JPH055275A - Production of processed cloth of silk fibroin - Google Patents

Abstract

PURPOSE:To obtain cloth having luster and handle of silk and water absorbing properties industrially, readily and inexpensively by providing cloth with a solution prepared by adding a stabilizer composed of a specific copolymer to an aqueous solution of silk fibroin, drying and heat-treating. CONSTITUTION:A stabilizer comprising a polycarboxylic acid-based polymer such as especially a copolymer of polyoxyethylene, methacrylic acid and glycidyl methacrylate is added to an aqueous solution of waste fiber of silk as a raw material and calcium or magnesium hydrochloride, etc., to give a solution, which is applied to cloth by vat method, the cloth is dried, heat-treated and washed to give lightweight cloth having silky handle, luster of silk, elasticity, repulsion, water-vapor absorption and excellent durability readily and inexpensively.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a silk-fibroin-treated cloth.

[0002]

2. Description of the Related Art Silk has a quiet deep luster, a soft texture,
It has a unique lofty, elegant dignity that is unmatched by other fibers, such as graceful drape, and is highly regarded as the top material among fibers. Therefore, many processing methods for imparting silk characteristics to fibers other than silk have been proposed.

For example, as a post-processing method, a method has been proposed in which a urethane resin or a silicone resin is added to improve resilience and a soft feeling, or an amino acid resin is added to express a squeaky feeling. For gloss, a method of applying a polymer having a refractive index similar to that of silk by a padding method or a coating method has been proposed. However, all of them are inferior in appearance effect or durability.

On the other hand, treatment with an aqueous dispersion of silk fibroin powder has been proposed, but there is a problem that the stability of the solution and the durability after the treatment are poor. That is, it is difficult to express the original luster, texture, repulsion and hygroscopicity of silk in ordinary fiber processing, and no silk close to natural silk has been found yet.

[0005]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present inventors have completed the present invention as a result of diligent research on the physical properties and feel of silk and focusing on silk fibroin. An object of the present invention is to provide a method for producing a fabric having silk luster, texture, repulsion and hygroscopicity and excellent in durability of those properties.
Another object is to provide a method for producing such a fabric industrially easily and inexpensively.

[0006]

In order to achieve the above object, the present invention has the following constitution. That is, a method for producing a silk-fibroin-treated cloth, which comprises applying a liquid obtained by adding a stabilizer comprising a polycarboxylic acid-based polymer to an aqueous silk-fibroin solution to a cloth, and then drying the cloth and performing a dry heat treatment or a wet heat treatment to wash the cloth. Use as a summary.

The present invention will be described in detail below. The solvent of silk fibroin applied to the present invention is copper-ethylenediamine aqueous solution, copper hydroxide-ammonia aqueous solution (Schweiser reagent), copper hydroxide-alkali-glycerin aqueous solution (Lohe's reagent), lithium bromide aqueous solution, calcium or magnesium or zinc. Examples thereof include aqueous solutions of hydrochlorides, nitrates or thiocyanates, and aqueous solutions of sodium thiocyanate, but calcium or magnesium hydrochlorides or nitrates are preferred from the viewpoint of cost and use. The silk fibroin is obtained by scouring silk waste fibers produced as a by-product in a raw silk factory or a silk spinning factory with Marcel soap and soda ash by a usual method to reduce residual sericin to 1% by weight or less. The concentration of silk fibroin in the silk fibroin aqueous solution is usually 0.5 to 20% by weight, and particularly preferably 1.0 to 10.0% by weight, although it varies depending on the kind of solvent and the amount of the solvent. The silk fibroin aqueous solution applied to the present invention may be used as it is, but it is preferably used after debasing and / or desalting in terms of product quality and process. The debasing or desalting treatment is usually carried out by dialysis using a tube or a semipermeable membrane.

In the present invention, the stabilizer added to the silk fibroin aqueous solution is a stabilizer having dispersibility, shearing force stability, fibroin fixing property, and the like, and examples thereof include polycarboxylic acid type polymers. Particularly preferred in the cleaning of the present invention is a copolymer of polyoxyethylene, methacrylate, methacrylic acid and glycidyl methacrylate. The polyoxyethylene component in the copolymer is
It is believed to give the fabric a soft, silky feel. Regarding the ratio of the silk fibroin component of the present invention to the stabilizer component such as liquid dispersibility, shearing force stability and fibroin fixing property, the silk fibroin component may be mixed at least 10% by weight in consideration of the texture of the processed fabric. It is necessary, and particularly preferably at least 30% by weight, especially 50% by weight or more. Stabilizer component is at least 10% by weight or more, especially 20
It is preferably at least% by weight. The ratio of the silk fibroin component and the stabilizer component can be appropriately determined depending on the desired quality such as feeling or durability, but usually 50 to 80% by weight of the silk fibroin component and 20 to 50% by weight of the stabilizer component are used. ..

The cloth used in the present invention is a synthetic fiber such as polyester, nylon or acrylic, a cellulosic fiber such as cotton, rayon or hemp, a semi-synthetic fiber such as acetate or triacetate, and a blended or mixed woven fabric of various fibers. fabric,
Examples include knitted fabrics and non-woven fabrics.

In the method of the present invention, the method of applying silk fibroin to the cloth is not particularly limited, but a pad method, a spray method, a roller method and the like can be applied. or,
In order to exhibit good adhesion and uniform film-forming property of silk fibroin to the cloth, the cloth is pretreated, for example, polyester fiber is subjected to alkali treatment, nylon fiber is subjected to acid treatment, or oxygen, nitrogen, air, argon or other inorganic gas system is used. Low temperature plasma treatment may be performed.

The cloth to which silk fibroin is applied is dried,
Further, by performing a moist heat treatment, the durability of the film is improved and a strong film can be formed. The moist heat treatment is performed at 90 ° C. or higher, preferably 110 ° C. or higher. The silk fibroin-treated fabric of the present invention has a uniform thin film wrapping the fibers, and this silk fibroin film is no longer soluble in water and is wash-resistant.

After that, by washing with warm water, an appropriate rubbing action is added, the adhesion between the fibers is relaxed, and the finish feeling is softly improved. In the present invention, the washing step is important, and as a condition, the treatment is carried out by using Wins, jigger, open soaper or the like at a range of 30 to 80 ° C, preferably 40 to 60 ° C, in which the dye by dyeing or the silk fibroin after heat treatment is not eluted. Furthermore, the silk fibroin solution applied to the present invention may contain a softening agent, an antistatic agent, an antiseptic agent, a toning agent, a water absorbing agent, a reaction catalyst and the like, if necessary.

The silk-fibroin-treated cloth obtained by the method of the present invention covers the surface of the fiber with a silk-fibroin film, but considering the flexibility and the feel of the fiber, the amount of the silk-fibroin attached is at most 10% by weight with respect to the cloth. It is usually 0.1 to 5.0% by weight, preferably 0.2 to 5.0% by weight. The thickness of the film is usually 0.01 to 10 μm.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, all parts are parts by weight. The test method which is the basis of the numerical values in the examples is as follows. (1) Increasing rate Weight after treatment-Weight before treatment ─────────────── × 100 (%) Weight before treatment (2) Tear strength JIS L-1096 D method ( 3) Washing test JIS L-0217 103 method (4) Surface fluff JIS L-1076 A method (pilling test method) (5) Texture KES (manufactured by Kato Iron Works Co., Ltd.) Texture tester. (Displayed as a hand value based on the standard for thin outerwear for women's clothing)

Regarding the colloidal solution of silk fibroin used in the examples, first, silk spinning waste was used as a raw material for silk fibroin, and 100 parts of this was mixed with a solution of 30 parts of Marcel soap and 3000 parts of water at 95 to 98 ° C.
Stir for hours, reduce residual glue to 0.1% or less,
After washing with water, it was dried with hot air at 80 ° C. Calcium chloride (CaC
(l ₂ .2H ₂ O) (66 parts) was mixed with 34 parts of water to prepare 100 parts of 50% calcium chloride aqueous solution, and the mixture was heated to 110 ° C. To this, 30 parts of scoured refined spinning waste was added while stirring for 5 minutes, and then stirred for another 30 minutes to completely dissolve.
The obtained silk fibroin-calcium chloride solution was cooled and then dialyzed and desalted with a cellulose tube. That is, a cellulose tube having an inner diameter of 7 to 8 cm and a length of 1 m was used, and this was filled with a silk fibroin solution, and both ends were sealed, and then the salt concentration was reduced to 0.1% or less over 15 to 25 hours in running water. Reduced. The desalted dialysate has a silk fibroin concentration of about 5.5% by weight. This was diluted with hot water to prepare a silk fibroin colloidal solution.

EXAMPLE 1 Nylon half tricot 15 parts by weight of 8% by weight silk fibroin colloidal solution, 23 mol of polyoxyethylene, 40 mol of methacrylate, 40 mol of methacrylic acid and 30 mol of a copolymer of 10 mol of glycidylmethacrylate 30% by weight solution 2
Of water and 83 parts of water, squeeze the pick-up rate to 80%, dry at 120 ° C, and heat at 110 ° C with an HT steamer.
Wet heat treatment was performed at 0 ° C. and a steam amount of 0.5 kg / cm ² for 10 minutes. Further, it was washed with warm water of 55 ° C. for 10 minutes and dried.

Comparative Example 1 The same treatment as in Example 1 was carried out except that the nylon half tricot was not washed with warm water. Next, Example 1 and Comparative Example 1
Table 1 shows the weight increase rate and the feel (touch) of the product obtained in 1.

[0018]

[Table 1]

EXAMPLE 2 15 parts of 8% by weight silk fibroin colloidal solution of polyester processed yarn fabric and 2 parts of 30% by weight copolymer of 23 mol of polyoxyethylene, 45 mol of methacrylate, 45 mol of methacrylic acid and 5 mol of glycidyl methacrylate. It was dipped in a working liquid of 83 parts of water, squeezed to a pickup rate of 80%, dried at 120 ° C., and steamed at 115 ° C. for 10 minutes. Further, it was washed with warm water of 55 ° C. for 10 minutes and dried. Table 2 shows the rate of increase and the texture (hand value) of the product obtained in Example 2. From Table 2, it can be seen that the product obtained in Example 2 has less loss of the processing agent due to washing, the texture is firm,
It was silky with firmness and squeaky feeling. For comparison, Table 2 shows the texture (hand value) of the unprocessed polyester textured yarn woven fabric which is not soaked with the processing liquid.

[0020]

[Table 2]

Example 3 The polyester processed yarn woven fabric is dipped in the processing liquid of the treatment of Example 2 and the following water-absorbing compound added, squeezed to a pickup rate of 80%, dried at 120 ° C. and dried at 115 ° C. for 1 hour.
A steam heat treatment was performed for 0 minutes. Further, it was washed with warm water of 55 ° C. for 10 minutes and dried. Silk fibroin 8% by weight colloidal solution 13 parts The same copolymer solution as in Example 2 2 parts Block type N, N, N-distearylmethyl aminopolyethylene glycol etherified polyester quaternary ammonium salt 10% by weight emulsion 5 parts water 80 parts Table 3 shows the weight gain, feel (touch) and water absorption of the product obtained in Example 3. From Table 3, water-absorbing performance can be imparted by immersing in a working fluid containing a water-absorbing compound.

[Table 3]

[0022]

Industrial Applicability According to the method of the present invention, it is possible to provide a cloth having a soft and silky texture, silk luster, repulsion and hygroscopicity, and excellent durability of these properties. it can. Further, water absorbing performance can be imparted by adding a water absorbing compound to the processing solution of the present invention. The present invention is a method capable of industrially easily and inexpensively producing such a fabric, and is extremely useful industrially.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Isamu Nakamura 1-5-9 Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka

Claims (1)

Claim: What is claimed is: 1. A silk fibroin aqueous solution to which a stabilizer comprising a polycarboxylic acid polymer has been added, is applied to a cloth, which is then dried and subjected to dry heat or wet heat treatment for washing. A method for producing a silk-fibroin-processed fabric, which is characterized.