JPH0768671B2 - Method for modifying cellulosic fibers - Google Patents

Description

TECHNICAL FIELD The present invention relates to an improvement in a method for modifying a cellulosic fiber, and in particular, a relatively easy dipping treatment causes a very small decrease in strength and an improvement in texture in a short time. To obtain a modified cellulosic fiber.

[Conventional technology]

As a method of modifying the cellulosic fiber material to improve physical properties such as hygroscopicity, water absorption, and gloss, a method of treating cellulosic fiber with an aqueous solution containing cellulase (Japanese Patent Publication No.
52-48286), a method of pretreating the fiber with an aqueous swelling agent solution (Japanese Patent Laid-Open No. 58-54082) is also proposed.

[Problems to be Solved by the Invention]

However, according to these conventional methods, although the feeling is improved, the strength is largely decreased and it takes a relatively long time. Further, the method of JP-A-58-54082 is a two-step method which requires pretreatment. It is a treatment method and has a problem that the handling is complicated compared to the one-bath or the same-bath treatment method.

Therefore, the object of the present invention is to improve the above-mentioned problems, and by the one-bath processing method which is relatively short and easy to process, the decrease in the strength of the cellulosic fiber is small, and the feeling is
It is to provide a method for improving water absorption and the like.

[Means for Solving the Problems]

The present invention is a method for modifying a cellulosic fiber, which comprises treating the cellulosic fiber with a cellulase-containing aqueous solution in combination with a polyether-modified silicone.

The polyether-modified silicone used in the present invention is preferably a compound represented by the following formula (1) or (2).

In the formula, m, l and a are integers of 1 or more, n and b are 0 or integers of 1 or more, and X is an alkyl group having 2 to 8 carbon atoms and having an amino group, an epoxy group or a carboxy group at the terminal. And R represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

In the formula, m and a each represent an integer of 1 or more, b represents 0 or an integer of 1 or more, and R represents hydrogen or an alkyl group having 1 to 4 carbon atoms.

The polyether-modified silicone represented by the formula (1) includes, for example, TSF 4440 manufactured by Toshiba Silicone Co., Ltd. and Y-7499 manufactured by NUC Silicone Co., Ltd., and the polyether-modified silicone represented by the formula (2) Are, for example, product names L-7001 and L-7002 manufactured by NUC Silicone. These may be mixed and used.

Cellulases that can be used in the present invention include cell crust (trade name, manufactured by Novo Co., Ltd.) made from cells of the genus Trichoderma, and Aspergil.
ls) cellulosin AC-8 (trade name, manufactured by Ueda Chemical Industry Co., Ltd.) made from cells of the genus.

In carrying out the method of the present invention, cellulase is usually used.
An aqueous solution of 0.1 to 2.0% by weight is prepared, and a polyether-modified silicone is added to this so as to be 0.01 to 1.0% by weight, and more preferably an organic acid such as acetic acid or oxalic acid is used to adjust the pH to 4 to 4.
Adjust to 6 to obtain a treatment liquid. In the treatment, the temperature of the treatment liquid is usually in the range of 30 to 60 ° C, preferably 40 to 55 ° C. If the treatment temperature is higher than 60 ° C, the enzyme titer will be decreased more quickly, which is not preferable.

The treatment time depends on the cellulase concentration of the treatment liquid, pH, treatment temperature and the shape and type of the fiber to be treated, and is not limited, but is usually 30 minutes to 5 hours in the method of the present invention.
The cellulosic fibers treated with the above treatment liquid are washed with water, dehydrated and dried.

The weight loss rate and tear strength retention rate of the cellulosic fibers treated as described above are usually 2 to 10% and 10 respectively.
0-80%, and its texture has a smooth unique pliability,
It also exhibits excellent water absorption.

Examples of the cellulosic fiber product treated according to the present invention include yarns such as cotton, hemp and rayon, and knitted fabrics.

[Action]

Compared to the cellulase treatment method alone or the cellulase treatment method after pretreatment with an acid, an alkali, a metal salt, etc., the method of the present invention uses a polyether-modified silicone aqueous solution in combination to allow the cellulase to permeate the fiber in one bath. In addition to improving the property, the effect is enhanced and the effect of uniformly modifying the surface of the fiber in a short time is brought about. Therefore, the strength decrease of the fiber due to cellulase is very small, the water absorption is enhanced, and the effect of softening the texture is brought about.

〔Example〕

Next, examples of the present invention will be specifically described, but it goes without saying that the description does not limit the present invention.

Each test value was measured as follows.

(2) Tear strength retention rate: Tear strength was measured by the JIS, L-1096 Bendulum method,
It was defined as the% ratio to the tear strength of the untreated sample.

(3) Feeling evaluation method: ○: Good flexibility △: Slight flexibility is recognized ×: No flexibility (blank texture) Example 1 Both warp and weft yarns are single 40th 0.5% by weight of cellulase (Cell Crust: Novo Co.) of 100% cotton 100% silket exposed twill fabric with 120 threads per 1 in.
And 0.1% by weight of polyether-modified silicone (TSF 4440: manufactured by Toshiba Silicone Co., Ltd.), immersed in a bath adjusted to pH 5.0 with oxalic acid (bath ratio 1:30, bath temperature 54 ° C) and circulated. It was treated for 30 minutes. Then, it was washed with water and then dehydrated and dried.

The property evaluations of the cotton fabric obtained by the above treatments regarding the weight loss rate, the tear strength retention rate and the feeling are shown in Table 1 below.

Comparative Example 1 A cotton fabric was treated in the same manner as in Example 1 except that the bath in which the polyether-modified silicone was removed was used. The property evaluation of the obtained cotton fabric is shown in Table 1.

Comparative Example 2 In the bath liquid used in Example 1, a nonylphenol nonionic activator (H.
A cotton fabric was treated as in Example 1 except that 0.1% by weight of LB 13.3) was used. The property evaluation of the obtained cotton fabric is shown in Table 1.

Comparative Example 3 The cotton fabric used in Example 1 was pretreated by immersion in a 65 wt% sulfuric acid solution (20 ° C.) for 5 seconds, washed with water, and 1 wt% of sodium carbonate.
The solution was neutralized with an aqueous solution, washed with water, and then squeezed.

The squeezed cotton fabric was immersed in a 0.5% by weight cellulase water bath (cellulase; cell crust, bath ratio; 1:30, pH 4.5, bath temperature; 45 ° C.) in a wet state and treated for 8 hours while circulating the liquid. After washing with water and dehydration, caustic soda 0.2% by weight
Further, it was immersed in an aqueous solution containing 50% by weight of sodium thiosulfate (50 ° C.) for 30 minutes, washed with water, dehydrated and dried. Table 1 shows the obtained property evaluations.

Example 2 Example 1 except that the concentration of cellulase in the treatment liquid was 1% by weight and the polyether-modified silicone was 0.2% by weight.
A 100% hemp plain weave was treated in the same manner. Table 2 shows the obtained property evaluation.

Comparative Example 4 A 100% hemp plain fabric was treated in the same manner as in Example 2 except that the bath in which the polyether-modified silicone was removed was used. Table 2 shows the obtained property evaluation.

Comparative Example 5 In the bath solution used in Example 2, a nonylphenol-based nonionic activator was added in place of the polyether-modified silicone.
A 100% hemp plain weave was treated in the same manner as in Example 2 except that 2% by weight was used. Table 2 shows the obtained property evaluation.

Comparative Example 6 Comparative Example 5 except that the treatment concentration of cellulase was 1% by weight.
A 100% hemp plain weave was treated in the same manner. Table 2 shows the obtained property evaluation.

[Effect of the invention] As is clear from the data of the above-mentioned Examples and Comparative Examples, when treating the cellulosic fibers with cellulase according to the present invention, a treatment liquid containing a polyether-modified silicone was used, and With the bath treatment, the weight loss rate is small,
It is possible to obtain a fiber product having a high tear strength retention rate and an excellent feeling.

Claims (2)

[Claims] 1. A method for modifying a cellulosic fiber, which comprises treating a cellulosic fiber with a cellulase-containing aqueous solution by adding a polyether-modified silicone to the aqueous solution. 2. A polyether-modified silicone has the following general formula:
The method according to claim 1, which is represented by (1) or (2). (In the formula, m, l, and a are integers of 1 or more, n and b are 0 or an integer of 1 or more, and X is an amino group, an epoxy group, or a carboxy group having 2 to 8 carbon atoms. Represents an alkyl group of R is hydrogen or an alkyl group having 1 to 4 carbon atoms) (In the formula, m and a each represent an integer of 1 or more, b represents 0 or an integer of 1 or more, and R represents hydrogen or an alkyl group having 1 to 4 carbon atoms).