JPH0242943B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to a method for modifying textile products composed of silk fibers. More specifically, yarns, knitted fabrics, woven fabrics, and sewn products composed of silk fibers, as well as blended, twisted, and interwoven textile products whose main constituent is silk fiber, while retaining the excellent sensory characteristics unique to silk fibers. , relates to a modification processing method that can improve functional properties such as abrasion resistance, yellowing resistance, moisture resistance, wrinkle resistance, and washing resistance, which have been pointed out as drawbacks in the past.

Conventional technology Silk fiber products have a unique feel, appearance, texture, etc. as natural fibers, and have been widely used.However, in addition to high quality with the sensory and functional properties of synthetic fibers, silk fiber products are also low priced. Inspired by this, 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 whose effectiveness has been measured.

As for the method (1) above, for example, an epoxy polymer and an alkali metal hydroxide or an alkaline alkali metal that has a swelling effect on silk fibers and has an addition reaction catalytic effect between silk fibers and the epoxy polymer are used. A modification processing method that improves shrink-proofing and wash-and-wear properties by soaking silk fiber products in a solution containing salts, squeezing and drying the product, and then subjecting it to dry heat or steam treatment (Japanese Patent Publication No. 38-25198) (Government). If the epoxy polymer used in this product is water-soluble, it can be used directly as an aqueous solution; if it is water-insoluble, alcohol, acetone,
It is dissolved in a mixed solvent of water and a water-soluble solvent such as dioxane, or used as an emulsified dispersion by an appropriate method. Also, an aqueous emulsion containing a specific epoxy compound and one or more neutral salts,
By heating protein fibers in an aqueous solution, an organic solvent solution, or a mixture of a water-miscible organic solvent and water, the wrinkle resistance when dry or wet can be improved.
Modification methods that permanently impart properties such as shrink resistance, light resistance, and chemical resistance are also known (Japanese Patent Publication No. 47-24199).
Publication No.). 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 degrees Celsius or less, resulting in heat-alkaline, acid, and resistance properties. Method for imparting desirable properties such as discoloration, wrinkle resistance, and shrink resistance (Japanese Patent Publication No. 52-38131
), silk fibers are immersed in an aqueous solution of a polyhydric alcohol-based epoxy compound and an alkali metal salt of a monocarboxylic acid, and after removing the liquid, a moist heat treatment is performed to improve wrinkle recovery, light resistance, alkali resistance, and dyeing. A method for obtaining a material with improved practical performance in terms of properties, etc. (Japanese Patent Application Laid-open No. 60-81369), in which silk fibers are impregnated with an aqueous solution containing polyhydric alcohol diglycidyl ether and a catalyst so that 30 to 300% by weight remains. A method has also been proposed (Japanese Patent Application Laid-open No. 85078/1983) in which the material is maintained in the same state and imparts wrinkle resistance, shrink resistance, and color resistance.

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 is 10% or less, and then formaldehyde vapor at 100°C or higher 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 inherent excellent properties of silk fibers such as luster, and physical properties such as strength and elongation (Special Publication No. 7239/1983) After treating with a solution of urea or thiourea and a formaldehyde-based initial condensation resin, the fibers are dried until the moisture in the fibers is reduced to 10% by weight or less, and then treated with formaldehyde vapor at a temperature of 100°C or higher. Method for preventing wrinkle formation under high humidity (Japanese Patent Publication No. 48-24437), an aliphatic, alicyclic or aromatic compound having at least two hydroxyl groups and a molecular weight of 400 or less, or ethanolamine or amino After treatment with a single or mixed solution of aliphatic amines having two groups and a molecular weight of 400 or less, the fibers are dried until the moisture in the fibers is reduced to 10% or less, and then heated at 100°C.
A method of imparting wash-and-wear properties by applying formaldehyde vapor as described above 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 of improving dry wrinkle resistance and crease retention by applying a conventional pad dry cure method using a cellulose-reactive crosslinking agent (Japanese Patent Application Laid-Open No. 62-231079);
A method of imparting excellent dyeing properties, antistatic properties, light fastness, wrinkle resistance, bulkiness, pleatability, etc. by graft polymerizing with a vinyl compound after treatment with an epoxy compound (Japanese Patent Laid-Open No. 62-250275 (Japanese Unexamined Patent Application Publication No. 1983-1999), a method of modifying fibers into disperse dye dyeable fibers by treating with an epoxy compound and then graft polymerizing with a hydrophobic vinyl compound
250276) etc. are known.

In addition, in order to streamline the treatment with epoxy compounds, a method (specially JP-A No. 60-252771), 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 treatment without pre-drying (JP-A No. 61-682).
Publication No. 2), etc. have also been 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. 52-38131) is suitable, and the present inventors have previously proposed a specific processing method and apparatus for this wet processing technology (Japanese Patent Application No. 52-38131). 62−
No. 58061).

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 moving on to the next process of organic solvent treatment of the epoxy compound due to the need to control the tension of the fabric in a wet state. First, fuzzing on the surface of the fabric is likely to occur due to rubbing, and this tendency increases particularly as the width of the fabric increases and the basis weight of the fabric increases.

(2) The two-phase method is difficult to store and manage the fabric 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 between the beginning and end of the long fabric, which is soaked and dehydrated at low speeds, and the influence of room temperature, which varies depending on the season.

(3) The treatment time with an epoxy compound in an organic solvent is a relatively long time for one process, 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. The productivity is not necessarily 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 invention 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 improves 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. The inventors have discovered that the above object can be achieved by forming a cross-linked bond between the two, and based on this finding, 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 with a boiling point of 100°C or higher and water, and then presses the composition. The present invention provides a method for modifying silk fiber products, which is characterized by liquefaction and wet heat treatment in high-temperature steam.

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 to 51:49, particularly preferably 90:10 to 70:
It is in the range of 30. If the water content in the polar aprotic solvent is less than 5% by weight, the wet stability of the treated silk fiber product, such as wet wrinkle resistance, will be significantly reduced, and if it exceeds 49% by weight, the desired effect will not be achieved. I can't get enough. 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 moisture to the outside of the fiber, the coexisting polar aprotic solvent is moved, and the crosslinked constituent components are also accompanied by this, resulting in relatively more crosslinking around the fiber surface.
It is presumed that an excellent surface modification effect is imparted by depositing a portion of the low-weight epoxy polymer.

On the other hand, such as acetone or tetrahydrofuran
When a mixed solvent of a polar aprotic solvent with a boiling point of 100°C or less and water is used, the solvent easily evaporates in the superheated steam, and the effect of the mixed solvent system of the present invention cannot be obtained. .

The epoxy compound used in the method of the present invention is a conventionally known compound having at least two epoxy groups, but preferably has a molecular weight of 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 superheated steam under normal pressure. Water content decreases.

In order to impregnate silk fiber products with these treatment compositions, conventional methods such as immersion at room temperature or in a heated bath, spray application, etc. can be employed.

In addition, pressure mangle, vacuum dewatering, centrifugal dewatering, etc. are used as a method for squeezing, 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.

The silk fiber product that has been uniformly squeezed in this way is directly introduced into superheated steam at 100°C or higher to accelerate the reaction. Steaming conditions are usually below 150℃, 10
However, since coloring of the fabric may occur in proportion to the temperature and time, it is preferably 110°C or less and about 10 minutes. In addition, when the fabric impregnated with the treatment composition is continuously introduced into the superheating steamer,
It is desirable to provide a retention zone between the squeezing step and the steaming step in order to increase the shrink resistance of the product and ensure uniform processing. In addition, with saturated steam at a temperature of 100°C or higher, 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, reactions using normal steaming at temperatures below 100°C require 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 processing process, making it easier to manage the production process, reducing processing costs and stably improving product quality. In other words, improvement effects comparable to those of the two-phase method were obtained in terms of yellowing resistance, moisture resistance and wrinkle resistance, and washing resistance.In particular, in terms of abrasion resistance, it was confirmed that the effect was outstanding compared to the conventional method. It has excellent durability and can significantly change the conventional dyeing operation that had to avoid scratches, streamlining the dyeing process and improving dye fastness.

Examples Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

Example 1 A narrow silk fabric with a 2/2 twill structure consisting of 2 flat yarns out of 27 warp silk yarns and 4 pieced yarns out of 27 weft silk yarns was scoured and dried according to a conventional method, and then dimethyl was added at a weight ratio of 95:5. It is immersed at room temperature in a treatment composition consisting of a solution of 10 kg of glycerin glycidyl ether and 8.3 kg of rhodan soda dissolved in 85 kg of a mixed solvent of sulfoxide and water, squeezed to 95% using a mangle, and shaken off onto a conveyor lattice. After 30 seconds, the mixture was continuously introduced into a high-temperature steamer maintained at 105°C in a suspended form, 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 narrow silk fabric thus obtained was measured using the JISL-1042C method. As a result, untreated fabric has a shrinkage rate of 10% in both warp and weave, while treated fabric can suppress the shrinkage rate to within 0.5%, making it an excellent wash-and-wash product.
It showed wearability. Furthermore, as a result of high-speed dyeing of the bleached fabric with a metal-containing dye using a wince dyeing machine, the color density of the treated fabric was higher than that of 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 Five pieces of satin with a width of 112 cm, consisting of 21 pieces of warp silk thread and 4 piece pieces of 21 weft silk threads, were refined according to a conventional method.
After drying, it was immersed in a solution at 40°C with the same composition as in Example 1 except that a mixed solvent of dimethyl sulfoxide and water at a weight ratio of 90:10 was used, and the liquid was vacuum removed to a 90% extraction rate. Shake it out on the lattice, 30
After staying there for a second, the mixture was introduced into a high-temperature steamer in a suspended state while forming a loop with a length of 1.5 m, 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. In addition,
No significant modification effect was obtained in either the fabrics impregnated with the above solution that were steamed in saturated steam at 110°C for 3 minutes or dry heat treated at 110°C for 3 minutes. Regarding light resistance, coloring of the treated fabric was significantly suppressed compared to untreated fabric, and it was effective in preventing yellowing.

Example 3 A 40-inch wide five-ply sateen consisting of 2 plain warp yarns of 21 yarns and 80 double combed weft yarns was scoured with oxygen, bleached with hydrogen peroxide, and dried according to a conventional method. On the other hand, 5 ethylene glycol diglycidyl ether was added to a mixed solvent of dimethylformamide and water at a weight ratio of 80:20.
A solution was prepared containing % by weight and 3% by weight of sodium acetate. The solution was kept at 30°C, 2-Dip,
Using the 2-nip method, the five sateen sheets were filled with the reaction solution to a pick-up of 90%, shaken off onto a conveyor, and allowed to stay for 40 seconds. Work-up was done by steaming for a minute. The obtained treated fabric was printed using a conventional flat-type automatic screen printing machine using a color paste containing an acid dye, dried, and further impregnated with a cellulose-reactive crosslinking agent according to a conventional method, dried, and sewn into apparel. Afterwards, 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 0.5 on average.
The grade level has been improved. In particular, even when using an automatic screen printing machine with a printing speed of 21 meters per minute, no fuzzing due to rubbing was observed, and it was confirmed that this greatly contributed to improving productivity.

On the other hand, the untreated fabric was treated with a cellulose-reactive crosslinking agent, resulting in a significantly rough texture and a decrease in wash-and-wear properties and pleat retention.

Example 4 Two pieces of raw silk 21 were taken into a skein shape, and subjected to enzymatic scouring and drying according to a conventional method. The weight ratio of this silk kneaded thread is
After soaking 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 75:25 dimethylacetamide and water, the solution was evenly permeated into the skein. The liquid was removed by centrifugation and the liquid was squeezed to a liquid extraction rate of 80%. The resulting treated skein was suspended from a rotating stainless steel pipe 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 produce a weakly cationic, nonionic thermally reactive type. It has been given the usual flexible antistatic finish using water-soluble urethane. Using the obtained treated yarn
As a result of knitting 32-gauge tricot, it was found that untreated yarn, in which only the modification process using an epoxy compound was omitted, was either difficult to knit due to yarn breakage, or had to be knitted at an extremely slow speed. However, we were able to improve productivity to a level comparable to that of synthetic fibers. The finished product also had excellent washing resistance.

Example 5 The results were obtained by knitting in the same manner as in Example 4 except that silk spun No. 72 twin yarn and 28 gauge tricot were used.
The high productivity and excellent quality characteristics of the modification process were reconfirmed. In addition, when the obtained tricot is dyed with acid dyes, metal-containing dyes, disperse dyes, etc. using conventional methods, the color of the fabric becomes clear and deep, and the warp lines, which were the biggest drawback of conventional tricot dyeing, are removed. No spots were observed.

Example 6 Nightwear using silk habutae fabric (undyed sewn product) 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. Contained 20
After immersing in the solution at ℃ for 5 minutes, the liquid was removed by centrifugation until the liquid extraction rate was 60%. Take out the obtained treated sewn product onto a stainless steel basket and place it together with the basket.
After introducing the material into a high-temperature steamer maintained at 102°C and steaming it for 10 minutes, it was subjected to post-treatments such as sorbing according to 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.

Claims (1)

[Claims] 1. After impregnating 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 with a boiling point of 100°C or higher and water, A method for modifying silk fiber products, which comprises squeezing the liquid and subjecting it to moist heat treatment in high-temperature steam. 2. The method for modifying silk fiber products according to claim 1, wherein the weight ratio of the polar aprotic solvent with a boiling point of 100° C. or higher and water is in the range of 95:5 to 51:49. 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 1000 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.