JPH0219231B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for modifying silk fibers by graft processing. Conventionally, it has been known to graft vinyl compounds such as styrene and hydroxyethyl methacrylate onto silk fibers to increase the amount of silk fibers and to impart bulkiness, shrink-proofing properties, heat-setting properties, etc. to the silk fibers. However, these methods had an adverse effect on silk's characteristic feel, luster, moisture absorption, and dyeability. In recent years, this drawback has been somewhat improved by using acrylamide and methacrylamide, but this time the disadvantage is that the advantages of conventional graft processing, such as shrink-proofing and bulkiness, cannot be sufficiently obtained. It was hot. The present invention eliminates all of these drawbacks and creates silk with excellent wrinkle resistance, morphological stability, light fastness, bulkiness, etc. without impairing the original characteristics of silk such as luster, texture, dyeability, and moisture absorption. To provide a method for obtaining silk fiber products with high yield. The method of the present invention applies the following general formula to silk fibers: (However, X is hydrogen or a methyl group, and Y is hydrogen or an alkyl group) is grafted onto the monomer, and then the silk fiber is impregnated with an acidic catalyst and heat-treated. That is, in the present invention, silk fibers grafted with the monomer represented by general formula (1) are further impregnated with an acidic catalyst, and heat treated at 100°C or higher.
By causing a crosslinking reaction to occur in the alkoxymethyl groups or hydroxymethyl groups in the graft polymer, it is possible to improve the wrinkle resistance, shape stability, etc. of silk fiber products to a very high degree. As the acidic catalyst, any catalyst that is generally used for anti-wrinkle treatment of cotton with a thermosetting resin can be used, and it is particularly preferable to use various organic acids alone or in combination with an organic acid and magnesium chloride. As organic acids, formic acid, acetic acid, citric acid, etc. are easy to use, and from the viewpoint of crosslinking effect and whiteness, the combined ratio of these organic acids and magnesium chloride is about 1/2 to 1/10 by weight. desirable. The silk fibers treated by the method of the present invention may be in any form such as thread, woven fabric, knitted fabric, non-woven fabric, etc.
It may also be mixed with other fibers, woven together, or knitted together. Further, typical monomers of formula (1) used in the present invention include acrylamide or methacrylamide derivatives in which Y is hydrogen or an alkyl group having 1 to 6 carbon atoms, such as methoxymethylacrylamide, Ethoxymethylacrylamide, isopropoxymethylacrylamide, n-
Propoxymethylacrylamide, n-butoxymethylacrylamide, hydroxymethylmethacrylamide, etc. are all effectively used. Grafting of these monomers onto silk fibers is carried out using a catalyst such as a persulfate under normal pressure or pressure, as in normal grafting, but especially at temperatures above 150°C, particularly at 200°C. It is preferable to carry out the heating at a higher temperature. In the present invention, silk is modified using a derivative of acrylamide or methacrylamide in which one hydrogen atom of the amino group is replaced with an alkoxymethyl group or a hydroxymethyl group. Compared to , it not only has higher grafting efficiency, but also has a remarkable effect of improving wrinkle resistance, shape stability, bulkiness, etc., and it is easier to obtain so-called stiff silk fiber products, so it is especially suitable for processing thin fabrics. Demonstrates excellent effects. In addition, when the main focus is on improving practical performance such as wrinkle resistance and shrink resistance, significant effects can be obtained by impregnating the grafted silk fiber with an acidic catalyst and baking with hot air or steam. can. Next, the present invention will be described in more detail with reference to Examples. Example 1 Using 50 g of refined Hiraha Futai (with 6 monme) as a sample, 1.5 g of 1.5 g of butoxymethyl acrylamide, 20 g of Texanol SH (surfactant), 2 g of potassium persulfate (catalyst), and 3 g of formic acid (80%) were prepared. Immerse in a treatment bath (bath ratio 1:30) at room temperature, gradually heat the treatment bath with gentle stirring under a pressure of 3 kg/cm ² , bring it to 280°C for 20 minutes, and keep it at this temperature for 30 minutes. Continued processing. Thereafter, the sample was taken out, washed lightly with water, and soaked in a bath containing soap (2 g/) and hydrosulfite (0.5 g/) for 80 min.
℃ for 20 minutes and then washed with water. The dry weight of the grafted product thus obtained was increased to 67 g (weight increase rate, ie, grafting rate: 34%; grafting efficiency: 85%), resulting in a product with a firm texture. This is the product. This product was divided into two halves, one half was impregnated with an aqueous solution containing 5% magnesium chloride and 1% citric acid, the squeezing rate was 90%, and hot air baking was performed at 120°C for 10 minutes. After acid treatment and baking, the product had high repellency and a firm texture. This is the product. The results of physical property tests and dyeing tests of these products are compared with the results obtained for untreated Hirahabutae and Hirahabutae grafted with methacrylamide according to the conventional method, and are shown in Tables 1 and 2. It is shown in Table 2.

【table】

[Table] As shown in Table 1, the products obtained by the method of the present invention have almost no change in bending resistance and moisture absorption rate, and have good bulkiness (thickness) and morphological stability, similar to products not treated with acid catalyst. (shrinkage rate), wrinkle resistance, light resistance, etc., and furthermore, wrinkle recovery and shrink resistance are significantly improved compared to finished products. Next, in terms of dyeability, the product of the present invention has
As shown in Table 2, it was confirmed that the effect was equivalent to or better than that of the untreated product. Example 2 A sample of 50 g of refined Hirahabutae (with 6 momme) was prepared in a 1.5 treatment bath (bath ratio 1: 30) was grafted in the same manner as in Example 1 to obtain a product with a dry weight of 65 g (grafting ratio 30%; grafting efficiency 75%).
This product is a product. The product was divided into two halves, one of which was passed through a bath containing 5% magnesium chloride and 1% acetic acid, squeezed to 90% and baked at 120° C. for 10 minutes. This product is a product. The results of physical property tests for these products are shown in Table 3 in comparison with the results for untreated Hirababutae. In this example, as in Example (1), the product of the present invention was a firm product with significantly improved bulkiness and wrinkle resistance, with almost no change in hygroscopicity and bending resistance. I understand.

[Table] Note: The physical property test method is the same as Table 1.

Claims (1)

[Claims] 1 Silk fiber has the following general formula (wherein, X is hydrogen or a methyl group, and Y is a hydrogen or alkyl group) is grafted onto the monomer, and then the silk fiber is impregnated with an acidic catalyst and heat-treated. Modification treatment method. 2. The method according to claim 1, wherein the grafting process is carried out under pressure in the presence of a polymerization catalyst. 3. The method according to claim 1 or 2, wherein the acidic catalyst is a mixture of organic acid and magnesium chloride in a weight ratio of 1/2 to 1/10.