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Chemical Engineering Journal 239 (2014) 284289

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Chemical Engineering Journal


journal homepage: www.elsevier.com/locate/cej

Fixation of vitamin E microcapsules on dyed cotton fabrics


K. Son a, D.I. Yoo b, Y. Shin a,
a b

Dept. of Clothing & Textiles/Human Ecology Research Institute, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 500-757, Republic of Korea Dept. of Polymer and Fiber System Engineering, Chonnam National University, 77 Yongbong-ro, Buk-gu, Gwangju 500-757, Republic of Korea

h i g h l i g h t s
 Fixation of vitamin E microcapsules

g r a p h i c a l a b s t r a c t

on dyed cotton knit by pad-dry-cure method.  Softener was treated in a simultaneous step with microcapsules or in a separate step.  Microcapsules particles containing vitamin E were stable to the process of laundering, rubbing and ironing.  The K/S value and hue of dyed fabrics were hardly affected by process conditions or process order.  Colorfastness to repeated washing was improved by microcapsules and softener treatments.

a r t i c l e

i n f o

a b s t r a c t
The xation of vitamin E microcapsules was carried out by pad-dry-cure method on dyed cotton knit. Cotton knit was dyed with natural indigo, and subsequently treated with microcapsules containing vitamin E. In order to improve the hand of the microcapsules-treated fabric, a softener was treated in a simultaneous step with microcapsules or in a separate step after dyeing process. It was conrmed by SEM analysis that microcapsules were xed on cotton bers. Melamineformaldehyde microcapsules containing vitamin E was stable during the process of repeated washing, rubbing and ironing. LCMS analysis indicated that the amount of vitamin E decreased gradually with elapsed time. Regardless of the softener treatment order, softness improved and air permeability decreased. The K/S value and hue of dyed fabrics were hardly affected by process conditions or process order. Colorfastness to repeated washing was improved by microcapsules and softener treatments. Based on the obtained experimental results, it can be concluded that the xation of vitamin E microcapsules on dyed cotton knit by pad-dry-cure method was very reliable in terms of durability of microcapsules and color stability of the treated fabrics. 2013 Published by Elsevier B.V.

Article history: Received 31 July 2013 Received in revised form 4 November 2013 Accepted 15 November 2013 Available online 25 November 2013 Keywords: Vitamin E Pad-dry-cure Natural indigo Cotton Softener Colorfastness

1. Introduction Recently, there has been a growing concern of consumers for natural dyed and functional fabrics. To meet this, researches on natural dyed fabrics with functionality are being conducted [1 4]. A new terminology, so-called cosmetic textiles, is a consequence of the fusion of cosmetics and the textile industry through
Corresponding author. Tel.: +82 62 530 1341; fax: +82 62 530 1349.
E-mail address: yshin@jnu.ac.kr (Y. Shin). 1385-8947/$ - see front matter 2013 Published by Elsevier B.V. http://dx.doi.org/10.1016/j.cej.2013.11.034

various techniques, such as micro-encapsulation and has now opened up new target groups and sustainable markets in the textile industry [5,6]. The group of textiles that works to provide a moisturizing effect on human skin is called cosmetic textiles for moisturizing [5]. Vitamin E belongs to the group of liquid-soluble vitamins and the its chemical term is alpha-tocopherol. Since vitamin E shuts out hazardous oxygen which is the cause of skin aging, and offers a superior moisturizing effect, it is often used as a functional cosmetics material [5]. Furthermore, vitamin E has been widely used

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as a useful ingredient in drug medicine, food, etc. [79]. However, vitamin E is subject to oxidation due to the low reliability on external factors, such as heat and oxygen. These disadvantages make it difcult to apply vitamin E directly to textile nish [10]. In cosmetic textile elds, micro-encapsulation techniques containing core materials, or functional materials, such as fragrant [1113], phase change material [14,15], and antimicrobials [16] are being applied in order to improve safety and durability of functional materials [17,18]. Also, with microcapsules containing vitamin E for underwear, T-shirts and bedding, which all have direct contact with the skins, the effect of vitamin E on the skin will be able to be sustained for a long period of time [19]. Meanwhile, the application of natural dyes on textile materials is gaining worldwide popularity due to the increasing awareness of environment, ecology and pollution control [2022]. Natural indigo showing distinctive blue color is one of the oldest known dyestuffs. In particular, it is excellent in colorfastness and functionality such as antimicrobial properties, deodorization and anti-insect properties, compared with other natural dyes [23]. The objective of this study was to develop natural dyed fabrics with moisturizing effect. We applied vitamin E microcapsules nishing onto natural indigo dyed cotton knit to impart moisturizing functionality. Scoured and bleached cotton knit was dyed with natural indigo powder and subsequently padded with melamine formaldehyde microcapsules containing vitamin E. To improve the hand of treated fabric, softener was treated in a simultaneous step with microcapsules or in a separate step. Scanning electron microscopy (SEM) was used to conrm the presence and morphology of the microcapsules. The amount of vitamin E of treated fabrics was evaluated by LC/MS analysis. The effect of microcapsules treatment on physical properties, color and colorfastness were investigated. 2. Experimental part 2.1. Materials The fabric used in this study was scoured and bleached 100% cotton, which is characterized in Table 1. Natural indigo dye was prepared from Polygonum tinctorium using the Korean traditional niram method and contained 15.2%(w/w) of indigo and 0.757%(w/w) of indirubin [24]. Melamineformaldehyde microcapsules containing vitamin E acetate was supplied in the slurry state by Polychrom Co. Ltd. (Korea). Vitamin E acetate, also known as tocopheryl acetate, is used as an alternative to vitamin E itself. It is believed that acetate is slowly hydrolyzed once it is absorbed into the skin, regenerating vitamin E [25]. The mean particle size of the microcapsules was 2.36 lm. Anionic softener (Prosoft) and acrylic binder (Poly Fix-A) were also used in its commercial form (Polychrom, Co. Ltd., Korea). All of the other chemicals were reagent grade. 2.2. Preparation of dyed fabric sample The reduction of natural indigo was achieved gently shaking the dye solution with 20 g/L of natural indigo powder and 5 g/L of sodium hydrosulte in a liquor ratio of 1:50 at 70 C for 30 min. The dyeing was done by dipping in a reduced dye bath at 45 C for

30 min. Dipped samples were followed by air oxidation for 30 min. After complete oxidation, the samples were rinsed in tap water and dried. Scheme 1 presents the dyeing process in this study. 2.3. Fixation of the microcapsules on dyed fabrics The dyed fabrics were impregnated for 10 min to enhance penetration with an aqueous solution composed of 3% (owb) microcapsules and 3% (owb) acrylic binder in a liquor ratio 1:20, padded by two-dips/two-nips method, dried at 80 C for 5 min and cured at 150 C for 3 min. 3% (owb) softener was applied either as additive during microcapsules padding or after microcapsules treatment. Sample codes, according to the treatment process, are shown in Table 2. The add-ons for the microcapsules-treated fabrics were calculated according to the formula:

Add on % b a=a 100


where a is the fabric weight of the sample before treatment, and b is the weight of the sample after treatment. 2.4. Evaluation of treated fabrics The surface of the microcapsules-treated fabrics was observed using a scanning electron microscope (SEM: JSM 5400F, JEOL Inc., Japan). The amount of vitamin E was quantied as an acetate content through an organic solvent extraction method using liquid chromatographymass spectrometer (LCMS: HP 1100 series, Agilent technologies Inc., USA). Ionization mode was API-ES, mass lter mode was Q-pole and detector was HED-EM. The solution for analysis was extracted from 2 g of vitamin E microcapsules-treated fabric at 23 C for 2 h with 50 mL of methanol using a shaking water bath; 1 mL of these was utilized for analysis, and moreover, the acetate content was calculated from the prebuilt calibration curve. Stiffness (drape stiffness; ASTM test method D 1388-64) and air permeability (Frazier method; ASTM test method D 737-96) were evaluated using the standard procedures. Stiffness was assessed by the resistance to bending. Air permeability was the rate of air ow through a fabric under differential pressure between the two fabric surfaces. The Color value of dyed fabrics were evaluated in terms of the dye uptake (K/S values at 660 nm), the H V/C Munsell color values, CIE L a b coordinates and color difference (DE), using a Macbeth Coloreye 3100 spectrophotometer under Illuminant D65 with a 10 standard observer. Colorfastness to washing, rubbing, ironing and light of the dyed and microcapsules-treated fabrics were estimated by the following standard methods. Using a Launder-O-meter (Atlas Electric Device Co., Houston, TX), the washing test was carried out according to the AATCC test method 61-1989 at 40 C for 45 min in water, which had a volume of 200 mL with 0.5% light detergent. The rubbing test was carried out using a standard crockmeter (DL-2007, Daelim Co., Ltd., Korea) under dry and wet conditions according to the AATCC test method 8-2005. The ironing test was conducted in hot pressing under dry and damp conditions (AATCC test method 1332004). The light fastness test was evaluated according to the AATCC test method 16-2004 (option 3) using Xenon Test Chamber

Table 1 Characteristics of knitted fabric. Fiber Weave Density (threads, in.1) Wale Cotton Plain 40 Course 56 155 0.40 Weight (g m2) Thickness (mm)

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K. Son et al. / Chemical Engineering Journal 239 (2014) 284289

Scheme 1. Flow chart of dyeing process.

Table 2 Sample codes according to the treatment process. Sample code D D/MC D/MC-S D/MC/S Treatment process Dyeing Dyeing ? microcapsules treatment Dyeing ? microcapsules and softener treatment Dyeing ? microcapsules treatment ? softener treatment

(Q-SUN, Xe-1-B, Q-Panel Lab Products, USA) after irradiation for 20 h. Colorfastness rating for washing, rubbing and ironing were assessed by a color change against the standard gray scale, and light fastness rating was assessed by the color difference (DE) using a spectrophotometer (values 15; where 1 = poor and 5 = excellent). 3. Result and discussion 3.1. Morphology of vitamin E microcapsules-treated fabrics Fig. 1 shows SEM photographs of the treated cotton knit according to vitamin E microcapsules and softener treatment process. The spherical shaped microcapsules and binder were located at interstices between bers and on the ber surface. D/MC/S sample has ner and more evenly distributed coatings than D/MC and D/ MC-S sample. It was conrmed by SEM analysis that microcapsules were xed on cotton bers. Fig. 2 shows the microscopic views of the fabrics tested at the given washing, rubbing and ironing conditions. The shape of microcapsules observed on the ber surface after 20 washing cycles, rubbing and ironing was similar to the SEM photographs prior to the tests (Fig. 1). Most of the microcapsules also maintained the round shape rather than a broken or distorted shape. Among samples in Fig. 1, the D/MC and D/MC/S samples showed slight decrease the binding of bers after treats. This reveals that melamineformaldehyde microcapsules are stable throughout the processes of washing, rubbing and ironing. We also deduced from the SEM observation that a softener treatment on the microcapsules-treated fabric did not affect the durability of the microcapsules. 3.2. Release of vitamin E from the microcapsules-treated fabrics To investigate the release of vitamin E from the microcapsulestreated fabrics, the amount of vitamin E of the washed samples

with 5 and 20 cycles were measured by LC/MS analysis. The results are presented in Table 3. The amount of vitamin E after 5 washing decreased by 345 lg/g (5.47%) compared to the sample without washing. After 20 washing, the amount of vitamin E slightly decreased by 61 lg/g (1.02%) compared to the sample washed 5 cycles. We found that the decrease in the amount of vitamin E during repeated washing was minimal. As observed in the SEM photographs (Fig. 2), the minimal change was speculated as a result of the superior durability of the microcapsules. On the other hand, the amount of vitamin E on the treated fabric decreased gradually with elapsed time for up to 18 weeks of storage, as shown in Fig. 3. The amount of vitamin E released for 6 weeks in earlier stage was around 120.44 g/m2. Thereafter, the amount of vitamin E released for 12 weeks was decreased to around 42.82 g/m2. Therefore, the rough number of vitamin E diffused through the wall of microcapsules might be about 1.534 1023/m2 for 6 weeks and then it was decreased to 5.455 1022/m2. This result indicated that vitamin E was released slowly and gradually through microcapsules wall. 3.3. Physical properties of vitamin E microcapsules-treated fabrics Add on, stiffness and air permeability of the treated samples according to natural indigo dyeing, vitamin E microcapsules and softener treatment processes are shown in Table 4. Add-ons of D/ MC-S and D/MC/S samples discernibly showed higher values of 0.250.30 than that of D/MC sample. Air permeability is an important factor in comfort of textile materials applied special nishing technique [6]. After dyeing and microcapsules treatments, the stiffness of the fabrics increased very slightly, while air permeability decreased. As shown in the SEM photographs of Fig. 1, the xation of the microcapsules with binder resulted stiffer and less air permeable fabrics [15]. Also, the decrease in air permeability was possibly due to the impregnation of cotton fabric with microcapsules; the coated microcapsules would ll up the gap between yarns, making the airow pass more difcult through the fabric [6]. Regardless of the softener treatment order, softness improved and air permeability decreased with the addition of softener. Yet, D/MC/S sample, which was treated softener in a separate step, was stiffer and less air permeable compared with D/MC-S sample, which was treated softener simultaneously. It can be attributed by more coating of softener in a separate D/MC/S sample [3]. Softener was more universally used in textile nishing than any other of nishing agent. It could reduce the friction between bers and yarns,

(a) D/MC

(b) D/MC-S
Fig. 1. SEM photographs (X1000) of microcapsules-treated fabrics.

(c) D/MC/S

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Samples

Washing (20 cycles)

Rubbing (dry condition)

Ironing (damp test)

D/MC

D/MC-S

D/MC/S

Fig. 2. SEM photographs (X1000) of microcapsules-treated fabrics after washing, rubbing and ironing test.

Table 3 Amount of vitamin E according to the washing in vitamin E microcapsules-treated fabrics (D/MC-S samples). Washing (cycles) 0 5 20 Amount of vitamin-E (lg/g) 6308 112 5963 52 5902 24

Table 4 Add-on and physical properties of dyed and microcapsules-treated fabrics. Samples Control D D/MC D/MC-S D/MC/S Add-on (%) 1.92 0.05 2.22 0.03 2.17 0.02 Stiffness (cm) 1.48 0.01 1.50 0.01 1.52 0.03 1.43 0.03 1.45 0.06 Air permeability (cm3/min/cm2) 109.46 1.99 107.44 1.52 101.91 2.52 97.87 2.37 90.83 4.37

1100

neous treatment of softener with microcapsules was more efcient than the separate treatment in points of better physical properties and simpler procedure. 3.4. Color of the vitamin E microcapsules-treated fabrics Table 5 presents the K/S values and color properties according to indigo dyeing, vitamin E microcapsules and softener treatment processes. The K/S value of dyed fabrics did not change signicantly after subsequent treatments with different preparation microcapsules or softener. The hue (H, 3.7 PB) of the dyed sample shifted slightly to 4.24.3 PB after the microcapsules and softener treatment. Lightness of the treated sample was decreased after separate softener treatment (D/MC/S). The results showed that softener could affect the shade of dyed fabrics. Some of softeners such as silicones would cause the shade to become darker. This is optical phenomenon which the proportion of reected light decreases in a medium with decreasing refractive index [28]. In addition, the decrease of absolute a value and absolute b values after the microcapsules and softener treatments represented that both green color decreased and blue color decreased. The color difference (DE), as a result of microcapsules and softener treatment, was in the range of 0.822.44. In particular, D/MC/S sample

Amount of vitamin E (g)

1000

900

800

700 0 2 4 6 8 10 12 14 16 18 20

Elapsed time (weeks)


Fig. 3. Release of vitamin E according to the elapsed time of D/MC-S samples (100 cm 100 cm).

gave the treated fabric soft handle and improved drape property [26,27]. From these results, It was considered that the simulta-

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K. Son et al. / Chemical Engineering Journal 239 (2014) 284289 Table 5 K/S value and color properties of treated fabrics. Treatment D D/MC D/MC-S D/MC/S K/S value (660 nm) 6.85 6.67 6.43 6.91 H V/C 3.7 PB 4.2 PB 4.3 PB 4.2 PB 3.6/3.5 3.6/3.4 3.7/3.5 3.4/3.2 L 38.56 37.53 38.61 35.21 a 2.39 1.59 1.57 1.52 b 14.76 14.38 14.63 13.86

DE
0.82 0.02 1.46 0.06 2.44 0.04

a; Red(+)/green() color axis. b; Yellow(+)/blue() color axis, DE; color difference.

showed the largest color difference of 2.44, as indicated by the relatively large change in L, a and b values. While D/MC and D/MCS sample had no color difference to the naked eye, the color difference in D/MC/S sample was visible to the naked eye. This result was caused by the coating of softener on the surface of the dyed and microcapsules-treated fabrics. Parvinzadeh and Naja reported that post-treatment with anionic, cationic, nonionic, micro and macro emulsion silicone softeners changed color coordinates such as L, a and b values of all cotton fabrics dyed with direct dyes or sulfur dyes [29,30].

3.5. Colorfastness of the vitamin E microcapsules-treated fabrics The fastnesses to washing, rubbing, ironing and light of the dyed fabrics were evaluated as per standards. The degrees of fastness are indicated by numbers, 1 representing the lowest and 5 the highest. The colorfastness of dyed fabric (D) were relatively good as the above 3/4 rating (Table 6). The solubility and the rate of movement of the dye outward from the ber are the factor determining fastness to washing. It is worth to mention that water insoluble dye such as indigo dye usually shows better fastness as compared to water soluble dye [31]. Through microcapsules and softener treatment, all of the fabric samples showed an equal or higher colorfastness ratings compared to the indigo dyed fabric. The application of softener on the textile materials ensure that they contain some moisture which make them soft. The swelled fabric due to having high surface obviously results to poor wash and rubbing fastness [31]. However, the softener treated samples (D/MC-S and D/MC/S) have shown acceptable washing and rubbing fastness with improving softness (Table 4). In practical point of view, it is very important that the color retention according to repeated washing or continuous light exposure of natural dyed fabric with functionality. To investigate the color retention of vitamin E microcapsules-treated fabrics, the color difference (DE) of the treated samples were determined after washing up to 20 cycles and after light exposure for 40 h. Color difference by repeated washing of 5 and 20 cycles are shown in Fig. 4. Regardless of the treatment process, color difference increased. Color difference of the dyed samples (D) were in the range of 1.632.28. On the other hand, color difference of the microcapsules and softener treated samples were in the range of 0.761.73. The color difference of the dyed sample got larger than that of the other samples as more washing repeated. It speculated

Fig. 4. Effect of washing cycles on the color difference of treated samples.

Fig. 5. Effect of light time on the color difference of treated samples.

Table 6 Colorfastness data of the treated fabrics. Treatment Washing (5 cycles) Color change D D/MC D/MC-S D/MC/S 4 4/5 4/5 4 Stain 4 4/5 4/5 4/5 Rubbing Dry 4 4/5 4/5 4/5 Wet 3/4 3/4 4 4 Ironing Dry 5 5 5 5 Damp 4/5 4/5 4/5 5 3/4 3/4 3/4 3/4 Light (20 h)

that vitamin E microcapsules and softener on the ber surface prevented dye molecules washing out more or less. Fig. 5 shows the color difference after light exposure of 5, 10, 20 and 40 h. With an extension of exposure time to 40 h, no more color difference occurred. Especially, D/MC-S and D/MC/S samples showed more fading than D/MC sample. It was reported that softener treatment caused more fading of cotton fabrics dyed with direct dye or sulfur dye for 2 days [29,30]. Color difference after light exposure for 40 h was in the range of 1.504.25, which was larger than that of repeated washing. The treated samples in this study seems to choose drying method of less light exposure.

4. Conclusion The xation of vitamin E microcapsules was carried out by paddry-cure method on dyed cotton knit. Cotton knit was dyed with natural indigo, and subsequently treated with microcapsules con-

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taining vitamin E. In order to improve the hand of the microcapsules-treated fabric, a softener was treated in a simultaneous step with microcapsules or in a separate step after dyeing process. The treated fabrics were evaluated for SEM observation, amount of vitamin E, physical properties, and color properties. It was conrmed by SEM analysis that microcapsules were xed on cotton bers. Melamineformaldehyde microcapsules containing vitamin E was stable during the process of repeated washing, rubbing and ironing. LCMS analysis indicated that the amount of vitamin E decreased gradually with elapsed time. Regardless of the softener treatment order, softness improved and air permeability decreased. The K/S value and hue of dyed fabrics were hardly affected by process conditions or process order. Colorfastness to repeated washing was improved by microcapsules and softener treatments. Based on the obtained experimental results, it can be concluded that the xation of vitamin E microcapsules on dyed cotton knit by pad-dry-cure method was very reliable in terms of durability of microcapsules and color stability of the treated fabrics. Acknowledgements This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by Ministry of Education, Science and Technology (No. 20100021015). References
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