JPH03185183A - Web processed with silk fibroin-synthetic polymer mixture and preparation thereof - Google Patents

Abstract

PURPOSE:To prepare the subject processed web having the touch, luster and elegance of silk and having properties nearer to those of the silk than conventional silk-like fibers by imparting a mixture solution of silk fibroin-synthetic polymer to the surfaces of fibers in a web and subsequently subjecting the fibers to a wet thermal treatment. CONSTITUTION:For example, the waste fibers of silk in a raw silk factory or silk-spinning factory are refined and purified to prepare a silk fibroin aqueous solution. The aqueous solution is mixed with preferably a polyurethane resin and subsequently imparted to the surfaces of fibers (e.g. cellulosic, semi-synthetic or synthetic fibers) in a web by a pad method, etc., in an amount of 0.1-10wt.% based on the weight of the web, followed by drying and subjecting the web to a wet-thermal treatment to form the film of the mixture on each fiber. The method permits to provide the web having the touch and luster of the silk, further having increased tension and stiffness and having the characteristic stick-slip touch of the silk, excellent washing resistance and the more silk-like properties than those of conventional silk-like fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a silk fibroin-synthetic polymer processed fabric and a method for producing the same.

(Conventional technology) Silk has a unique elegance and dignity that is unrivaled by other fibers, such as a quiet deep luster, a soft texture, and an elegant drape, and is highly regarded as the top material among fibers. It is evaluated. Therefore, many processing methods have been proposed to impart silk characteristics to fibers other than wire. For example, polyester fibers are treated with alkaline to reduce weight and have a soft texture; cellulose fibers are treated with enzymes to reduce weight and have a soft finish; rayon and cotton are treated with urethane resin to improve their elasticity and soft feel. Methods have been proposed, such as adding silicone resin or adding amino acid resin to create a squeaky feel. In addition, methods have been proposed to improve gloss, such as applying a polymer having a refractive index similar to that of silk using a padding method or a coating method.

However, all of them are inferior in appearance effects or durability.

On the other hand, treatment with an aqueous dispersion of silk fibroin powder has been proposed, but there are problems in that the stability of the solution and the durability of the treated layer are poor. In other words, the luster, texture, and elasticity inherent in silk compared to normal WA textile processing.

It is difficult to exhibit hygroscopicity and has not yet been discovered.

(Problems to be Solved by the Invention) The present inventors have completed the present invention as a result of intensive research into the physical properties and texture of silk and focusing on silk fibroin.

An object of the present invention is to provide a fabric that has the luster, texture, repulsion properties, and hygroscopicity of silk, and is also excellent in the durability of these properties. Another object of the present invention is to provide a method for manufacturing a filter fabric industrially easily and inexpensively.

Means for Solving the Problems) In order to achieve the above object, the present invention has the following configuration. That is, the first invention has silk fibroin on the fiber surface.
The gist is a silk fibroin-synthetic polymer-processed fabric having a film made of a synthetic polymer, in which the amount of the film attached is 0.1 to 10% by weight based on the weight of the fabric; In the second invention, a synthetic polymer is dissolved in an aqueous silk fibroin solution, and the resulting mixed aqueous solution is applied to a fabric.

The gist of this invention is a method for producing silk buproin-synthetic polymer-processed fabric, which is characterized by drying and moist heat treatment.

The present invention will be explained in detail below.

In the present invention, fabrics include cellulose fibers such as cotton, rayon, and linen, semi-synthetic fibers such as acetate and triacetate,
Synthetic fibers such as polyester, nylon, acrylic, and blends of various fibers, mixed woven fabrics, knitted fabrics, and non-woven fabrics are included.
The effects of the present invention are particularly great for fabrics using polyamide fibers such as nylon, which are difficult to modify using normal processing methods.

In the present invention, synthetic polymers include polyacrylic acid ester resins, polyurethane resins, silicone resins, and the like. These may be used alone or in combination. In particular, those using polyurethane resin have excellent durability, and it is preferable to use a prepolymer of end-blocked incyanate. Such end-blocked incyanate prepolymers are made by reacting with isocyanate groups such as sodium bisulfite, acetylacetone, ethyl acetoacetate, diethyl malonate, etc. to create temporally stable compounds and then heat-treating them. It is a compound containing at least one blocked incyanate group in the molecule that dissociates and regenerates the incyanate group, and is obtained by polymerizing an acrylic or methacrylic compound and a silicone-modified, fluorine-modified, etc. modified acrylic or methacrylic compound. emulsions of polyurethane prepolymers made of diisocyanates and polyols, emulsions of natural polysaccharides such as starch and cellulose, and emulsions of natural proteins.

It is preferable to use a catalyst for the dissociation of the end-blocked incyanate prepolymer, such as zinc octylate, which is a metal salt of a fatty acid;
Examples include zirconium octylate, zinc laurate, zinc stearate, and the like.

By using the above-described end-blocked incyanate prepolymer, the crystal structure changes from α-type to β-type as a result of the moist heat treatment described later, and the adhesion of the insolubilized silk buproin protein to the polyamide fibers becomes stronger. It can be done.

The silk fibroin-synthetic polymer processed fabric of the present invention covers the fiber surface with a silk fibroin-synthetic polymer film, but considering the flexibility and texture of the fibers, silk fibroin
The amount of synthetic polymer deposited on the fabric is at most 10% by weight, usually 0.1 to 10.0% by weight, preferably 0.2 to 5% by weight.
．． It is 0% by weight. The thickness of the film is usually 0.01 to 1.
It is 0μ. In addition, the ratio of the silk buproin component and the synthetic polymer component of the present invention is such that, considering the texture of the processed fabric, the silk buproin component must be mixed in an amount of at least 10% by weight, particularly at least 50% by weight, especially 50! % or more is preferable. The synthetic polymer component is preferably at least 10% by weight, particularly preferably 20% by weight or more. The ratio of the silk fibroin component to the synthetic polymer component can be determined as appropriate depending on the desired quality such as texture or durability, but it is usually 50 to 80% by weight of the silk fibroin component and 20% by weight of the synthetic polymer component.
~50% by weight is used.

The solvent for silk buproin used in the present invention is
As described in Publication No. 38449, etc.

For example, copper-ethylenediamine aqueous solution, copper hydroxide-ammonia aqueous solution (Schweiser reagent), copper hydroxide-alkali-glycerin aqueous solution (Rohe reagent), lithium bromide aqueous solution, calcium, magnesium or zinc hydrochloride, nitrate or thiocyanate. Examples include aqueous solutions and sodium thiocyanate aqueous solutions, but calcium or magnesium hydrochloride or nitrate are preferred from the viewpoint of cost and use. Silk fibroin is obtained by scouring silk tanjiri fibers, which are by-produced at raw silk mills or silk spinning mills, using Marcel soap and soda ash in the usual manner to reduce residual sericin to 1% by weight.
Apply the following code. The a degree of silk fibroin in the silk fibroin aqueous solution varies depending on the type of solvent and the amount of adhesion, but it is usually 0.6-2ON amount%, especially 1.0-10.05i
% is suitable.

The silk fibroin aqueous solution applied to the present invention may be used as it is, but from the viewpoint of product quality and process, it is preferable to use it after debasing and/or desalting. The desalting or desalting treatment is usually carried out by dialysis using a semipermeable membrane such as a tube or film.

In the method of the present invention, the method of applying the silk fibroin and synthetic polymer aqueous solution to the fabric is not particularly limited, but a pad method, spray method, roller method, etc. can be applied.

In addition, in order to develop good adhesion and uniform film-forming properties of silk fibroin and synthetic polymers to fabrics, the fabrics are subjected to pretreatment, such as alkali treatment for polyester fibers, acid treatment for nylon fibers, or oxygen, nitrogen, air, or Low-temperature plasma treatment may be performed using a system such as argon.

The fabric coated with silk fibroin-synthetic polymer is dried,
A strong film can be formed by further performing a moist heat treatment. The moist heat treatment is carried out at a temperature of 90°C or higher, preferably 110°C or higher. For this reason, it is preferable to use superheated steam in the moist heat treatment, especially
Treatment at 0''C for 1 to sa minutes is preferred.

The silk fibroin-synthetic polymer processed fabric of the present invention has a uniform thin skin that envelops mM, and the silk fibroin-synthetic polymer film is no longer soluble in water and is wash resistant. .

The silk fibroin-synthetic polymer aqueous solution applied to the present invention may contain a foreign protein such as atelocollagen, hydrolyzed collagen, gelatin, casein, etc. in order to stabilize the silk fibroin solution, that is, to prevent gum-up. The amount of foreign protein used is preferably 20 to 100% by weight based on silk fibroin. If it exceeds 100% by weight, film forming properties are poor and the texture becomes rough and hard.

Furthermore, the silk buproin-synthetic polymer aqueous solution applied to the present invention may contain a softener, an antistatic agent, a preservative, a toning agent, a stabilizer, a reaction catalyst, etc., as necessary.

(Example) Hereinafter, the present invention will be specifically explained with reference to Examples.

In addition, in the examples, all parts indicate parts by weight.

Further, the test method that is the basis for the numerical values in the examples is as follows.

(2) Tear strength JIS L-1098D method (3) Washing test JIS L-0217103 method (4) Surface fuzz JIS L-1078A method (pilling test method) (5) Texture KEY (manufactured by Kato Iron Works) style Measured with a matching tester. (Displayed as hand value based on standards for thin fabrics for women's outerwear) (6) Water absorption test (1) Drop method JIS L-1096A method (11)
) Bileg method JIS L-1096B method (7) Antistatic property test (+1 * Friction voltage JIS L-1094B method (
11) Half-life JI8' L-1094A method (2G
"C±40% RHkc Te1ull constant) (8)
Measured using a KES-FT precision rapid thermal measurement device manufactured by Kadochik.

(TTiERMOLABOI TYPE) (Touch Cold/Temperature Sensation: qmax Contact Cold/Temperature Sensation represents the warmth or coldness at the moment of touch. If the object feels cold at the moment of touch, a large number indicates
@Things that feel this way are expressed in small numbers.

(11) Thermal conductivity 2K (9) Whiteness Color measurement using Macbeth I type colorimeter Shown as reflectance at 450 nm.

First, using silk spinning waste as a silk fibroin raw material, 100 parts of this was mixed with 50 parts of Marcel soap and 3 g of water.
The solution was stirred and refined for 5 hours at 95 to 98°C to reduce the remaining layer to 0.1% or less, washed with water, and then dried with hot air at 80°C.

Calcium chloride (Oa01t4H10) 66 parts water 3
4 parts were mixed to prepare 100 parts of a 50% calcium chloride aqueous solution and heated to 110°C. Add to this the refined spinning waste 3
After adding 0 parts with stirring for 5 minutes, the mixture was further stirred for sO minutes to completely dissolve.

The obtained silk fibroin-calcium chloride solution was cooled and then desalted by dialysis using a cellulose tube. That is, the inner diameter of the cellulose tube is 7 to B cm.

A 1 m long tube was used, filled with a silk fibroin solution, both ends of which were sealed, and the salt concentration was reduced to 0.1% or less in running water for 15 to 25 hours.

Silk fibroin af of desalted dialysate 5.5% by weight
That's about it. This was diluted with hot water to prepare a 5% by weight colloidal solution of silk fibroin.

Example 1 Two types of cotton fabrics shown in Table 1 were subjected to hair burning, desizing, scouring, bleaching, mercerization, dyeing, and fixing treatments using commonly known methods.

Table 1 The cotton fabric was soaked in the aqueous solution shown below and the pick-up rate was 7.
It was reduced to 0% and dried at 120° C. for 2 minutes.

Silk fibroin 5% by weight solution [gos Inplanil DLN 5 parts (Bayer (m!!!, polyurethane emulsion solid content 45%) Yodozol PE400 2M5 (manufactured by Endspun N.N.C., polyethylene softener) water
After that, the cotton fabric was steam-treated at 105° C. for 20 minutes.

Comparative Example 1 A cotton fabric after the same fix treatment as in Example 1 was immersed in the aqueous solution shown below to reach a pick-up rate of TO% at 120°C.
Drying was performed for 2 minutes.

Yodozol PE400 'fi part (manufactured by Hirobo N80■, polyethylene softener) water
9
Thereafter, the cotton fabric was steam-treated at 105°C for 20 minutes.

Comparative Example 2 A cotton fabric after the same fix treatment as in Example 1 was immersed in the aqueous solution shown below, and the pick-up rate was reduced to 0%.
Drying was performed at °C for 2 minutes.

5% by weight aqueous solution of silk buproin 20 parts Yodozol PE4G0 2 parts (Kanebo NSC
■Made with polyethylene softener) water
After 78 copies,
The cotton fabric was steam-treated at 105''C for 20 minutes.

Next, the weight increase rate (%) of the products obtained in the examples and comparative examples,
Pilling (grade), weft tear strength (f), and hand value values are shown in Table 2.

As is clear from Table 2, the products obtained in the examples have less shedding of processing agents during washing, less pilling after washing, no loss of strength, and a firm, firm and squeaky texture. You can see that it has a silky texture.

Furthermore, visual observation revealed that the luster was similar to that of silk.

In addition, instead of the Inplanal DLN of Example 1, KM
-2002T (manufactured by Shin-Etsu Chemical Group, silicone resin, solid content 40%) was manufactured in the same manner as in Example 1, and in place of Inplanil DLN in Example 1, Poncoat 8136 ( A product produced in the same manner as in Example 1, except that 3 parts of polyacrylic acid ester mQ! (manufactured by Dainippon Ink ■, solid content: 45%) was used, also produced the same effects as in Example 1.

Example 2 Triangular cross-section 6 nylon fiber using bright yarn of 36 denier 71B filament was knitted into a half tricot at 58 gauge. This is usually refined, bleached, and
After heat setting and dyeing with an acid dye, a fixing treatment was performed with tannic acid to obtain a nylon half tricot for inner wear.

Next, use a trowel pad with a pick-up rate of 80% using treatment solutions (4) and (B) shown in section f, dry at a temperature of 1 sO°C for 45 seconds, and then dry at a temperature of 150°C for 8 minutes. A moist heat treatment was performed using superheated steam using a high-temperature chamber and a steamer manufactured by Arioli, followed by final setting at a temperature of 160° C. for 1 minute.

Treatment liquid (4) 5.0% by weight fibroin solution 20% by weight 3.8
Casein solution 20% by weight Elastron MF-9 (Daiichi Kogyo 2% by weight urethane prepolymer of end-blocked isocyanate manufactured by Daiichi Kogyo Seiyaku ■) Elastron Catalyst 64 0.25% by weight (Fatty acid metal ring manufactured by Daiichi Kogyo Seiyaku ■) urethane decomposition) Treatment liquid (B) 5.0% by weight fibroin solution 30% by weight 5, O
Casein solution 30% by weight Elastron MF-95% by weight Elastron 0at84 0.25% by weight The physical properties of the obtained processed fabrics are shown in Tables 3 to 6.

Example 3 In a similar process to Example 2, the end-blocked incyanate urethane prepolymer Elastron M
In place of F-9, Superflex E-2000 (polyurethane emulsion manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), which is a non-reactive polyurethane emulsion, was used, and at the same time, a reaction catalyst was not added. Table 5 shows the physical properties of the obtained processed cloth.

Example 4 In the same process as in Example 2, moist heat treatment was performed using a high temperature steamer at a temperature of 105°C for 8 minutes using an Arioli steamer.

Table 3 shows the physical properties of the obtained processed cloth.

Comparative Example 3 In the same treatment as in Example 2, dry heat treatment was performed at a temperature of 150° C. for 8 minutes instead of heat treatment.

Table 3 shows the physical properties of the obtained processed cloth.

Example 5 In the same treatment as in Example 2, the treatment was carried out without adding the casein solution in the treatment liquid.

Table 6 Thermophysical property values of processed fabric *100% silk 140/2 spun silk sheeting (effects of the invention) As detailed above, the silk fibroin-synthetic polymer processed fabric of the present invention has the texture and luster of silk. In addition, it has an increased tension and waist feel, and also has the creaky feeling unique to silk, and its surface moisture absorption and moisture release are similar to silk, and it feels warmer to the touch, making it more It exhibits performance similar to that of silk, despite its low adhesion rate, and also has excellent washing resistance. or,
The method of the present invention can efficiently process such fabrics, and its usefulness is obvious.

Procedural Amendment Written Patent Application No. 313975, filed on September 4, 1990, Patent Application No. 313975 2, Name of the invention: Silk fibroin-synthetic polymer processed fabric and its manufacturing method 3, Relationship with the person making the amendment Patent applicant's address: Tokyo 5-17-4 Sumida, Sumida-ku, Tokyo 1-5-90 Tomobuchi-cho, Bejima-ku, Osaka 534, Kanebo Co., Ltd. Patent Department Tel: (06) 921-1251 4. Date of amendment order Voluntary 6. Details subject to amendment ``Detailed Description of the Invention'' section of the book.

7. Contents of amendment fil Insert the following sentence between the first and second lines of page 6 of the specification.

“A water-soluble polymer compound may be added to the synthetic polymer, such as natural and synthetic polymers and their derivatives such as starch, guar gum, and tamarind gum.

Examples include sodium alginate, gelatin, carboxymethyl cellulose, hydroxyethyl cellulose, etc.
Furthermore, a polymer compound that dissolves in water in an acidic aqueous solution having a pH of 3 to 6, does not react with the synthetic polymer, or has poor adhesiveness is preferred.

Further, the proportion of the water-soluble polymer compound to the silk fibroin-synthetic polymer is 2 to 60% by weight, more preferably 5 to 20% by weight.
% is preferred.

By adding a water-soluble polymer compound, in the one-time process,
The compound falls off from the film, forming micropores of about 0.01 to 10 microns, which contribute to improving heat absorption and water absorption, as well as increasing the squeaking sensation. (2) Insert the following sentence between page 8, line 19 and line 20 of the specification.

In addition, in order to form a strong film, the fabric may be immersed in an acidic aqueous solution with a pH of 3 to 6. Various acids can be used as such acids, but weak acids are particularly preferred, and organic acids such as acetic acid and lactic acid are preferred. Acid, phosphoric acid.

Examples include inorganic acids such as ammonium sulfate.

The immersion treatment is performed in an acidic aqueous solution at 10 to 60°C for 2 to 30 minutes, followed by washing with water and drying. (3) Specification No. 22
Insert the following sentence before "(effects of the invention)" on the 9th line of the page.

“Example 6 Using the following treatment liquid (A) or (B), heat treatment was performed in the same manner as in Example 2, and then acetic acid 10 c c / l
40°C, 10°C in an acid solution adjusted to pH 4-5.
After processing for 1 minute, it was washed with water, dried, and subjected to a final set at a temperature of 160° C. for 1 minute.

Treatment liquid (A) 5.0% by weight fibroin solution 30% by weight 3.
0% by weight casein solution 30% by weight/gelatin
0.5% by weight Elastron MF
-9 (Urethane prepolymer of terminal profluorinated isocyanate manufactured by Daiichi Kogyo Seiyaku ■) 3% by weight Elastron Catalyst 64 (Fatty acid metal base urethane catalyst manufactured by Daiichi Kogyo Seiyaku ■) 0.25% by weight Treatment liquid (B) 5. 0% by weight fibroin solution 30% by weight 3.0% casein solution 30% by weight Duck Algin N
5PL (Kamogawa Kasei Kogyo special sodium alginate) 0.5% by weight Elastron MF-93% by weight Elastron Catalyst 640.25% by weight Example 7 The same treatment as in Example 6 except that only the heat treatment was not performed, but the other conditions were the same. processed.

Comparative Example 4 Same treatment as Example 6, but without acid treatment,
The rest was treated in the same way.

Comparative Example 5 The same treatment as in Example 6 was performed except that the heat treatment and acid treatment were not performed.

Comparative Example 6 In the same treatment as in Example 6, gelatin and sodium alginate were not added, and the other treatments were performed in the same manner.

The physical property values obtained in the above processing are
Shown in the table.

Claims (1)

[Scope of Claims] 1) A fabric having a film made of silk fibroin-synthetic polymer on its fiber surface, wherein the amount of the film attached is 0.1 to 10% by weight based on the weight of the fabric. Fibroin - synthetic polymer processed fabric. 2) A method for producing a silk fibroin-synthetic polymer processed fabric, which comprises dissolving a synthetic polymer in an aqueous silk fibroin solution, applying the resulting mixed aqueous solution to a fabric, drying it, and subjecting it to a moist heat treatment.