JP2995442B2 - Method for producing silk fibroin-graft polymer processed fabric - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a process for producing a silk fibroin-polymer processed fabric on a fiber material.

[0002]

2. Description of the Related Art Silk has a unique high-grade elegance that is unrivaled by other fibers, such as quiet deep luster, soft texture, and graceful drape. Have been. For this purpose, many processing methods have been proposed for imparting the properties of silk to fibers other than silk. For example, for polyester fiber, a method of softening the texture by reducing the weight by alkali treatment, and for cellulose fiber, a method of softening and reducing the weight by an enzyme,
Further, in rayon or silk, a method of applying a urethane resin or a silicone resin to improve resilience and softness, or applying an amino acid-based resin to express a feeling of creaking has been proposed. . Further, as a method of increasing 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, both have poor appearance effects or durability.

[0003] On the other hand, a treatment using a silk fibroin solution has been proposed, but there is a problem that durability after the treatment is poor. That is, it is difficult to express the inherent luster, repulsion, and moisture absorption of silk with good durability in ordinary fiber processing, and a method for producing a fabric having excellent properties close to silk has not yet been found.

[0004]

DISCLOSURE OF THE INVENTION The present inventors have made intensive studies on imparting the physical properties and feel of silk fibroin to other materials, and as a result, completed the present invention. The purpose of the present invention is to have silk luster, texture, repulsion, moisture absorption,
Moreover, it is an object of the present invention to provide a method for industrially easily and inexpensively producing a cloth having these properties and excellent durability.

[0005]

To achieve the above object, the present invention has the following arrangement. That is, in the first invention, a treatment liquid obtained by dissolving an aqueous solution or dispersion of a monomer mixture composed of various monomers and the like in a silk fibroin aqueous solution is applied to a cloth, and then polymerized on the cloth. A gist of the present invention is a method for producing a silk fibroin-graft polymer processed fabric. Further, the second invention is to prepare a silk fibroin dispersion in which fine powder of silk fibroin is uniformly dispersed, and then dissolve an aqueous solution or dispersion of a monomer mixture composed of various monomers and the like in this dispersion. The gist of the present invention is a method for producing a silk fibroin-graft polymer processed fabric, which comprises applying the obtained treatment liquid to the fabric and polymerizing the treated solution on the fabric.

Hereinafter, the present invention will be described in detail. The silk fibroin-graft polymer-treated fabric obtained by the method of the present invention is a uniform thin film made of silk fibroin-graft polymer, which wraps around the fiber surface constituting the fabric, and the surface polymer film is No longer soluble in water ~
It does not fall off and has washing resistance. Such a durable crosslinked fibroin film is formed by graft polymerization of a mixture described below. In the above-mentioned processed cloth, the amount of silk fibroin attached to the weight of the cloth is at most 5% by weight in consideration of the flexibility and texture of the cloth, and is 0.1 to 5.0% by weight, preferably 0.5 to 3% by weight. 0.0% by weight. In addition, from the viewpoint of the flexibility and texture of the cloth, the amount of the coating film is preferably 0.2 to 10.0% by weight based on the weight of the cloth. The thickness of the coating is usually 0.01 to 10 μm.

In the present invention, the fabric on which the film is formed includes cellulose fibers such as cotton, rayon and hemp, semi-synthetic fibers such as acetate and triacetate, polyester,
Blends or blends of synthetic fibers such as nylon and acrylic and various fibers. Examples of the form include a woven fabric, a knitted fabric, and a nonwoven fabric. In particular, the effect of the present invention is remarkable for a cloth or a polyester cloth using polyamide fibers such as nylon which are difficult to modify by a normal processing method.

Next, for producing the above-mentioned processed fabric,
The method of the present invention will be described in detail. The method for producing a silk fibroin-grafted polymer-processed fabric of the present invention comprises the steps of: adding an aqueous solution of silk fibroin to a bifunctional monomer represented by the following components (a) to (c): (a)

[0009]

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(B) hydroxyl group, carboxyl group, amino group,
A treatment liquid (aqueous solution) obtained by adding three components, a monomer containing a sulfonic acid group or a phosphoric acid group, and (c) a monomer containing an aziridine group or a polyfunctional compound containing two or more aziridine groups. A solution or a dispersion) is applied to the cloth and then polymerized on the cloth to form a crosslinked film on the cloth (hereinafter referred to as a solution method).

Further, in the method for producing a silk fibroin-graft polymer-treated fabric of the present invention, the following components (a) to (c) are represented by the following general formula in a dispersion of silk fibroin powder. Bifunctional monomer

[0012]

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(B) hydroxyl group, carboxyl group, amino group,
A treatment liquid obtained by adding a monomer containing a sulfonic acid group or a phosphoric acid group, and (c) a monomer containing an aziridine group or a polyfunctional compound containing two or more aziridine groups is applied to the cloth. After that, it is characterized by being polymerized on a cloth (hereinafter referred to as a powder method).

According to the above two production methods of the present invention, the above-mentioned monomer is graft-polymerized to silk fibroin by radical polymerization, and insoluble fibers are formed on the surface and / or in the vicinity of the surface of the fiber constituting the fabric. A crosslinkable film is formed,
This film enables silk processing of a fibrous material to which silk fibroin is fixed, which can withstand several tens of home washings and dry cleanings. Then, by using a normal fiber processing method, it is possible to impart the inherent luster, texture, repulsion and moisture absorption of silk with high durability. Furthermore, the method of the present invention can also eliminate the disadvantages of synthetic fibers such as easy charging, poor water absorption, and difficulty in removing dirt.

As the silk fibroin aqueous solution used in the solution method of the present invention, known ones can be widely used.
For example, JP-B-58-38449 and JP-A-3-18.
What is described in No. 5183 can be applied. That is,
As described in JP-B-58-38449, a copper-ethylenediamine aqueous solution, a copper hydroxide-ammonia aqueous solution (Schweizer reagent), a copper hydroxide-alkali-glycerin aqueous solution (Lohe reagent), a lithium bromide aqueous solution, calcium or An aqueous solution of magnesium or zinc hydrochloride or nitrate or thiocyanate, an aqueous solution of sodium thiocyanate, scouring waste fibers by-produced in a silk mill or silk spinning mill using Marcel soap and soda ash in a usual manner, It is obtained by dissolving silk fibers having residual sericin of 1% by weight or less.

In the solution method of the present invention, the concentration of silk fibroin in the aqueous solution of silk fibroin varies depending on the type and amount of the solvent, but is usually 0.5 to 20.0% by weight, particularly 1.0 to 10.0% by weight. % Is preferred. As the silk fibroin aqueous solution applied to the present invention, the above-mentioned ones may be used as they are, but it is preferable to use them after debasing and / or desalting in terms of product quality and process. Here, the abasic or desalting treatment is usually performed by dialysis using a semipermeable membrane of a tube or a film.

On the other hand, as the silk fibroin dispersion used in the powder method of the present invention, known dispersions can be widely used, and for example, those described in Japanese Patent Application No. 3-138216 can be applied. The one described in Japanese Patent Application No. 3-138216 discloses crystallization of regenerated silk coarse powder from an aqueous solution of silk fibroin or embrittled coarse powder obtained by treating silk fibers with an acid or alkali. Water or organic solvent of fine powder of modified silk fibroin obtained by wet-pulverizing a coarse powder having a degree modified to 1/2 or less of natural fiber with a ball mill using water or an organic solvent as a dispersion medium. A dispersion having a volume average particle size of 5 μm or less.

Next, the components (a) to (c) added to the aqueous solution of silk fibroin in the method of the present invention will be described. The compounds shown below are those described in the above (a), (b) and
This is a specific example of the compound (c), and the present invention is of course not limited thereto. First, as an example of the compound (a),

[0019]

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[0020]

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[0021]

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[0022]

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Examples of the compound (b) include acrylic acid, methacrylic acid, styrene sulfonic acid, maleic acid, itaconic acid, croutonic acid, vinyl sulfonic acid,
-Allyloxy 2-hydroxypropanesulfonic acid, 2-
Acrylamide 2-methylpropanesulfonic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate,

[0024]

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[0025]

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[0026]

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And examples of the compound (c) include:

[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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And the like. As a specific processing method,
After applying an aqueous solution or dispersion containing the compound of (a), (b) and (c), silk fibroin and a radical polymerization catalyst to the fiber material, dry heat treatment, steam treatment, radiation irradiation, ultraviolet irradiation or And a treatment method for performing polymerization by microwave irradiation or the like.

The amount of (a) used is 1 to 10% by weight in the impregnating solution.
The ratio of (a) :( b) :( c) is preferably in the range of 1: 0.1-1: 0.1-1. As the type of the solvent, water or a mixed solvent of a soluble solvent (alcohols, dimethylformamide, acetone, dimethylsulfoxide, etc.) can be used. As the radical polymerization catalyst, a water-soluble or water-insoluble peroxide or azo compound is used. If the monomer mixture is not easily soluble in water, a surfactant such as nonionic or anionic may be added. As the silk fibroin component, it is necessary to mix at least 5% by weight of an aqueous solution of silk fibroin or a dispersion of silk fibroin in a monomer solution, and usually 10 to 80% by weight is used in consideration of texture. Is preferred.

In the silk fibroin-monomer aqueous solution used in the present invention, when a silk fibroin aqueous solution is used as the silk fibroin solution, a heterologous protein such as atelocollagen is used to stabilize the aqueous solution, that is, to prevent gum up. , Hydrolyzed collagen, gelatin, casein and the like. The amount of the heterologous protein used is preferably 20 to 100% by weight based on the silk fibroin. If it is more than 100% by weight, the film formation is poor and the texture becomes coarse and hard.

[0036]

The present invention will be described below in detail 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) Fixation rate [(weight after treatment-weight before treatment) / weight before treatment] x 100 (%) (2) Fixation rate of silk fibroin Example fixation rate-Comparative example (without silk fibroin) ) Adhesion rate (%) (3) Washing test JIS L-0217 103 method (4) Texture KES (manufactured by Kato Iron Works Co., Ltd.) Measured with a texture tester (based on the standard value for thin clothing for women's outer clothing) (5) Water absorption test (I) Dropping method JIS L-1096 A method (II) Bylex method JIS L-1096 B method (6) Antistatic test Friction charge voltage JIS L-1094 B method (7) Contact Thermal sensation Measured by Kato Tech KE8-F7 precision quasi-thermal measuring device (THERMOLABOII TYPE) (I) Contact thermal sensation: qmax The contact thermal sensation feels warm with a large number if it feels cold at the moment of touch. The is represented by small numbers. (II) Thermal conductivity K

A: Method for Preparing Silk Fibroin Aqueous Solution in Examples Using silk spun waste as a raw material, 100 parts thereof were stirred and scoured with a solution of 30 parts of Marcel soap and 3000 parts of water at 95 to 98 ° C. for 3 hours. The residue was reduced to 0.1% or less, washed with water and dried at 80 ° C. with hot air. Next, 34 parts of water was mixed with 66 parts of calcium chloride (CaCl ₂ .2H ₂ O) to prepare 100 parts of a 50% calcium chloride aqueous solution, and the mixture was heated to 110 ° C. 30 parts of the refined spinning waste was added thereto with stirring for 5 minutes, and then stirred for 30 minutes to completely dissolve. After cooling the resulting silk fibroin calcium chloride solution, the solution was dialyzed and desalted with a cellulose tube. That is, the inner diameter of the cellulose tube is 7 to 8
A silk fibroin solution having a diameter of 1 cm and a length of 1 m was filled therein, and after sealing both ends, the salt concentration was reduced to 0.1% or less in running water for 15 to 25 hours. The silk fibroin concentration of the desalted dialysate was about 5.5% by weight.

B: Method for Preparing Silk Fibroin Dispersion in Examples 500 parts of the silk fibroin aqueous solution obtained in the above A was stirred at a high speed for 2 to 3 hours, and gel particles (crystallinity 15%, β structure ratio 58%) The silk fibroin is regenerated as an aggregate of ()). Furthermore, stirring was continued at a high speed, and then about 40 parts of a 30% concentrated ammonium sulfate aqueous solution was mixed, and the mixture was further stirred for 1 hour to perform a process (β-formation process) of the silk fibroin crystal from α structure to β structure. The gel was broken into small particles to obtain a coarse powder (crystallinity: 49%, β structure ratio: 100%). 30 parts of the above coarse powder was mixed with 270 parts of water or an organic solvent, and was wet-pulverized at room temperature for 24 hours in a 1-liter hard porcelain ball mill. A ball made of hard porcelain having a diameter of 3 mm was used and mixed with 500 ml. The dispersion liquid of the fine powder of modified silk fibroin thus obtained was in the form of a white emulsion, and the average particle diameter was 2.13 μm.

A: Solution Method Example 1 A treatment liquid having the following composition was prepared. 5.0% by weight silk fibroin aqueous solution 15.0% Compound of the structural formula (2) 3.0% Methacrylic acid 2.5% Compound of the structural formula (12) (PAZ, manufactured by Nippon Shokubai Co., Ltd.)
-33) 1.5% V-50 (Azo-based polymerization catalyst manufactured by Wako Pure Chemical Industries, Ltd.)
0.3% The above-mentioned treatment liquid is applied to a polyester feil woven fabric (having a basis weight of 110).
g / m ² ), and the mixture is squeezed with a mangle to an impregnation ratio of 70%.
Drying and setting were performed. The obtained work cloth exhibited a fixation rate of 3.5% as compared with that before the treatment. The silk fibroin fixation rate was 2.0%.

Example 2 A treatment liquid having the following composition was prepared. 5.0% by weight silk fibroin aqueous solution 20.0% Compound of structural formula (4) 3.0% Acrylic acid 2.5% Compound of structural formula (9) 1.5% Ammonium persulfate 0.5% The liquid was applied to a polyester cashmere fabric (basis weight 115
g / m ² ) and the degree of impregnation is reduced to 68% with a mangle. The microwave frequency is 2450 MHz and the output is 6.0 with a microwave processing device Apollotex (manufactured by Ichikin Kogyo Co., Ltd.).
While irradiating with KW, steam treatment was performed for 15 minutes under the conditions of direct steam 1.0 kg / cm ² and indirect steam 3.0 kg / cm ² . Thereafter, washing with hot water, drying and setting were performed. The obtained work cloth showed a sticking rate of 3.9% as compared with that before the treatment. The silk fibroin fixation rate was 2.4%.

Example 3 A treatment liquid having the following composition was prepared. 5.0% by weight aqueous solution of silk fibroin 20.0% Compound of the structural formula (5) 3.0% Methacrylic acid 2.5% Compound of the structural formula (12) 1.5% Ammonium persulfate 0.5% The liquid was impregnated in a polyester double woven fabric, squeezed with a mangle to a squeezing rate of 40%, and irradiated with 3 Mrad of 1.5 MeV, 50 μA electron beam in a nitrogen atmosphere by a handicap type electrostatic accelerator. Next, it was washed with hot water at 90 ° C. for 1 minute, dried, set at 180 ° C. for 30 seconds, and the fixation ratio was determined to be 3.9%. The silk fibroin fixation rate was 2.7%.

Comparative Example 1 A compound of the structural formula (2) 3.0% methacrylic acid 2.5% A compound of the structural formula (12) (manufactured by Nippon Shokubai Co., Ltd.) PAZ
-33) 1.5% V-50 (Azo-based polymerization catalyst manufactured by Wako Pure Chemical Industries, Ltd.)
Impregnated with a treatment liquid having a composition of 0.3%, and impregnated with a mangle at an impregnation rate of 7%.
After squeezing to 0%, steam heat treatment was performed at 110 ° C. for 10 minutes, followed by washing with hot water, drying, and setting. The obtained work cloth showed a fixation rate of 1.5% as compared with that before the treatment.

Comparative Example 2 A 5.0 wt% aqueous solution of silk fibroin 20.0% 3.0 wt% aqueous solution of casein 20.0% Elastron MF-9 (Daiichi Kogyo Seiyaku Co., Ltd.) Impregnated with a treatment liquid having a composition of 0.25% Elastron Catalyst-64 (a fatty acid metal salt-based urethane catalyst manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) Let mangle maturation rate 7
After squeezing to 0%, steam heat treatment was performed at 110 ° C. for 10 minutes, followed by washing with hot water, drying, and setting. The obtained work cloth exhibited a fixation rate of 1.0% as compared with that before the treatment.

Comparative Example 3 A polyester cashmere fabric similar to that in Example 2 was prepared by adding 3.0% of the compound of the structural formula (4) 2.5% of acrylic acid 1.5% of the compound of the structural formula (9) 1.5% of ammonium persulfate 0 Impregnated with a treatment liquid having a composition of 0.5%, and impregnated with a mangle at an impregnation rate of 7%.
After narrowing down to 0%, the microwave processing apparatus Apollotex uses a microwave frequency of 2450 MHz and an output of 6.0 KW.
1.0kg / c direct steam while irradiating microwave with
Steam treatment was performed for 15 minutes under the conditions of m ² and indirect steam of 3.0 kg / cm ² . Thereafter, washing with hot water, drying and setting were performed. The obtained work cloth showed a fixation rate of 1.5% as compared with that before the treatment.

Comparative Example 4 A 5.0% by weight aqueous solution of silk fibroin 40.0% Elastron MF-9 (manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd., urethane polymer of terminally blocked isocyanate) was added to the same polyester cashmere fabric as in Example 2. ) 7.0% Elastron Catalyst-64 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., fatty acid metal salt-based urethane catalyst) impregnated with a treatment liquid having a composition of 0.5%, and impregnated with a mangle of 7
After narrowing down to 0%, the microwave processing apparatus Apollotex uses a microwave frequency of 2450 MHz and an output of 6.0 KW.
1.0kg / c direct steam while irradiating microwave with
Steam treatment was performed for 15 minutes under the conditions of m ² and indirect steam of 3.0 kg / cm ² . Thereafter, washing with hot water, drying and setting were performed. The obtained work cloth showed a sticking rate of 1.2% as compared with that before the treatment.

Comparative Example 5 A compound of the formula (5) 3.0% methacrylic acid 2.5% A compound of the formula (12) 1.5% Impregnated with a treatment solution having a composition of 0.5% ammonium sulfate, and squeezed with a mangle to 4
The electron beam of 1.5 MeV and 50 μA was reduced to 3% by a handicap type electrostatic accelerator in a nitrogen atmosphere.
Irradiated. Next, wash with hot water at 90 ° C. for 1 minute,
It was set at 80 ° C. for 30 seconds, and the adhesion rate was determined.
It was 0%.

Comparative Example 6 The treatment liquid used in Comparative Example 2 was impregnated in the same polyester wing double woven fabric as in Example 3, squeezed with a mangle to a squeezing ratio of 40%, and a handicap type electrostatic accelerator in a nitrogen atmosphere. Irradiate 3 Mrad with an electron beam of 1.5 MeV and 50 μA. Next, it was washed with hot water at 90 ° C. for 1 minute, dried, and dried at 180 ° C.
The temperature was set at 30 ° C for 30 seconds.
Met.

The performance of the processed fabrics obtained in Examples 1 to 3 and Comparative Examples 1 to 6 was evaluated by the above evaluation method. The results are shown in Tables 1 and 2.

[0049]

[Table 1]

[0050]

[Table 2]

From the results shown in Tables 1 and 2, the silk fibroin-polymer processed cloth (Examples 1 to 3) of the present invention was
Compared to the processed fabrics obtained in Comparative Examples 1 to 6, it has a silky texture and luster, further increases the feeling of tension and waist, and gives a unique squeaky feeling to silk. It can be seen that the moisture release is close to silk. In addition, the processed fabrics obtained in Examples 1 to 3 have a warm feel when touched, exhibit a performance closer to that of silk despite a low adhesion rate, and have excellent washing resistance. I understood.

B: Powder Method Example 4 A treatment liquid having the following composition was prepared. 5.0% by weight silk fibroin dispersion 20.0% Compound of structural formula (2) 3.0% Methacrylic acid 2.5% Compound of structural formula (12) (PAZ, manufactured by Nippon Shokubai Co., Ltd.)
-33) 1.5% V-50 (Azo-based polymerization catalyst manufactured by Wako Pure Chemical Industries, Ltd.)
0.3% The above-mentioned treatment liquid is applied to a polyester feil woven fabric (having a basis weight of 110).
g / m ² ), and the mixture is squeezed with a mangle to an impregnation ratio of 70%.
Drying and setting were performed. The obtained work cloth exhibited a fixation rate of 4.0% as compared with that before the treatment.

Example 5 A treatment liquid having the following composition was prepared. 5.0% by weight silk fibroin dispersion 20.0% Compound of structural formula (4) 3.0% Acrylic acid 2.5% Compound of structural formula (9) 1.5% Ammonium persulfate 0.5% The treatment liquid was applied to a polyester cashmere fabric (basis weight 115
g / m ² ), and the mixture is squeezed to an impregnation ratio of 70% with a mangle. The microwave frequency is 2450 MHz and the output is 6.0 with a microwave processing device Apollotex (manufactured by Ichikin Kogyo Co., Ltd.).
While irradiating with KW, steam treatment was performed for 15 minutes under the conditions of direct steam 1.0 kg / cm ² and indirect steam 3.0 kg / cm ² . Thereafter, washing with hot water, drying and setting were performed. The obtained work cloth exhibited a fixation rate of 4.5% as compared with that before the treatment.

Example 6 A treatment liquid having the following composition was prepared. 5.0% by weight silk fibroin dispersion 20.0% Compound of structural formula (5) 3.0% Methacrylic acid 2.5% Compound of structural formula (12) 1.5% Ammonium persulfate 0.5% The treatment liquid was applied to a polyester double woven fabric (with a basis weight of 87 g /
m ² ), squeezed by a mangle to a squeezing ratio of 40%, and 1.5 mm with a handicap type electrostatic accelerator in a nitrogen atmosphere.
An electron beam of MeV, 50 μA was irradiated at 3 Mrad. Next, the film was washed with hot water at 90 ° C. for 1 minute, dried, set at 180 ° C. for 30 seconds, and the fixation ratio was determined to be 4.1%.

Examples 4 to 6 and Comparative Examples 1 and 3
The performance evaluation was performed on the processed fabrics obtained in Steps 5 and 5 by the evaluation method described above. The results are shown in Tables 3 and 4.

[0056]

[Table 3]

[0057]

[Table 4]

From the results shown in Tables 3 and 4, the silk fibroin-polymer processed cloth of the present invention (Examples 4 to 6) was
Compared to the processed fabrics obtained in Comparative Examples 1, 3 and 5, it has a silky texture and luster, further increases the feeling of tension and waist, and gives a unique squeaky feeling to silk. It can be seen that the moisture absorption and release are similar to those of silk. In addition, the processed fabrics obtained in Examples 4 to 6 felt warm when touched, exhibited performance closer to silk despite low adhesion, and had excellent washing resistance. I understood.

[0059]

As described in detail above, the silk fibroin-polymer processed fabric obtained by the production method of the present invention has the texture and luster of silk, and further has an increased tension and a feeling of stiffness, which is unique to silk. A squeaky feeling can also be obtained, and the moisture absorption and release of moisture on the surface become similar to silk. In addition, the tactile sensation when touched is felt warm, and exhibits a performance closer to silk despite its low adhesion rate.
Also has excellent washing resistance. Further, by using the method (solution method and powder method) of the present invention, a fabric having such excellent characteristics can be efficiently processed.

────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Junji Sano 3-39-28, Tomimatsu-cho, Amagasaki-shi, Hyogo (72) Inventor Isamu 1-5-9-603, Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka 72) Inventor Hideo Yoshidome 3-6-15 Tenjinyama-cho, Kishiwada-shi, Osaka (72) Inventor Yasuo Shimano 5-63, Honcho, Komatsu-shi, Ishikawa Pref.House 10 (72) Inventor Shuichi Murakami Chiyo, Matsuto-shi, Ishikawa No. 7-3-6 Nonishi (72) Inventor Yoshihiro Umezawa 2-152 Yagicho, Kanazawa City, Ishikawa Prefecture (56) References JP-A-4-306236 (JP, A) JP-A-3-185183 (JP) , A) JP-A-5-71073 (JP, A) JP-A-5-163677 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) D06M 13/00-15/72

Claims (2)

(57) [Claims] 1. The following components are added to an aqueous solution of silk fibroin.
(a) to (c): (a) a bifunctional monomer represented by the following general formula: (b) A monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group or a phosphate group, and (c) a monomer containing an aziridine group or a polyfunctional compound containing two or more aziridine groups. A method for producing a silk-fibroin-graft polymer-processed cloth, comprising applying the treatment liquid obtained in the above to a cloth and polymerizing the treated liquid on the cloth. 2. A dispersion of a silk fibroin powder in the following components (a) to (c): (a) a bifunctional monomer represented by the following general formula: (b) A monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group or a phosphate group, and (c) a monomer containing an aziridine group or a polyfunctional compound containing two or more aziridine groups. A method for producing a silk-fibroin-graft polymer-processed cloth, comprising applying the treatment liquid obtained in the above to a cloth and polymerizing the treated liquid on the cloth.