Two-step durable press treatment of cotton fabric

Weilin Xu, Weigang Cui, Wenbin Li and Weiqi Guo

Textile Research Centre, Wuhan Institute of Science and Technology, Wuhan 430073, China Email: weilin_xu@hotmail.com

Coloration Technology

In this paper cotton fabrics were treated by two different methods with polycarboxylic acids (citric acid and butanetetracarboxylic acid) for durable press performance. The first was a two-step method in which the fabric was initially treated with citric acid and then treated by butanetetracarboxylic acid. The other was a mixed method in which the fabric was treated with a solution containing the two mixed polycarboxylic acids. Following the treatments, the wrinkle recovery angle, strength and strength retention of the resulting fabric were measured and compared.

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Introduction
It has been reported in the literature that in the future polycarboxylic acids may replace traditional formaldehyde reagents for durable press finish of cotton fabrics [16]. It is clear that cellulose esterification with a polycarboxylic acid proceeds first to form a cyclic anhydride and then to form an ester with the hydroxy group in the cellulose macromolecule [7]. When sodium hypophosphite (SHP) is added as a catalyst, the temperature at which esterification occurs is lowered. Butanetetracarboxylic acid (BTCA) can form two or more ester bonds in such a reaction, thus this acid can crosslink two macromolecules effectively. However, the high price of BTCA greatly affects its wide application in the textile industry. In order to reduce the cost, an alternative method was developed in which low concentrations of BTCA (1.5%) were combined with an inexpensive acid, such as citric acid (4.5%) [7]. This method resulted in a fabric with an improved durable press performance when compared with untreated fabric, but with a lower performance than that treated with 6% BTCA alone. In the cellulose macromolecule there are actually three different environments for the hydroxy groups and these can influence the macromolecules activity in the esterification reaction [3]. Some of the hydroxy groups are very active and can easily react with some poorly active crosslinking reagents such as citric acid, whereas, some can only react with highly active crosslinking agents such as BTCA. In the mixed method, the activities of citric acid and BTCA in the treating solution cannot be fully utilised because their activities are not the same in the crosslinking reaction. It is considered that only when the reaction of citric acid and BTCA with the macromolecules is specifically controlled can their effect be fully utilised. The work described in this paper compares the effects of two different treatment methods. In the first method, the fabric is initially treated with citric acid and then further treated by BTCA separately, and the second method
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involves the treatment of fabric with a mixed solution containing citric acid and BTCA at differing concentrations.

Experimental
Materials Undyed 100% plain cotton fabric (182.0 g/m 2) was desized, scoured and bleached by the supplier (Wuhan No. 1 Spinning and Weaving Factory). Before use it was fully washed and dried. Each fabric sample was 20 cm2. 1,2,3,4-Butanetetracarboxylic acid (BTCA) and citric acid were purchased from Aldrich Chemical Company. The catalyst used in this study, sodium hypophosphite (SHP), was obtained from Beijing Chemical Inc. and was of analytical grade. The chemical structures of BTCA and citric acid are shown in structures 1 and 2, respectively.

CH2 CH CH CH2

COOH COOH COOH COOH 1

CH2 CH2 2 COOH COOH

HO C COOH

Fabric durable press treatment Prior to treatment, all samples were immersed in 1% citric acid solution for 30 min, after which they were fully washed with distilled water and dried at 110 C. In the two-step process, the fabric was immersed in the aqueous treating solution containing citric acid and the catalyst SHP at different concentrations (weight percentage in the aqueous solution). The fabric was then passed through squeeze rolls and immersed in the treating solution, and was then passed through squeeze rolls again to give a specified wet pick-up of ca. 85%. The fabric was pre-dried at 85 C for 10 min, and cured in a second oven
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Cell CH COOH CH COOH CH COOH

Heat Catalyst

Cell CH C O
Heat Catalyst Cell OH

Cell CH C O CH COOH CH C O Cell

CH C O O CH C O CH COOH

CH C O
Cell OH

CH COOH CH COOH

CH C O O CH C O

Figure 1 Formation of ester crosslinks in cotton fibre

for 2 min at 180 C. This process was then repeated to treat the fabric with differing concentrations of BTCA and SHP. In the mixed treating method, the fabric was treated in the solution containing different concentrations of citric acid and BTCA together with the catalyst SHP. After it was squeezed (85% wet pick-up), it was then pre-dried at 85 C for 10 min, and cured in a second oven for 2 min at 180 C. The catalyst concentration was the same as that of the specific crosslinking agent in the two-step method. In the mixed method the catalyst concentration was the same as the total crosslinking agent concentration (i.e. 5.1%). Testing methods Mechanical properties were measured on an Instron tester (model 3410) at a 50 mm gauge length and with a crosshead speed of 100 mm/min. The width of the sample was 15 mm. Standard methods were used to measure conditioned wrinkle recovery angle (AATCC 66-1996).

Results and Discussion

Mixed method In order to compare the efficiency of the two methods, the fabric was first treated with the more traditional pad and cure method, i.e. with the mixed citric acid and BTCA solution. The results of the performance of the treated fabric in terms of wrinkle recovery angle (WRA), strength and strength retention are shown in Table 1. Compared with the untreated samples, it is evident that the WRA of the treated samples is increased whereas the strength is decreased. Equal concentrations of citric acid and BTCA in the treating solution of 2.55% give the highest dry WRA of the treated fabric (280). Increasing

the citric acid concentration and decreasing the BTCA concentration beyond 2.55% in the mixed solution, resulted in a corresponding decrease in WRA of the treated fabric. It has been reported previously that by using the mixed method, the quantity of BTCA necessary for obtaining satisfactory durable press treatment can be reduced [7]. However, the results in Table 1 show that the durable press properties of the treated fabric were not greatly improved when less than 2% BTCA was added to the treating solution. As mentioned in the Introduction, there are different kinds of hydroxy groups present in the cellulose macromolecule, each of which have differing activities. Crosslinking between the polycarboxylic acid and the cotton cellulose (Cell) does not utilise all the available carboxylic groups in the reaction, as shown in Figure 1. Citric acid has fewer carboxylic groups in the molecule than BTCA, thus its crosslinking efficiency is lower. Also, the a hydroxy group in the citric acid molecule greatly reduces its effectiveness as a durable press finishing agent because it influences the interaction of the adjacent carboxylic group with the hydroxy groups of the cellulose macromolecule [7]. Thus, in the mixed method, the effect of citric acid is greatly reduced because the activity of BTCA is much higher than that of citric acid. BTCA can first react with the active hydroxy groups in the fibre, after which citric acid only has the chance to react with any unreacted hydroxy groups in the fibre because of its poor reactivity. This means in the mixed treatment method citric acid has less effect than previously presumed. Two-step method The two-step treatment process leads to further improvements of the durable press properties of the fabric (Table 2). The citric acid is first added to the treatment solution where it initially reacts with the active hydroxy groups in the fibre. The BTCA is then added to react with the remaining hydroxy groups with poorer reactivity. In this manner, the citric acid can be used to full effect and the high activity of the BTCA can further improve the performance. In this method the catalyst concentration was the same as the crosslinking reagent in the treatment. In order to first compare the individual effects of citric acid or BTCA on the WRA, the fabric was treated with varying concentrations of the crosslinking agents separately and the results are shown in Figure 2 for the dry WRA. This figure clearly shows that treatment with BTCA generally results in a higher dry WRA, with 5.1% of BTCA giving the highest WRA of 292. As for citric acid, the highest value of dry WRA obtained is 264 at a concentration of 5.1%.
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Table 1 Wrinkle recovery angle (WRA) and strength of the fabric treated by the mixed method WRAb () Conc.a (%) Untreated sample 0.85 1.70 2.55 3.40 4.25 + + + + + 4.25 3.40 2.55 1.70 0.85 Dry 112 274 272 280 260 248 Wet 103 253 251 262 249 237 Strengthb (N) 774 370 414 386 368 374 Strength retention (%) 100 47.8 53.4 49.8 47.5 48.3

a Weight percentage of citric acid + BTCA, respectively b Warp + filling

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Table 2 Wrinkle recovery angle (WRA) and strength of the treated fabrics by the two-step method WRAb () Wet 218 223 237 242 244 261 226 247 261 265 268 269 234 249 269 262 271 276 273 272 274 273 279 273 267 267 268 269 273 276 282 286 276 274 273 264
WRA, o

300 280

Citric acid conc.a (%) 0.85 1.70 2.55 3.40 4.25 5.10 0.85 1.70 2.55 3.40 4.25 5.10 0.85 1.70 2.55 3.40 4.25 5.10 0.85 1.70 2.55 3.40 4.25 5.10 0.85 1.70 2.55 3.40 4.25 5.10 0.85 1.70 2.55 3.40 4.25 5.10

BTCA conc.a (%) Dry 0.85 0.85 0.85 0.85 0.85 0.85 1.70 1.70 1.70 1.70 1.70 1.70 2.55 2.55 2.55 2.55 2.55 2.55 3.40 3.40 3.40 3.40 3.40 3.40 4.25 4.25 4.25 4.25 4.25 4.25 5.10 5.10 5.10 5.10 5.10 5.10 236 240 256 264 264 270 244 264 272 280 284 288 250 268 282 284 292 294 284 284 286 288 290 296 280 284 284 286 290 296 300 304 294 290 288 280

Strengthb Strength (N) retention (%) 412 316 314 308 308 302 376 310 312 308 310 300 340 312 306 308 310 310 332 310 312 312 302 288 328 320 318 302 306 306 344 314 280 270 286 280 53.2 40.8 40.5 39.7 39.7 39.0 48.5 40.0 40.3 39.7 40.0 38.7 43.9 40.3 39.5 39.7 40.0 40.0 42.8 40.0 40.3 40.3 39.0 37.2 42.3 41.3 41.0 39.0 39.5 39.5 44.4 40.5 36.1 34.8 36.9 36.1

260
1% BTCA 3% BTCA 5% BTCA 2% BTCA 4% BTCA 6% BTCA

240 220 1 2 3

4
Conc., %

Figure 3 Relation between crosslinking agent concentration and the dry WRA of the fabric treated by the two-step method

a Weight percentage b Warp + filling

300 280 260

WRA, o

240 220 200 180 1 2 3 4

Conc., % CA-treated dry WRA CA-treated wet WRA BTCA-treated dry WRA BTCA-treated wet WRA

However, using the mixed method even higher values of WRA can be obtained, as can be seen from the results in Table 2 and Figure 3. By initially treating a fabric with a certain concentration of citric acid followed by further treatment with BTCA, values of dry WRA can be obtained which are greater than either the one-step method or treatment with BTCA alone. A maximum value of dry WRA of 304 is obtained for initial treatment with 1.7% citric acid followed by 5.1% BTCA (Figure 3). As for an industrial application of this method, we believe addition of 4.3% citric acid is the most suitable. At this concentration of citric acid yellowing of the treated fabric is not very evident, and when the fabric is further treated by 1.7% BTCA, a WRA of greater than 280 is obtained. Generally, strength loss in the cotton fabric durable press treatment is unavoidable and serious strength loss was observed in this experiment. Strength loss mainly arises for two reasons. Firstly, there are two kinds of crosslinks: inter- and intra-macromolecular. Previous results showed that almost 20% of strength loss comes from the intra-macromolecular crosslinks [3,4]. This strength loss can be improved by exerting the fabric at a certain strength during the curing treatment so as to reduce the intra-macromolecular crosslinks in the fibre [3]. The second reason for strength loss is mostly due to the acidity of the treating solution. This leads to an irreversible depolymerisation of the macromolecules during the high temperature curing step [4,810]. In the two-step treatment, the fabric strength retention is observed to be much lower than that of the fabric treated by the mixed method. This is perhaps mostly due to the fabric undergoing two curing treatments at high temperature which therefore leads to further depolymerisation of the macromolecule.

Conclusions
This paper reports the durable press results of cotton fabrics following two different kinds of treatment, the mixed and two-step methods. Applying the two-step treatment results in improved WRA values when compared with the mixed method. It is assumed that in
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Figure 2 Relation between crosslinking agent concentration (citric acid or BTCA) and WRA of the treated fabrics

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the mixed treatment, BTCA is more active than citric acid, and this prevents the citric acid from fully reacting with hydroxy groups in the fibre. However, when the fabric is first treated by citric acid, any groups left unreacted can then be further esterified by BTCA, thus further improving the WRA of the fabric. The results show that a satisfactory WRA of higher than 280 can easily be achieved by a two-step method when the sample is first treated with 4.3% citric acid and then treated with 1.7% BTCA. Strength retention of the fabric treated by the twostep method is less than that of the fabric treated by the mixed method, which is mainly due to the longer curing time in the two-step method.

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