JPH0342351B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a treatment method for improving the quality of silk fiber products, and in particular, it highly suppresses the occurrence of "wrinkles" when worn and eliminates fine wrinkles caused by washing, without impairing the excellent properties unique to silk fibers. The present invention relates to a treatment method that prevents generation and shrinkage and imparts wrinkle resistance, easy care properties, and shape stability to silk fiber products. As is well known, silk fibers have a unique, elegant texture and luster, as well as excellent mechanical properties such as strength and elasticity. However, when silk fibers are used for clothing, they tend to wrinkle when worn, and even when washed under mild conditions with a neutral detergent, they tend to wrinkle and lose their shape. In order to prevent these defects of silk fibers, thermosetting resins conventionally used for wrinkle-proofing of cellulose fibers, such as uremic toxins, ethylene urea-based, glyoxal-based, glyoxal-based, and melamine-based initial condensates, are used. Attempts have been made to use a condensation catalyst in conjunction with a condensation catalyst, but no significant effect was obtained, and instead the result was a negative effect of impairing the feel and luster characteristic of silk. That is, there is a big difference in that cellulose fibers are made using spun yarns, whereas most silk fibers are made from filament fibers. Also, in terms of molecular structure, cellulose fibers have many hydroxyl groups in their main chain molecules, so the distance between the functional groups is short, whereas silk fibroin has different functional groups such as hydroxyl groups, amino groups, and carboxyl groups. are sparsely distributed in small quantities, and the distance between the functional groups is large. Therefore, even if an attempt is made to form intermolecular crosslinks by the processing method described above, the spacing between the functional groups is too large for the crosslinking agent or the initial condensation. Since the growth limit of the polymer is exceeded due to the acceleration of the reaction, it is difficult to form crosslinks between functional groups through the polymer, and the crosslinking agent fills and hardens exclusively in the molecular gaps or is bonded to one end of the functional groups. In other words, only a graft-like branch is formed, and the amount of crosslinking agent involved in crosslinking is extremely small, and the frequency of intermolecular crosslinking is low. Therefore, in order to obtain a sufficient effect by such a method, a large amount of crosslinking agent is required, which causes disadvantages such as impairing the texture and luster of silk. It has been difficult to obtain durable wrinkle-proofing properties, shrink-proofing properties, easy care properties, and shape stability while retaining the unique advantages of silk fibers. As a result of various studies in order to eliminate the above-mentioned drawbacks, the present inventor found that grafting silk fibers with N-alkoxymethylacrylamide and N-alkoxymethylmethacrylamide (hereinafter referred to as N-alkoxymethyl(meth)acrylamide) works well. He discovered that good results could be obtained and first filed a patent application in 1982.
It was proposed as No. 1595. As a result of further studies on this improved method, the present inventor found that when silk fiber products are treated with N-alkoxymethyl (meth)acrylamide under specific conditions, durable morphological stability is imparted and the texture is reduced. The present invention was completed by discovering that it is possible to easily obtain a product that does not have to be produced. That is, the method of the present invention applies the general formula to silk fiber products. (wherein, X is hydrogen or a methyl group, and Y is an alkyl group); at least one catalyst selected from a condensation catalyst and a polymerization catalyst;
It is characterized by being impregnated with a treatment liquid containing an organic acid and then subjected to dry heat or wet heat treatment. The silk fiber products of the present invention include woven fabrics containing silk fibers,
It includes knitted fabrics, nonwoven fabrics, threads, and products using these, and the alkyl group Y of the above compound, that is, N-alkoxymethyl (meth)acrylamide, is not particularly limited, but generally has 1 to 4 carbon atoms.
Preferably, it is an alkyl group. As condensation catalysts, those used in the processing of general thermosetting resins, such as heavy metal chlorides, heavy metal nitrates, and organic amines, are all effective, but magnesium chloride is especially effective for silk fiber products. It is preferable because it has the least negative effects (yellowing, deterioration), and the best effect can be obtained by using it in combination with an organic acid. The amount used is 5-50g of MgCl ₂ and 0.5-10g per treatment bath.
Formic acid, acetic acid, citric acid, tartaric acid and the like are effective organic acids, but acetic acid is most preferably used. On the other hand, water-soluble radical initiators are effective as polymerization catalysts, and persulfuric acid Na, K, NH ₄ salts are particularly effective in the method of the present invention, and it is desirable to use them in the range of 1 to 10 g/. . In the present invention, a condensation catalyst or a polymerization catalyst may be used alone, but the condensation catalyst promotes the condensation reaction of the alkoxymethyl groups of N-alkoxymethyl (meth)acrylamide, and the polymerization catalyst promotes the condensation reaction of the alkoxymethyl groups of N-alkoxymethyl (meth)acrylamide, and the polymerization catalyst Since the polymerization reaction is promoted, it is desirable to use both catalysts together. When a condensation catalyst and a polymerization catalyst are used together, it is preferable to appropriately adjust the degree of the condensation reaction and polymerization reaction. If only the condensation reaction is allowed to proceed, shrink-proofing properties can be achieved, but since the filling effect into the silk fabric fibers is insufficient, wrinkle-proofing, especially the improvement of wrinkle-proofing properties when wet, tends to be insufficient, and only the polymerization reaction takes priority. In this case, there is almost no deterioration in the texture, but the anti-shrinkage and anti-wrinkle effects may not be achieved sufficiently. Therefore, although the effect can be exhibited even if the condensation catalyst and the polymerization catalyst are used separately, it is particularly preferable to use both catalysts in the same bath. In addition, the amount of N-alkoxymethyl (meth)acrylamide used is generally preferably 100 to 500 g/, and by further using acrylamide or methacrylamide in combination, the intrafiber plasticizing effect is enhanced and silk fibers are It is also possible to suppress a decrease in strength and elongation and tear strength of the product. Typical N-alkoxymethyl (meth)acrylamides used in the present invention include N-methoxy, N-ethoxy, N-n propoxy, N-isopropoxy, N-butoxy, N-isobutoxy, and N-tert-butoxy-methylacrylamide (or methacrylamide). The higher the alkyl group Y in the alkoxyl group, the greater the effect of improving the bulkiness and shrink resistance of the product, but the best effect on wrinkle resistance can be obtained with an ethoxy compound or a propoxy compound. Furthermore, when comparing acrylamide derivatives and methacrylamide derivatives, the latter has higher polymerization reaction efficiency and results with higher reproducibility, which is advantageous in terms of production control in industrial production. In the present invention, silk fiber products are impregnated with a treatment solution containing such N-alkoxymethyl (meth)acrylamide and a catalyst and then heat treated. Any method can be used, and the impregnation rate is approximately 70% or more, especially 80% of the weight of the silk fiber product.
It is preferably about 150%. Both dry heat and moist heat are useful as heat treatment methods, and the dry heat method has a high effect of improving dry wrinkle resistance, while the moist heat method has a high effect of improving moisture wrinkle resistance. The temperature is 120 to 140℃ for dry heat method and 100 to 120℃ for wet heat method.
15 to 60 minutes at ℃ is appropriate. Next, the present invention will be explained in more detail with reference to Examples. Example 1 Soak refined 12 momme silk habutae in the following treatment bath,
The liquid was squeezed to a 95% pick-up using a two-roll mangle. N-isopropoxymethyl methacrylamide
200g Non-ionic penetrant 1g Sodium persulfate 4g Magnesium chloride 12g Acetic acid 2g Total volume with water added 1000ml This saturated sample was fixed on a pin frame and heated at 75°C.
It was dried for 3 minutes and then subjected to dry heat treatment at 125°C for 15 minutes.
After treatment, it was soaped at 65°C for 15 minutes in a bath containing 3 g of Marcel soap and 1.5 g of hydrosulfite, washed with hot water, washed with water, and dried. A fabric with a stiff texture was obtained with a polymerization increase rate of 18.6%. As a result of the same processing without using sodium persulfate in the formulation, the weight increase rate was 15.5
%, a fabric with a firm feel was obtained, but the bulkiness seemed to be somewhat lacking. As a result of applying the same processing to the formulation except for magnesium chloride, the weight increase rate was 13.2
%, a fabric with considerable flexibility was obtained, but the repellency seemed to be somewhat lacking. Example 2 Refined 12 momme silk habutae was immersed in the following treatment bath.
Squeeze 85% liquid into a pick-up using this roll mangle. N-n propoxymethyl methacrylamide 200g Methacrylamide 50g Nonionic penetrant 1g Potassium persulfate 5g Magnesium chloride 12g Acetic acid 2g Total volume with water added 1000ml This saturated sample was steamed at 100°C for 20 minutes without drying. . After the treatment, soaping, washing with water, and drying were carried out in the same manner as in Example 1. Weight increase rate 21.8%
A soft and stiff fabric was obtained. Example 3 Refined 12 momme silk habutae was immersed in the following treatment bath.
The liquid was squeezed to %. N-Ethoxymethylacrylamide 250g Non-ionic penetrant 1g Sodium persulfate 5g Magnesium chloride 15g Acetic acid 3g Total volume including water 1000ml This saturated sample was dried at 75°C for 3 minutes and then at 130°C.
It was subjected to dry heat treatment for 15 minutes, soaped, and washed with water. A stiff fabric with a weight increase rate of 18.8% was obtained. The physical property test results of processed samples obtained in each example are shown in the following table.

【table】

[Table] In the case of Example 1, in which a condensation catalyst and a polymerization catalyst were used in combination as catalysts, the strength and elongation and tear strength were somewhat lowered, but the wrinkle recovery and washing resistance were lowered.
The wearability has been improved to the highest level, and the resin adhesion efficiency is also high.
On the other hand, in the same process using only a condensation catalyst (Example 1), a considerably significant quality improvement effect was obtained, but it was slightly inferior to Example 1.
In addition, in the case of processing using only a polymerization catalyst (Example 1), a considerable improvement in wet wrinkle recovery is observed, but the improvements in dry wrinkle recovery, wash/wear properties, and shrink resistance are not so great, and the amount of resin deposited is also the lowest. small. In Example 2, methacrylamide was used in combination to obtain an internal plasticizing effect, and the condensation/polymerization reaction was carried out by moist heat treatment, but in this case, the improvement in dry wrinkle recovery was slightly lower, but other physical properties were All of them were ranked highest, and the most balanced processing effect was obtained. In Example 3, an acrylamide derivative with low resin adhesion efficiency was used, so the concentration of the processing agent was increased.
Although the heat treatment conditions were also strengthened, results slightly inferior to those of Example 1 were obtained. However, a considerably high performance improvement effect is still recognized. From the above results, it is possible to impart practical performance to silk woven and knitted fabrics using the treatment method of the present invention, making it possible to use silk in wide-width fabrics, and in particular to develop demand for formal men's wear and casual products. It is expected that this will happen.

Claims (1)

[Claims] 1. A silk fiber product with a general formula (wherein, X is hydrogen or a methyl group, Y is an alkyl group), at least one catalyst selected from a condensation catalyst and a polymerization catalyst, and a treatment liquid containing an organic acid is impregnated, A method for improving the quality of silk fiber products, characterized by dry heat or wet heat treatment. 2. The method according to claim 1, wherein the treatment liquid contains a polymerization catalyst, a condensation catalyst, and an organic acid.