Enhancement of colour fixation behaviour of cotton fabric via solgel process

Y. J. Yin and C. X. Wang*

Cotton fabrics dyed with reactive dyes were treated with composite silicon sol by traditional pad drycure process in order to investigate the colour fixation properties. The results show that the hue values of the fabrics change little and the dry and wet rubbing fastnesses are improved by more than half a grade. The fade rate of washing at 60uC decreased by y30% due to the protection of composite silicon sol thin film on the surface of cotton fabric. The DE value of the fabric dyed with reactive red dye exposed in the Xenotest could be decreased from 17?6 to 7?4. The data demonstrate that the composite silicon sol treatment has no important effect on the handle of fabrics, indicating that the composite sol method is an effective way to improve the colour fastness of cotton fabrics.
Keywords: Composite silicon sol, Rubbing fastness, Washing fastness, Light fastness, Reactive dye, Chromatic values, Handle, Cotton fabric

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Introduction
Reactive dye is one of the most popular dyes used on textile dyeing. Most reactive dyes are suitable for cellulose bres.1 There are also reactive dyes that react specically with wool; some are found within the Lanaset grouping of dyes for protein bres. Unlike other dyes, it actually forms a covalent bond with the cellulose or protein molecule.2 Once the bond is formed, the dye molecule has become an actual part of the cellulose bre molecule. No wonder a garment that has been dyed in bright bre reactive colours with white clothing can be safely washed, without endangering the whites in the least, even if it is all different bright colours, or even solid black. However, a serious problem often occurs in dyed fabric with reactive dyes, low dye uptake.3 A lot of reactive dye molecules often do not form bonds with bres; instead, they often combine only by the weak physical adsorption caused by the van der Waals forces and the hydrogen bonds, which makes its fastness poor and restricts its wide application and amounts of export in a certain degree. Generally, two methods are usually used to improve the fastness of the dyed fabric, to select the dyes with high fastness or to use some special reagents in treatment process,4,5 such as UV protected substance, dyeing xative and antirubbing.6 The solgel process is a versatile solution process for making ceramic, glass materials and others. The solgel process involves the evolution of inorganic networks through the formation of a colloidal suspension (sol) and gelation of the sol to form a network in a continuous liquid phase (gel).7 The precursors for

synthesising these colloids consist of a metal or metalloid element surrounded by various reactive ligands. The specic reaction mechanism is a hydrolysis reaction which induces the substitution of OR groups linked to silicon by silanol SiOH groups. These chemical species may react to form SiOSi (siloxane) bonds which lead to the silica network formation. This phase establishes a three-dimensional network.8,9 The application of silica sol is of great scientic and technical interest nowadays. It can be used on various substrates like glass, paper and textile.10,11 Some people reported that silica sol can improve the dyeing fastness. Recently, similar inorganic compounds like titanium and zinc oxide have been used in the solgel process on textiles.12 The reports on titania sol used on fabric to modify the optical properties in visible and UV light often appear in many journals and papers.1315 However, the study of composite silicon sol used on coatings on fabrics is few. The aim of this study is to determine the colour xation properties about the dyed cottons with the treatment of composite silicon sol, which is shown by the colorimetric value, rubbing fastness, fading per cent and light fastness.

Experimental
Materials
The cotton fabric (weight: 141?0 g m22) was produced by Jiangsu Hongdou Industrial Co. Ltd. The tetraethoxysilane (TEOS) (28?4%), tetrabutyl titanate (TTB) (28?4%), ethanol (97?0%) and HCl were all obtained from Shanghai Sinopharm Chemical Reagent Co. Ltd. The 3-glycidoxypropyltrimethoxysilane (GPTMS) was gained from Hubei Jianghan Chemical Co. Ltd. The soap ake was prepared by Shanghai Jiachuan Chemical Engineering Co. Ltd. All the solvents and chemical reagents are analytical grade.

Key Laboratory of Eco-Textile, Ministry of Education, Jiangnan University, Wuxi 214122, China *Corresponding author, email wangchaoxia@sohu.com

W. S. Maney & Son Ltd 2009 Received 28 July 2008; accepted 4 September 2008 DOI 10.1179/143307509X402174

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Enhancement of colour fixation behaviour of cotton fabric via solgel process

Preparation of composite silicon sol

The composite silicon sol was prepared by hydrolysis of Si(OC2H5)4 (TEOS) mixed with Ti(OC4H9)4 (TTB) in acidic ethanol solution. A typical preparation was as follows: a mixture of 20 mL TEOS, 6 mL TTB, 0?4 mL GPTMS, 120 mL ethanol and 1 mL HCl (1 mol L21) was stirred together for 24 h at room temperature. The composite silicon sol was stored for 2 days before application to the dyed fabrics for the coating process.16

Electronic Apparatus Co. Ltd. The fabrics are rubbed with a dry rubbing cloth and a wet rubbing cloth. The staining of the rubbing cloths is measured by the greyscale.

Fastness to washing
The dyeing colour fastness is the colour resistant ability of fabric to external factors (extrusion, friction, soap, rain, sun, etc.) during the processing and using. It mainly includes washing, rubbing and light fastnesses. The washing fastnesses were tested according to the standard of ISO 150-C03:1989 using a 3 g L21 soap at 40 and 60uC for 30 min with the 12-A washing fastness tester supplied by China Wenzhou Darong Textile Machine Factory. The percentage of fading was calculated using the equation D~ rA {rB |100% 100{rB (2)

Dyeing of cotton fabric

The dyes used in this study are CI reactive red B-3G, CI reactive yellow B-4RFN and CI reactive blue BGF, and all of they were supplied by Shanghai Wande Co. Ltd. The fabrics were dyed with the following process: dye concentration 0?2%, sodium chloride 25 g L21, bath ratio 1 : 30, dipped at 40uC for 20 min, dyed at 60uC for 45 min, and then boiled with the soap, washed and dried.

Treatment of cotton fabric

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The dyed fabrics were dipped into the composite silicon sol for 5 min and padded with a P-130 padder produced by Taiwan Rapid Co. Ltd and the wet pick-up was 65% at room temperature. Fabrics was dipped and padded repeatedly as above. Then the fabrics were dried at 60uC for 20 min and cured at 120uC for 3 min.

where rA is the reectance after the washing testing and rB is the reectance before the testing. The values of rA and rB were determined at the most signicant minimum of the reectance spectra of the dyed textiles (B-3G: l5510 nm, B-4RFN: l5430 nm, BGF: l5670 nm).19,20

Fastness to light
All light fastnesses were tested with an ATLAS-150S light fastness device obtained from German SDL Atlas Ltd. The textile samples were exposed in the Xenotest for 120 h with humidity 60% and radicalisation 80%. Then the substrates which had been irradiated were assessed by the Xrite-8400 spectrophotometer under the illuminant D65 using the 10u standard observer. The degree of distinction was determined by DE value. The smaller the DE value, the better the light fastness.

Colour measurements
The colour properties of the dyed samples were determined with an Xrite-8400 spectrophotometer obtained from America X-Rite Co. Ltd under the illuminant D65 using the 10u standard observer.17,18 The values of L*, a*, b*, K/S and E were gained, which showed the colour performance of the fabrics. The three coordinates of CIELab represent the lightness of the colour (L*, L*50 yields black and L*5100 indicates white), its position between red/magenta and green (a*, negative values indicate green while positive values indicate magenta) and its position between yellow and blue (b*, negative values indicate blue and positive values indicate yellow) K 1{R2 ~ (1) S 2R where K is the absorption coefcient, S is the scattering coefcient and R is the fractional reectance (values from 0 to 1) of dyed substrate at the wavelength of minimum reectance. The K/S values are proportional to test fabric colour; therefore, the larger the K/S value, the larger the degree and intensity of the colour strength.

Handle measurements
The fabrics untreated and treated with composite silicon sol were evaluated for handle and softness by KES-FB2 Kawabata Evaluation System-Fabric. The handle change of fabrics is expressed by the bending rigidity and bending hysteresis moment. The smaller the values of the bending rigidity and bending hysteresis moment, the better the handle.21

Results and discussion

Effect of composite silicon sol on chromatic values
The chromatic values of the dyed fabrics treated with composite silicon sol can be seen in Table 1. It can be seen in Table 1 that the fabrics treated with composite silicon sol show less change in the chromatic values: the K/S value increases slightly (the range is less than 0?05), the L* value decreases and the values of a* and b* alter unconspicuously. For the fabric dyed with

Fastness to rubbing
The rubbing fastness was measured according to the standard of ISO 105-X12:1993 using Y5711 dyeing rubbing colour fastness device produced by Laizhou
Table 1 Chromatic values of fabrics dyed with reactive dyes Dye Reactive red B-3BF Reactive yellow B-4RFN Reactive blue BGF Sample Untreated Treated Untreated Treated Untreated Treated K/S 1.579 1.580 2.302 2.336 1.914 1.924 L* 70.06 69.90 81.29 80.99 76.88 76.55

a* 35.28 36.21 8.64 9.15 225.30 225.32

b* 13.83 14.68 54.24 56.19 217.60 218.03

C* 39.14 39.07 54.92 55.28 30.82 31.08

hu 22.89 22.05 80.95 81.15 215.51 215.46

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Enhancement of colour fixation behaviour of cotton fabric via solgel process

2 Effect of composite silicon sol on lighting performance 1 Effect of composite silicon sol on fade rate of washing at different temperatures

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reactive red B-3G, Da* is 0?93 and Db* is 0?85; with the yellow B-4RFN, Da* is 0?51 and Db* is 1?95; with the blue BGF, Da* is 0?02 and Db* is 0?43. It is obvious that the chromatic values of fabrics dyed with yellow B4RFN after composite silicon sol treatment are the most sensitive. It could be concluded that the shade is slightly changed, and a deeper colour can be achieved. With the treatment of the composite silicon sol, the surfaces of fabrics are gaining a transparent three-dimensional network for the transparent composite silicon sol. The transparent coating could not change the hue value. So it has little infection on the chromatic values of the dyed fabrics.

appear that the three-dimensional lm does not dissolve in H2O. The reason may be also that the friction coefcient of wet composite silicon sol lm is smaller than that of the dry composite silicon sol lm, so the friction force of dye molecules suffered in the wet surroundings is smaller than that suffered in the wet surroundings. The wet fastness caused is obviously improved.

Effect of composite silicon sol on fade rate of washing

The degree of fading is different within the washing process at 40 and 60uC. As can be seen in Fig. 1, a large decrease in the value at a high washing temperature 60uC is obtained. Hydrolysis is a serious fault of reactive dyes. The stability of covalent bonds between reactive dyes and bres is weak in H2O if some OH2 ions exist. The activity of bonds increases at a higher temperature. And a higher temperature would improve the hydrolysis reaction process, so the fade rate of washing at 60uC is larger than that at 40uC. Without the treatment, the degrees of fading rate in all cases are higher than 50%, but the values all decreased obviously by y30% after the treatment with composite silicon sol. It can be deduced that the improved fading fastness results from the composite silicon sol coating. The composite silicon sol lm improves the protection to dye molecules from the outside force when washing. The reason may be also that the friction coefcient of wet composite silicon sol lm is smaller than the dry composite silicon sol lm.

Effect of treatment by composite silicon sol on rubbing fastness

It can be seen in Table 2 that the dry rubbing fastness and the wet rubbing fastness of the fabrics treated with composite silicon sol are all increased by about half a grade. Especially, the wet rubbing fastnesses of dye reactive yellow B-4RFN and reactive blue BGF are enhanced by one grade. The improvement of rubbing fastness could result from the protection of the network which is formed on the fabric with the sol treatment. The three-dimensional network reduces the damage of the outside force to the dye molecules. It also may be that the friction coefcient of composite silicon sol lm is smaller than the that of cotton bre, so the friction force of dye molecules surrounded by composite silicon sol lm is smaller than that surrounded by cotton bres. The addition of epoxy group (GPTMS) in organic materials increases the protection by the action to the hydroxyl group of cotton bres. The data also indicate that the improvement of wet fastness is larger than that of the dry fastness. The wet fastnesses of reactive yellow B-4RFN and the reactive blue BGF are enhanced by one grade, and half a grade higher than the enhancement of dry fastness. This may
Table 2 Rubbing fastness of reactive dye Reactive red B-3G Untreated Dry rubbing fastness (grade) Wet rubbing fastness (grade) 34 2 Treated 45 23

Effect of composite sol concentrations on light fastness

The lighting performance is expressed by the change of DE value before and after the irradiation by the Xenotest. The data can be seen in Fig. 2. It could be concluded that the light fastness increases with decreasing DE value distinctly after the composite silicon sol treatment. Compared with the untreated fabrics, the DE value could be decrease to 7?4 from 17?6 after the fabric dyed with reactive red B-3G is treated with composite

Reactive yellow B-4RFN Untreated 4 3 Treated 45 4

Reactive blue BGF Untreated 4 3 Treated 45 4

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Enhancement of colour fixation behaviour of cotton fabric via solgel process

Table 3 Handle change of fabrics Bending rigidity, N cm2 cm21 Warp Untreated Treated 0.0135 0.0372 Weft 0.0261 0.0467 Bending hysteresis moment, N cm cm21 Warp 0.0174 0.0573 Weft 0.0235 0.0525

silicon sol and exposed in the Xenotest for 120 h. The improvement could result from the dye molecules trapped inside the titanium and silica matrix avoiding irradiating directly. This also may be caused by the reex action of the composite silicon sol lm or the absorption of the titanium and silica matrix.

colloidal particles formed a network on the cotton bre and the dye molecules are xed on this network, which reduces the function to the dyes effectively during the action of mechanical and photic force.

Acknowledgement
The authors are grateful to the financial support of the National Natural Science Foundation of China (no. 20674031) and the Program of Key Laboratory of Eco-Textile (Jiangnan University).

Handle measurements
The bending properties of fabrics untreated and treated with composite silicon sol are measured with KES-FB2 Kawabata Evaluation System-Fabric. The handle change of fabrics is expressed by the bending rigidity and bending hysteresis moment. Table 3 shows that compared with the one untreated with composite silicon sol, both of the bending rigidity and bending hysteresis moment of fabric treated with composite silicon sol are increased. The warp and the weft changes of bending rigidity are nearly the same, and the warp change of the bending hysteresis moment is more obvious than that of the weft one, but both of the increases are smaller than 0?04 N cm cm21. The data indicate that the softness is decreased. These decreases may be due to the fact that the uniform continuous lm formed from composite silicon sol impacts the bending properties, leading to the softness decline. However, the change of bending properties is very small, and the handle is not affected by the wear behaviour of fabrics.

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References
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Conclusion
This study concerns the preparation of composite silicon sol and the effect on colour xation property of dyed fabrics treated with composite silicon sol. Different methods are used to evaluate the properties of dyed fabrics with reactive dye. The results indicate that the modication by composite silicon sol on fabric dyed with reactive dyes is an effect method to improve the colour xation property, though there is a little change of the chromatic values and the handle. The fabrics treated with composite silicon sol present positive effects on the rubbing, washing and light fastness, and the wet rubbing fastness is improved at least half a grade. Simultaneously, there is no adverse effect on chromatic values of the dyed fabrics. It is presumed that the

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