JPH01266276A - Modified processing of silk yarn product - Google Patents

Abstract

PURPOSE:To improve wear resistance, yellowing and browing resistance, wrinkle resistance, etc., of silk yarn product, by dissolving an epoxy compound and a reaction catalyst in a mixed solution of a polar approtic solvent and water to give a composition, impregnating the composition into a silk yarn product and subjecting the yarn to wet heat treatment. CONSTITUTION:An epoxy compound such as a compound having two or more epoxy groups and <=1,000mol.wt. and a reaction catalyst (e.g., water-soluble neutral or weakly basic metallic salt) are dissolved in a mixed solvent of a polar approtic solvent having preferably >=100 deg.C boiling point, such as dimethyl sulfoxide and water in the weight ratio of 95:5-51:49 to prepare a composition, which is impregnated into a silk yarn product, pressed and then the silk yarn product is subjected to wet heat treatment in high-temperature steam at >=100 deg.C to readily improve functions such as wear resistance, yellowing and browning resistance, wetting resistance, wrinkle resistance and washing resistance while maintaining characteristic properties of silk yarn.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method for modifying textile products composed of silk fibers. More specifically, threads composed of silk fibers,
Knitted fabrics, woven fabrics, and sewn products, as well as blended, twisted, and interwoven fiber products whose main constituent is silk fiber, retain the excellent organoleptic properties unique to silk fiber, while maintaining abrasion resistance, which has traditionally been pointed out as a drawback. , yellowing resistance, moisture resistance and wrinkle resistance,
This invention relates to a modification method that can improve functional properties such as washing resistance.

Conventional technology Silk fiber products have been widely praised for their unique feel, appearance, and texture as natural fibers. Stimulated by price increases, various modification processes have been proposed and put into practical use. This modification process prioritizes cost reduction over sensory properties, and involves grafting with vinyl monomers, etc., mainly for the purpose of increasing weight, and imparts even more desirable functional properties while maintaining the excellent sensory properties of silk fibers. and a method for.

The latter method of imparting more desirable functional properties to silk fibers includes, for example, (1) using an epoxy compound, (2) applying a general resin processing modification method, and (3) synergistically combining the two. Examples include those that measure effectiveness.

As for the method (1) above, for example, an epoxy polymer and
A silk fiber product is immersed in a solution containing an alkali metal hydroxide or an alkaline salt of an alkali metal that has a swelling effect on silk fibers and has an addition reaction catalytic effect between silk fibers and the epoxy polymer. Modification method for improving shrink-proofing and wash-and-wear properties by dry heat or steam treatment after liquid drying (Japanese Patent Publication No. 38-25118)
can be mentioned. If the epoxy polymer used in this product is water-soluble, it can be used as it is as an aqueous solution,
If it is water-insoluble, it is dissolved in a mixed solvent of water and a water-soluble solvent such as alcohol, acetone, or dioxane, or used as an emulsified dispersion by an appropriate method. In addition, protein fibers can be prepared in an aqueous emulsion, an aqueous solution, an organic solvent solution, or a mixture of a water-miscible organic solvent and water containing a specific epoxy compound and one or more neutral salts. By heating treatment, wrinkle resistance when dry or wet,
A modification method for permanently imparting properties such as shrink resistance, light resistance, and chemical resistance is also known (Japanese Patent Publication No. 17-24199). In addition, "silk fibers are impregnated with an aqueous solution of a neutral salt of an alkali metal, and after squeezing, further impregnated with an organic solvent containing an epoxy compound, and then heat-treated at a temperature of 100°C or less, resulting in heat-resistant alkaline and acid-resistant properties. , a method for imparting desirable properties such as color fastness, wrinkle resistance, and shrink resistance (Japanese Patent Publication No. 52-38H1), in which silk fibers are placed in an aqueous solution of a polyhydric alcohol-based epoxy compound and an alkali metal salt of a monocarboxylic acid. A method of obtaining a material with improved practical performance in terms of wrinkle recovery, light resistance, alkali resistance, dyeing resistance, etc. by soaking, deliquing, and then heat treatment (Japanese Patent Laid-Open No. 1983
-81369), silk fibers are impregnated with an aqueous solution containing polyhydric alcohol diglycidyl ether and a catalyst.
Retains 0 to 300% by weight, wrinkle resistance,
Method for imparting anti-shrinkage and anti-discoloration properties (Unexamined Japanese Patent Publication No. 62-1s
No. 071) and the like have also been proposed.

As for the method (2) above, for example, after treating with a urea or thiourea solution, the fibers are dried until the moisture content in the fibers becomes 10% or less, and then formaldehyde vapor of IOO00 or more is applied to improve the texture and texture. A method for simultaneously imparting excellent wrinkle resistance with excellent durability and excellent light resistance without impairing the original excellent properties of silk fibers such as luster, and physical properties such as strength and elongation (Special Publication No. 1973- Publication No. 7239)
After treatment with a solution of urea or thiourea and formaldehyde-based initial condensation resin, the fibers are dried until the water content in the fibers is reduced to 10% by weight or less, and then treated with formaldehyde vapor at 100°C or higher. Method for preventing wrinkles under humidity (Special Publication No. 4S-2443
7), an aliphatic, alicyclic or aromatic compound having at least two hydroxyl groups and a molecular weight of 400 or less,
Or, after treating with ethanolamine or an aliphatic amine having two amino groups and a molecular weight of 400 or less, either alone or in a mixed solution, the fibers are dried until the moisture in the fibers is reduced to 10% or less, and then heated at +N°C or higher. A method of imparting wash-and-wear properties by applying formaldehyde vapor has been proposed (Japanese Patent Publication No. 48-41797).

Furthermore, as method (3), for example, after improving chemical resistance and wet wrinkle resistance by a two-phase method in which silk fibers impregnated with a neutral salt aqueous solution are heated in an organic solvent solution containing an epoxy compound, , a method in which a conventional pad dry curing method using a cellulose-reactive crosslinking agent is applied to improve dryness and crease retention (Japanese Patent Laid-Open No. 62-23
No. 1079), a method of imparting excellent dyeing properties, antistatic properties, light fastness, wrinkle resistance, bulkiness, pleatability, etc. by treating with an epoxy compound and then graft polymerizing with a vinyl compound (special Kaisho H-HOH No. 5 Publication)
, a method is known in which fibers are modified into disperse dye dyeable fibers by treatment with an epoxy compound and then graft polymerization with a hydrophobic vinyl compound (Japanese Unexamined Patent Publication No. 250276/1983).

In addition, in order to streamline the treatment with epoxy compounds, a method (specially 1986-
252771), and a method in which fibers are impregnated with a mist or foam composition containing an epoxy compound and a catalyst and subjected to microwave irradiation without pre-drying (Japanese Unexamined Patent Publication No. 6L-02). Proposed.

As can be inferred from the above proposals, the use of epoxy compounds is expected to yield the best results as a modification processing method for imparting various functionalities while retaining the original sensory characteristics of silk fiber products. be able to. Practically speaking, wet processing technology using a two-phase method (Japanese Patent Publication No. 52-38H1) is suitable, and the present inventors have previously proposed a specific processing method and apparatus for this wet processing technology (Japanese Patent Application No. 62
-0061).

However, these modification processing methods have the following problems.

(1) Silk fiber products impregnated with a neutral salt aqueous solution that serves as a catalyst require manual work to be avoided before proceeding to the next step of organic solvent treatment of the epoxy compound due to the need to control the tension of the fabric in a wet state. First, the surface of the fabric becomes fluffy due to rubbing, and this tendency increases especially as the width of the fabric increases and the fabric weight increases.

(2) The two-phase method involves difficulties in storage management of the cloth impregnated with a neutral salt aqueous solution until it is transferred to the complicated solvent treatment. In other words, complex countermeasures are required, including managing the moisture content of long fabrics that are soaked and dehydrated at low speeds, and the moisture content of the waste, as well as the effects of seasonal fluctuations in room temperature.

(3) The time required for treatment with an epoxy compound in an organic solvent is from the time the fabric is introduced into the equipment until the chemical solution is completely removed from the fabric after the reaction and then taken out. However, the productivity is not always satisfactory.

Problems to be Solved by the Invention The present invention aims to improve abrasion resistance, yellowing resistance, moisture resistance, wrinkle resistance, washing resistance, etc. through simple operations while retaining the excellent organoleptic properties unique to silk fibers. The purpose of this work is to provide a method for modifying silk fiber products that can improve their functional properties.

Means for Solving the Problems The present inventors have conducted various studies to develop a method for modifying silk fiber products that increases functional properties while maintaining organoleptic properties. After impregnating a silk fiber product with a treatment composition containing a compound and a reaction catalyst for the reaction with silk, the liquid is squeezed and subjected to a moist heat treatment in high-temperature steam, so that the inside of the swollen silk fiber can be removed in a relatively short period of time. It has been discovered that the above object can be achieved by forming a cross-linked bond between the two, and based on this knowledge, the present invention has been completed.

That is, the present invention impregnates a silk fiber product with a treatment composition prepared by dissolving an epoxy compound and a reaction catalyst in a mixed solvent of a polar aprotic solvent and water, and then squeezes the liquid and applies high-temperature steam. The present invention provides a method for modifying silk fiber products, which is characterized by carrying out a heat treatment in a medium.

The present invention will be explained in detail below.

Suitable polar aprotic solvents used in the method of the present invention include those having a boiling point of 100° C. or higher, such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, hexamethylphosphonic acid amide, and N-methylpyrrolidone. These polar aprotic solvents are mixed with water in any proportion to form a mixed solvent, and a stable treatment composition is prepared by dissolving the epoxy compound and the neutral salt catalyst in this solvent.

The weight ratio of polar aprotic solvent to water is preferably 95:
5-51:49, particularly preferably 9o:10-70:3
It is in the range of 0. Wet stability of treated silk fiber products when the water content in the polar aprotic solvent is less than 5% by weight;
For example, the wet wrinkle resistance is significantly reduced, and if it exceeds 49% by weight, the desired effect cannot be obtained sufficiently. It is assumed that these phenomena are related to the distribution state of cross-linking points between the silk fiber and the epoxy compound in the fiber cross section, where the reaction is promoted in high-temperature steam. That is, water in silk fibers subjected to steaming conditions using high-temperature steam evaporates until equilibrium is reached. Along with this movement of water out of the fiber, the coexisting polar aprotic solvent is moved, and the crosslinking components also occur, resulting in relatively more crosslinking around the fiber surface, and some epoxy resins are removed. It is presumed that an excellent surface modification effect is imparted by depositing a large amount of polymer.

On the other hand, zoo' like acetone and tetrahydrofuran
When a mixed solvent of water and a polar aprotic solvent having a boiling point of less than c is used, the solvent easily evaporates in the superheated steam, and the effect obtained by the mixed solvent system of the present invention cannot be obtained.

The epoxy compound used in the method of the invention is at least 2
Although it is a conventionally known one having 1 or more epoxy groups,
It is desirable that the molecular weight is 1000 or less.

Furthermore, among the conventionally known catalysts for promoting the reaction between the epoxy compound and silk fibers, water-soluble neutral or weakly basic metal salts are suitable.

The high-temperature steam used in the method of the present invention is obtained by superheating steam under normal pressure. decreases.

Silk fiber products can be impregnated with these treatment compositions by conventionally known methods, such as immersion at room temperature or in a heated bath;
Alternatively, a method such as spray application can be adopted.

Further, as a method of squeezing, pressurized muzzle vacuum dehydration, centrifugal dehydration, etc. are used, but it is important to uniformly control the adhesion of the treatment composition to the fibers. The extraction rate is not particularly limited, but is preferably in the range of 80 to 110% from the viewpoint of production control.

Silk fiber products that have been uniformly squeezed in this way are left with 10
The reaction is promoted by being introduced into superheated steam at 0°C or higher.

The steaming conditions are usually 150°C or less and 10 minutes or less, but since coloring of the fabric may occur in proportion to the temperature and time, steaming conditions are preferably 1106C or less and about 10 minutes.

In addition, when the fabric impregnated with the treatment composition is continuously introduced into the superheating steamer, a retention zone should be provided between the squeezing process and the steaming process in order to increase the shrink resistance of the product and ensure uniform treatment. is desirable. In addition, with saturated steam at temperatures above 100°C, the progress of the reaction is significantly delayed, the amount of reaction products is small, and at the same time, the mechanical tension applied to the fabric cannot be alleviated, which inevitably reduces the shrink-proofing properties of the product. . Furthermore, the reaction using normal steaming at 100° C. or lower requires long-term steaming, the amount of reaction products is extremely small, and it is difficult to control the steaming temperature.

Incidentally, even if a silk fiber product is simply dried and heat-treated after being filled with the reaction solution of the method of the present invention, no modification effect will be obtained at all.

Effects of the Invention According to the method of the present invention, whereas conventional modification processing methods had to adopt a batch method, continuous processing is possible throughout the entire treatment process, making it easier to manage the production process. , it is possible to reduce processing costs and stably improve product quality. In other words, improvement effects comparable to those of the two-phase method were obtained in terms of yellowing resistance, moisture seasoning resistance, wrinkle resistance, and washing resistance.In particular, with regard to abrasion resistance, outstanding effects were confirmed compared to conventional methods, and durability was improved. It has excellent durability and can significantly change the conventional dyeing operation that had to avoid the occurrence of chafing, streamlining the dyeing process and improving dye fastness.

EXAMPLES Next, the present invention will be explained in more detail by examples.
The present invention is not limited in any way by these examples.

Example 1 A narrow silk fabric with a 2/2 twill structure consisting of 2 plain yarns among 27 warp silk yarns and 4 pieced yarns among 27 weft yarns was scoured and dried in accordance with a conventional method, and then woven at a weight ratio of 95:5. 85 parts of a mixed solvent of dimethyl sulfoxide and water, 9 parts, and 1 part of glycerin glycidyl ether
0 kg and 8.3 J2 g of Rodan soda were immersed in a treatment composition at room temperature, and then treated using a mangle.
Squeeze the liquid to 5%, shake it off on the conveyor lattice, and
After a few seconds, the mixture was continuously introduced into a high-temperature steamer maintained at 105°C in a suspended state, and steamed at 105°C for 7 minutes. The length of the suspension loop was kept within 1 m to reduce tension on the fabric due to its own weight. The obtained steamed cloth was washed with hot water and water, then bleached and post-treated according to a conventional method. The shrinkage rate of the silk woven fabric thus obtained was measured by the JISL-1042C method. As a result, while the untreated fabric had a shrinkage rate of 10% in both warp and weave, the treated fabric was able to suppress the shrinkage rate to within 0.5%, exhibiting excellent wash and wear properties. .

Furthermore, as a result of high-speed dyeing of the bleached fabric with an alloy dye using a Wins dyeing machine, the color density of the treated fabric was higher than that of the untreated fabric, and the color fastness was improved by about half. The appearance of the dyed fabric was that compared to the untreated fabric, which had noticeable fluff due to rubbing, the treated fabric had less rubbing and clear twilling.

Example 2 After scouring and drying a 112 cm wide three-ply satin, consisting of 2 pieces of warp silk thread 21 and 4 pieces of weft thread 21, in a conventional manner, dimethyl sulfoxide was added in a weight ratio of 90:10. The sample was immersed in a 40°C solution having the same composition as in Example 1 except that a mixed solvent of water and water was used, vacuum deliquified to a liquid extraction rate of 90%, shaken off onto a conveyor lattice, and left to stay for 30 seconds. , while forming a loop with a length of 1.5 ffi, the sample was introduced into a high temperature steamer in a suspended state, and steamed at 110° C. for 3 minutes. After washing the steamed cloth with hot water and water, it was post-treated by bleaching with thiourea dioxide according to a conventional method. The resulting treated fabric was significantly more effective in suppressing fuzzing due to wet abrasion than the untreated fabric.

Note that neither the fabric impregnated with the above solution was steamed for 3 minutes in saturated steam at 110°C nor the fabric subjected to dry heat treatment at 110°C for 3 minutes, resulting in a significant modification effect. In addition, regarding light resistance, the coloring of treated fabrics was significantly suppressed compared to untreated fabrics, and was effective in preventing yellowing.

Example 3 A 40-inch wide three-ply sateen consisting of 2 plain warp threads and 80 weft combed threads was subjected to enzyme scouring according to a conventional method.
Hydrogen peroxide bleach and dry. On the other hand, the weight ratio is 80:2
A solution was prepared containing 5% by weight of egylene glycol diglycidyl ether and 3% by weight of sodium acetate in a mixed solvent of 0% dimethylformamide and water. The solution was heated to 30°C.
The above-mentioned three-layer satin was filled with the reaction solution to 90% pick-up using a 2-dip, 2-nip method, and after being shaken off onto a conveyor and allowed to stay for 40 seconds, it was suspended in a high temperature steamer. The sample was introduced at 100° C. and steamed for 2 minutes at 101° C. for post-treatment. The resulting treated fabric was printed using a color paste containing an acid dye using a regular flat type automatic screen printing machine, dried, and further impregnated with a cellulose-reactive crosslinking agent according to a conventional method.
After drying and sewing into apparel, it was pleated and heat treated.

The resulting treated fabric has clearer printed patterns and deeper dyeing than untreated fabric, and the dye fastness of each hue is also 0 on average.
．． Improved by grade 5. In particular, even when an automatic screen printing machine with a printing speed of 21 m/min was used, no fuzzing due to rubbing was observed, and it was confirmed that this greatly contributed to improving productivity.

On the other hand, untreated fabrics are treated with a cellulose-reactive cross-linking agent, which causes their texture to become noticeably rougher and harden, and their shear, wear and tear properties and pleat retention properties to deteriorate.

Example 4 Two out of 21 raw silks were cut into pieces, enzymatically refined and dried according to a conventional method. This kneaded silk thread was immersed for 2 minutes in a solution at 30°C containing 5% by weight of common salt and 10% by weight of glycerin triglycidyl ether in a mixed solvent of dimethylacetamide and water in a weight ratio of 75:25. After infiltrating the whole area uniformly, the liquid was removed by centrifugation to achieve a liquid extraction rate of 80%. The obtained treated material was suspended in a rotating stainless steel vibrator and introduced into a high-temperature steamer, where it was steamed at 103°C for 10 minutes, washed with hot water and water, and then bleached with hydrogen peroxide to induce a weak cationic and nonionic thermal reaction. It has been given the usual flexible antistatic treatment using water-soluble urethane. As a result of knitting a 32 gauge tricot using the obtained treatment system, it was found that the untreated system in which only the modification treatment step with an epoxy compound was omitted resulted in yarn breakage t;
Although knitting was difficult or had to be done at extremely low speeds, the productivity could be improved to a level comparable to that of synthetic fibers. The finished product also had excellent washing resistance.

Example 5 The knitting was performed in the same manner as in Example 4 except that spun silk No. 72 twin yarn and 28 gauge tricot were used, and the high productivity and excellent quality characteristics due to the modification treatment were reconfirmed. In addition, when the obtained tricot is dyed with acid dyes, alloy dyes, disperse dyes, etc. using a conventional method, the color of the fabric becomes clear and deep, and the major drawback of conventional tricot dyeing is the streak stains. was not recognized.

Example 6 Nightwear (undyed sewn products) using silk habutae fabric was mixed with 8% by weight of sodium thiosulfate and 15% by weight of phenyl glycidyl ether in a mixed solvent of N-methylpyrrolidone and water at a weight ratio of 70:30. 5 in a 20°C solution containing
After soaking for a minute, the liquid was removed by centrifugation until the liquid extraction rate was 60%. The obtained ruffled product was taken out onto a stainless steel basket, introduced together with the basket into a high-temperature steamer maintained at 102°C, and steamed for 10 minutes, then subjected to post-treatments such as soaping in accordance with conventional methods, and then Hand-dyed with acid dyes and complex salt dyes. The obtained sewn product showed superior wash-and-wear properties compared to untreated products, and had excellent washing resistance.

Patent applicant: Director of the Agency of Industrial Science and Technology Kozo Iizuka (and 2 others) Sub-Agent Akira Akira

Claims (1)

[Claims] 1. A treatment composition prepared by dissolving an epoxy compound and a reaction catalyst in a mixed solvent of a polar aprotic solvent and water is impregnated into a silk fiber product, and then the liquid is squeezed and heated at a high temperature. A method for modifying silk fiber products, which comprises performing a moist heat treatment in steam. 2 The weight ratio of polar aprotic solvent and water is 95:5 to 5
The method for modifying silk fiber products according to claim 1, wherein the ratio is in the range of 1:49. 3. The method for modifying silk fiber products according to claim 1, wherein the epoxy compound has at least two epoxy groups and a molecular weight of 1,000 or less. 4. The method for modifying silk fiber products according to claim 1, wherein the reaction catalyst is a water-soluble neutral or weakly basic metal salt.