samples Sericin (g/L) 0 25 50 75 100 0 25 50 75 100 50% GD (g/L) 40 40 40 40 40 DMeDHEU (g/L) 40 40 40 40 40 Magnesium chloride (g/L) 10 10 10 10 10 10 10 10 10 10 6% Acetic acid (ml/L) 17 17 17 17 17 17 17 17 17 17

UT G-0 G-25 G-50 G-75 G-100 DMe-0 DMe-25 DMe-50 DMe-75 DMe-100

8 6 %Add-on 4 2 0 0 20 40 60 80 100 Sericin conc. (g/L)

Fig. 1. Percentage of add-on of samples treated with sericin using GD and DMeDHEU When DMeHEU was used, absorption bands from either sericin constitution or sericin reaction appeared. Peaks at 1789 and 1750 cm-1 indicate reactions between DMeHEU and sericin. The bands at 1685, and 1515 and 1546 cm-1 indicate C=O stretching and NH bending respectively while 1460 cm-1 is from OH in plane bending in sericin as mentioned above. The surface morphology of samples examined by SEM is shown in Figure 4. The images show that
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GD DMeDHEU

cotton fibers of the untreated change from flat and ribbon-like structure in Figure 4 (a) to more cylindrical when treated with glutaraldehyde and DMeHEU (see Figure 4 (b) and (c)). In Figure 4 (d) and (e), (f) and (g), the shape of cotton fibers after sericin treatment look similar to that treated with glutaraldehyde and DMeDHEU alone, but the SEM images show that sericin molecules are bound on cotton fiber surfaces.

RJTA Vol. 11 No. 3 2007

Fig 2. FT-IR spectra of (a) untreated samples, (b) samples treated with GD only, (c) glutaraldehyde and sericin 25 g/L, (d) GD and sericin 50 g/L, (e) GD and sericin 75 g/L and (f) GD and sericin 100 g/L

Fig. 3. FT-IR spectra of (a) untreated samples, (b) samples treated with DMeDHEU only, (c) DMeDHEU and sericin 25 g/L, (d) DMeDHEU and sericin 50 g/L, (e) DMeDHEU and sericin 75 g/L and (f) DMeDHEU and sericin 100 g/L

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(a)

(b)

(c) (c) (g)

(d) (d)
( )

(e)

(e) (f)

(f) (f)

(g)

Fig. 4. SEM images of (a) Untreated (b) GD only (c) DMeDHEU only (d) GD and sericin 25 g/L (e) GD and sericin 100 g/L (f) DMeDHEU and 25 g/L, and (g) DMeDHEU and 100 g/L.

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Results of L*- and b*-values of samples dyed with Supranol Gleb 4GL are shown in Figures 5 and 6 respectively. L*-value of samples treated with GD only is lower than that of the untreated and samples treated with DMeDHEU only, thus, its b*-value is higher. The L*-values of samples

treated with GD and sericin, and DMeDHEU and sericin substantial decrease with increased concentration of sericin while their b*-values increase. The samples treated with DMeDHEU show lower L*- and higher b*-values than those treated with GD.

89 88 87 86 85 84 83 82 81 80 0 20

Glutaraldehyde DMeDHEU Untreated

L*-value

40 60 80 Sericin content (g/L)

100

Fig. 5. L-values of samples dyed with Supranol Gleb 4GL

100 90 b*-value 80 70 60 50 0 20 40 60 80 100 Sericin content (g/L)

Fig. 6. b-values of samples dyed with Supranol Gleb 4GL K/S of samples derived from Kubelka-Munk was plotted against the wavelength of reflectance light from 400 to 700 nm as shown in Figures 7 and 8 for GD and DMeHEU respectively. There is a relationship between K/S and the wavelength of reflectance color. As compared with the untreated, greater K/S values of the samples treated with GD only were investigated while almost equal values of samples treated with DMeHEU only were
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Glutaraldehyde DMeDHEU Untreated

observed. The color strength of samples substantially increased for samples treated with 25 g/L sericin, especially when DMeDHEU was used. The values of samples treated with GD and DMeHEU were found to continuously increase with increasing sericin concentration up to 75 g/L; further increase in the values were investigated in samples treated with 100 g/L sericin. Comparing the two crosslinking agents, DMeDHEU yields

RJTA Vol. 11 No. 3 2007

greater colour strength than GD as there is a high possibility for DMeDHEU to react with amino group in sericin backbone, and hydroxyl and

carboxylic groups in the side group of sericin through methylol group while aldehyde group of GD reacts with only hydroxyl group of sericin.

10 9 8 7 6 5 4 3 2 1 0 400 450 500 550 600

UT 0 g/L 25 g/L 50 g/L 75 g/L 100 g/L

K/S

650

700

Wave length (nm)

Fig. 7. K/S of samples finished with GD and dyed with Supranol Gleb 4GL

14 12 10 K/S 8 6 4 2 0 400 450 500 550 600 650 700 UT 0 g/L 25 g/L 50 g/L 75 g/L 100 g/L

Wave length (nm)

Fig. 8. K/S of samples finished with DMeDHEU and dyed Supranol Gleb 4GL

The results are attributed to the successful modification of cotton fiber surfaces with sericin when GD and DMeDHEU were used as

crosslinking agents; increasing concentration of sericin increased the sericin content in the cotton fibers.

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4.

Conclusion

[2]

Modification of cotton fibers with sericin was achieved by using glutaraldehyde and DMeDHEU as crosslinking agents in a pad-drycure process. Sericin added in finishing solutions was highly substantive for cotton fibers; increase in %add-on of samples with gradually increased concentration of sericin was received. Glutaraldehyde and DMeDHEU exhibited potential crosslinking agents for cotton fibers and sericin as proved by FTIR-ATR, SEM and dyeing method. FTIR-ATR spectra of samples treated with sericin showed absorption bands at 1515 and 1546 cm-1, and 1687 cm-1 corresponding to NH and -C=O of sericin respectively. The bands at 1747 and, 1789 and 1750 cm-1 indicated C=O of new groups which were regenerated from crosslinking reactions between GD and sericin, and DMeDHEU and sericin. SEM images showed changes in the shapes of cotton fibers; round fibers and sericin deposited on the surfaces of modified fibers were observed. Crosslinking reactions with GD and DMeDHEU bound sericin to cotton and were also proved by dyeing samples with acid dye. The affinity of dye for samples increased with increasing sericin as shown by the decreased L*-values and increased K/S and b*values. DMeDHEU was found to be more reactive to sericin than GD as the samples treated with DMeDHEU yielded greater K/S. It is useful to modify cotton fibers with sericin, and use them as medical textiles such as gauze or pad dressing to keep moisture absorbency and avoid damaging of wound from peeling off.

[3]

[4]

[5]

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Acknowledgements
The authors are indebted to National Metal and Materials Technology Center (Mtec), Thailand for financial support for the research and Christian Doppler Laboratory for Textile and Fibre Chemistry of Cellulosics, University of Innsbruck for analyzing samples by FTIR-ATR.

[10]

REFERENCES
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for soft smooth touch and good hygroscopicity and dyeability manufactured by treating articles comprising acrylics polymers or polyamides with aqueous solutions containing sericins and/or fibroins as byproducts of domestics silk yarn industries or silk yarn manufacturing plants and manufacture thereof, Japan Patent 2001-370851.

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