JPH06158545A - Silk fibroin-graft polymer-processed fabric and its production - Google Patents

Abstract

PURPOSE:To readily obtain silk fibroin-graft polymer-processed fabric having silk luster, handle, washing resistance, repulsion and water vapor absorption by forming a coating film comprising a specific amount of silk fibroin-graft polymer on the surface of a fiber. CONSTITUTION:An aqueous solution of silk fibroin is blended with a bifunctional monomer of formula I [R is directly bonded group of formula II, formula III, formula IV or CnH2n (n is 1-6); z is H or CH3; a and b are numbers to make a+b 0-50; x and y are numbers to make x+y 0-30 with the proviso that a+b+x+y>=10), a monomer containing OH, COOH, NH2, sulfo group or phosphate group [e.g. (meth)acrylic acid] and a monomer containing an aziridine group or a polyfunctional compound containing two or more aziridine groups to give a treating solution, Fabric of natural fiber or synthetic fiber is immersed in the treating solution, graft polymerization is carried out on the fabric to attach 0.1-5% owf silk fibroin and 0.2-10% pwf coating film comprising the silk fibroin-graft polymer to the fabric. The prepared fabric has luster and water vapor absorption close to those of silk and shows scroop feellng of characteristic silk.

Description

Detailed Description of the Invention

[0001]

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

[0002]

2. Description of the Related Art Silk has a unique and elegant dignity that is unrivaled by other fibers, such as quiet deep luster, soft texture, and elegant drape, and is highly regarded as the top material among fibers. Has been done. Therefore, many processing methods for imparting silk characteristics to fibers other than silk have been proposed. For example, in the case of polyester fiber, a method of reducing the weight by alkali treatment to finish the texture softly, and in the case of cellulosic fiber, a method of reducing the weight with an enzyme to finish softly,
For rayon and silk, methods such as adding urethane resin or silicone resin to improve resilience and softness, or adding amino acid-based resin to express crease feeling have 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, all of them are inferior in appearance effect or durability.

On the other hand, treatment using a silk fibroin solution has been proposed so far, but there is a problem that durability after treatment is poor. That is, it is difficult to develop the original luster, repulsion and hygroscopicity of silk in ordinary fiber processing with good durability, and a method for producing a fabric having excellent characteristics close to silk has not yet been found.

[0004]

DISCLOSURE OF THE INVENTION The inventors of the present invention have completed the present invention as a result of earnest studies on imparting the physical properties and feel of silk fibroin to other materials. The object of the present invention is to have silk luster, texture, repulsion and hygroscopicity,
Moreover, it is to provide a fabric excellent in durability of those properties. Another object of the present invention is to provide a method for producing such a fabric industrially easily and inexpensively.

[0005]

In order to achieve the above object, the present invention has the following constitution. That is, the first invention is a cloth having a film made of a silk fibroin-graft polymer on the fiber surface, and the amount of the silk fibroin attached is 0.1 to 5.0% by weight based on the weight of the cloth. And the amount of the above-mentioned coating adhered is 0.2 to the weight of the cloth.
The gist is a silk fibroin-graft polymer processed fabric of 10.0% by weight. The second aspect of the invention is to apply a treatment liquid obtained by dissolving an aqueous solution or dispersion of a monomer mixture composed of various monomers in a silk fibroin aqueous solution to a cloth, and then polymerize the cloth on the cloth. The gist is a method for producing a silk-fibroin-graft polymer-processed fabric, which is characterized in that Further, the third invention is to prepare a silk fibroin dispersion liquid in which fine silk fibroin powder is uniformly dispersed, and then dissolve an aqueous solution or dispersion liquid of a monomer mixture including various monomers in the dispersion liquid. The gist is a method for producing a silk-fibroin-graft polymer-processed fabric, which is characterized in that the obtained treatment liquid is applied to the fabric and then polymerized on the fabric.

The present invention will be described in detail below. The silk fibroin-graft polymer processed fabric of the present invention is such that a uniform thin film made of silk fibroin-graft polymer wraps the fiber surface constituting the fabric, and this surface polymer film is no longer in water. It does not dissolve or fall off, and has washing resistance. Then, such a durable cross-linked fibroin coating film is formed by graft-polymerizing a mixture described below. In the above-described processed fabric of the present invention, the amount of silk fibroin attached to the weight of the fabric is at most 5% by weight in consideration of the flexibility and texture of the fabric.
0.1 to 5.0% by weight, preferably 0.5 to
It is 3.0% by weight. In addition, from the viewpoint of the flexibility and texture of the cloth, the amount of the above-mentioned film attached is 0.2 to the weight of the cloth.
It is preferably 10.0% by weight. The thickness of the coating is usually 0.01 to 10 μm.

In the present invention, the cloth on which the above-mentioned film is formed includes cellulose fibers such as cotton, rayon and hemp, semi-synthetic fibers such as acetate and triacetate, polyester,
Examples include synthetic fibers such as nylon and acrylic fibers, and mixed fibers or mixed fiber products. Examples of the form include woven fabric, knitted fabric, and non-woven fabric. Among them, particularly, a cloth or a polyester cloth using polyamide fiber such as nylon, which is difficult to be modified by a usual processing method, has a remarkable effect by the present invention.

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-graft polymer-processed fabric of the present invention is the same as the following components in an aqueous silk fibroin solution: a bifunctional monomer represented by the following general formula.

[0009]

[Chemical 1]

A monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group, or a phosphoric acid group, and a monomer containing an aziridine group or an aziridine group are used.
A treatment liquid (aqueous solution or dispersion liquid) obtained by adding three components of a polyfunctional compound containing one or more of them is applied to the cloth and then polymerized on the cloth, and a crosslinked film is formed on the cloth. It is formed (hereinafter referred to as a solution method).

Furthermore, the method for producing a silk-fibroin-graft polymer-processed fabric according to the present invention comprises the following components in the dispersion liquid of silk fibroin powder: a bifunctional monomer represented by the following general formula.

[0012]

[Chemical 1]

A monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group or a phosphoric acid group, and a monomer containing an aziridine group or an aziridine group are used.
It is also characterized in that a treatment liquid obtained by adding a polyfunctional compound containing one or more of them is applied to a cloth and then polymerized on the cloth (hereinafter referred to as a powder method).

According to the above-mentioned two production methods of the present invention, the above-mentioned monomer is graft-polymerized on the silk fibroin by radical polymerization, so that the insoluble matter is formed on the surface of the fiber constituting the cloth and / or inside the surface close to the surface. A crosslinkable film is formed,
This coating enables silk processing of silk fibroin-immobilized fibrous materials that can withstand dozens of home launderings and dry cleanings. Then, by using an ordinary fiber processing method, it is possible to impart the original luster, texture, repulsion and hygroscopicity of silk with good durability. Furthermore, the method of the present invention can eliminate the drawbacks of the synthetic fibers, such as being easily charged, having poor water absorption, and being hard to remove stains.

As the silk fibroin aqueous solution used in the solution method of the present invention, known ones can be widely used.
For example, Japanese Patent Publication No. 58-38449 and Japanese Unexamined Patent Publication No. 3-18
The one described in Japanese Patent 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 (Schweiser reagent), a copper hydroxide-alkali-glycerin aqueous solution (Lohe's 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 raw silk factory or silk spinning factory using Marcel soap and soda ash by a conventional method, It is a solution of silk fiber having residual sericin of 1% by weight or less.

In the solution method of the present invention, the concentration of silk fibroin in the silk fibroin aqueous solution is usually 0.5 to 20.0% by weight, particularly 1.0 to 10.0% by weight, although it varies depending on the kind of solvent and the amount of adhesion. % Is preferred. The silk fibroin aqueous solution applied to the present invention may be the same as above, but is preferably debased and / or desalted from the viewpoint of product quality and process. Here, the debasing or desalting treatment is usually carried out by dialysis using a semipermeable membrane of a tube or a film.

On the other hand, as the silk fibroin dispersion liquid used in the powder method of the present invention, known liquids can be widely used, for example, those described in Japanese Patent Application No. 3-138216 can be applied. What is described in this Japanese Patent Application No. 3-138216 is crystallization of regenerated silk coarse powder from an aqueous silk fibroin solution or embrittlement coarse powder obtained by treating silk fibers with an acid or an alkali. Of fine powder of modified silk fibroin obtained by wet pulverizing with a ball mill a coarse powder whose naturalness is modified to 1/2 or less of natural fiber, using water or an organic solvent as a dispersion medium. A dispersion having a volume average particle diameter of 5 μm or less.

Next, components to be added to the silk fibroin aqueous solution in the method of the present invention will be described. The compounds shown below are specific examples of the compounds of the above and, and the present invention is, of course, It is not limited to these. First, as an example of the above compound,

[0019]

[Chemical 2]

[0020]

[Chemical 3]

[0021]

[Chemical 4]

[0022]

[Chemical 5]

Examples of the compound include acrylic acid, methacrylic acid, styrenesulfonic acid, maleic acid, itaconic acid, crotonic acid, vinylsulfonic acid, 2-
Allyloxy 2-hydroxypropanesulfonic acid, 2-acrylamido 2-methylpropanesulfonic acid, 2-hydroxyethyl methacrylate, hydroxypropyl methacrylate,

[0024]

[Chemical 6]

[0025]

[Chemical 7]

[0026]

[Chemical 8]

And the like, and examples of the compound of

[0028]

[Chemical 9]

[0029]

[Chemical 10]

[0030]

[Chemical 11]

[0031]

[Chemical 12]

[0032]

[Chemical 13]

Etc. As a concrete processing method,
, And a water-based solution or dispersion containing silk fibroin and a radical polymerization catalyst is applied to the fiber material, and then subjected to polymerization by dry heat treatment, steam treatment, radiation irradiation, ultraviolet irradiation, or microwave irradiation. There is a processing method to make it.

The amount used of 1 is preferably in the range of 1 to 10% by weight in the impregnation liquid, and the ratio of :: is 1 :.
It is preferably in the range of 0.1: 1: 0.1-1. As the type of solvent, water or a mixed solvent of soluble solvents (alcohols, dimethylformamide, acetone, dimethylsulfoxide, etc.) can be used. As the radical polymerization catalyst, water-soluble or water-insoluble peroxides and azo compounds are used. When the above monomer mixture is not readily soluble in water, a surfactant such as nonion or anion may be added. As the silk fibroin component, it is necessary to mix at least 5% by weight of an aqueous silk fibroin solution or a silk fibroin dispersion in a monomer solution,
Usually, it is preferable to use 10 to 80% by weight in consideration of texture.

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

[0036]

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) Sticking rate (2) Sticking rate of silk fibroin Example sticking rate-Comparative example (without silk fibroin) Sticking rate (%) (3) Washing test JIS L-0217 103 method (4) Texture KES (Kato Iron Works Co., Ltd. ) Made) measured by a texture tester (displayed as a hand value on the basis of the thin cloth for women's outerwear) (5) water absorption test (I) dropping method JIS L-1096 A method (II) Bayrek method JIS L-1096 Method B (6) Antistatic test Friction electrification voltage JIS L-1094 Method B (7) Contact temperature cooling sensation Measured by KATO TECH KE8-F7 precision quasi-thermal measuring device (THERMOLABO II TYPE) (I) Contact temperature cooling Feeling: qmax The contact thermal sensation is represented by a large numerical value when it feels cold when touched and a small numerical value when it feels warm. (II) Thermal conductivity K

A: Method for preparing an aqueous solution of silk fibroin in Examples Using silk spinning waste as a raw material, 100 parts of this was 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 residual glue was reduced to 0.1% or less, washed with water and dried with hot air at 80 ° C. Next, 34 parts of water was mixed with 66 parts of calcium chloride (CaCl ₂ .2H ₂ O) to prepare 100 parts of 50% calcium chloride aqueous solution, and heated to 110 ° C. To this, 30 parts of scoured refined spinning waste was added with stirring for 5 minutes, and further stirred for 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, the inner diameter of the cellulose tube is 7 to 8
The silk fibroin solution having a size of 1 cm and a length of 1 m was filled with the silk fibroin solution, and both ends were sealed, and then 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 high speed for 2-3 hours to give gel particles (crystallinity 15%, β structure ratio 58%). ) Regenerates silk fibroin as an aggregate. Further, stirring was continued at a high speed, then about 40 parts of 30% concentrated ammonium sulfate aqueous solution was mixed, and the mixture was further stirred for 1 hour, and as a result, the α-structure to β-structure of the silk fibroin crystal was treated (β-formation treatment). The gel body was crushed 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 wet-milled at room temperature for 24 hours with a 1 liter ball mill made of hard porcelain. A ball made of hard porcelain having a diameter of 3 mm was used and mixed with 500 ml. The dispersion liquid of the modified silk fibroin fine powder thus obtained was in the form of a white emulsion and had an average particle diameter of 2.13μ.

A: Solution Method Example 1 A treatment liquid having the following composition was prepared. 5.0 wt% aqueous silk fibroin solution 15.0% Compound of structural formula (2) 3.0% Methacrylic acid 2.5% Compound of structural formula (12) (Nippon Shokubai Co., Ltd., PAZ-33) 1 0.5% V-50 (manufactured by Wako Pure Chemical Industries, Ltd., azo-based polymerization catalyst) 0.3% The above treatment liquid was used as a polyester faille fabric (Basis weight 110).
g / m ² ) and after squeezing the impregnation rate to 70% with mangle, steam heat treatment is performed at 110 ° C. for 10 minutes, followed by washing with hot water.
It was dried and set. The obtained processed cloth showed a sticking rate of 3.5% as compared with that before the processing. The silk fibroin fixation rate was 2.0%.

Example 2 A treatment liquid having the following composition was prepared. 5.0% by weight aqueous silk fibroin 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 is a polyester cashmere fabric (with a basis weight of 115
g / m ² ) and squeezed with a mangle to make the impregnation rate 68%. Then, with a microwave treatment device APOLOTEX (manufactured by Ichikin Kogyo Co., Ltd.), microwave frequency 2450 MHz, output 6.0.
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 . Then, it was washed with hot water, dried and set. The obtained processed cloth showed a fixation rate of 3.9% as compared with that before the processing. Further, the silk fibroin fixation rate was 2.4%.

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

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

Comparative Example 2 A polyester fiuille fabric similar to that used in Example 1 was mixed with 5.0% by weight aqueous silk fibroin solution 20.0% 3.0% by weight aqueous casein solution 20.0% Elastron MF-9 (Daiichi Kogyo Seiyaku Co., Ltd.). Company-made, end-blocked isocyanate urethane polymer) 2.0% Elastron Catalyst-64 (Daiichi Kogyo Seiyaku Co., Ltd., fatty acid metal salt-based urethane catalyst) Impregnated with a treatment liquid having a composition of 0.25%. Let the mangle impregnate 7
After squeezing to 0%, steam heat treatment was performed at 110 ° C. for 10 minutes, washing with hot water, drying, and setting. The obtained processed cloth showed a sticking ratio of 1.0% as compared with that before the processing.

Comparative Example 3 A polyester cashmere fabric similar to that used in Example 2 was prepared by adding the compound of the above structural formula (4) 3.0% acrylic acid 2.5% to the compound of the above structural formula (9) 1.5% ammonium persulfate 0 Impregnation with a treatment liquid having a composition of 0.5% and an impregnation rate of 7 with mangle
After narrowing down to 0%, microwave frequency is 2450MHz, output is 6.0KW with microwave processing device APOROTEX.
Directly steam 1.0kg / c 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 . Then, it was washed with hot water, dried and set. The obtained processed cloth showed a sticking rate of 1.5% as compared with that before the processing.

Comparative Example 4 The same polyester cashmere fabric as in Example 2 was mixed with 5.0% by weight aqueous solution of silk fibroin 40.0% Elastron MF-9 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd., urethane polymer of end-blocked isocyanate). ) 7.0% Elastron Catalyst-64 (manufactured by Dai-ichi 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%, microwave frequency is 2450MHz, output is 6.0KW with microwave processing device APOROTEX.
Directly steam 1.0kg / c 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 . Then, it was washed with hot water, dried and set. The obtained processed cloth showed a sticking ratio of 1.2% as compared with that before the processing.

Comparative Example 5 A polyester winged fabric similar to that used in Example 3 was mixed with 3.0% of the compound represented by the structural formula (5), 2.5% of methacrylic acid and 1.5% of the compound represented by the structural formula (12). Impregnate a treatment liquid having a composition of 0.5% ammonium sulfate, and squeeze it to 4 with a mangle.
Squeeze to 0%, and use a hand-held electrostatic accelerator in a nitrogen atmosphere to generate an electron beam of 1.5 MeV and 50 μA at 3 Mrad.
Irradiated. Next, rinse with hot water at 90 ° C for 1 minute, dry, and then 1
It was set at 80 ° C. for 30 seconds and the sticking rate was calculated.
It was 0%.

Comparative Example 6 A polyester winged fabric similar to that used in Example 3 was impregnated with the treatment liquid used in Comparative Example 2, squeezed with a mangle to a squeezing ratio of 40%, and a handheld type electrostatic accelerator in a nitrogen atmosphere. Was irradiated with 3 Mrad of an electron beam of 1.5 MeV and 50 μA. Then, wash in hot water at 90 ° C for 1 minute, dry, and then 180
It was set at ℃ for 30 seconds and the sticking rate was calculated to be 0.6%
Met.

Performance evaluation was performed on the processed fabrics obtained in Examples 1 to 3 and Comparative Examples 1 to 6 by the above-described 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 above, the silk fibroin-polymer processed fabrics (Examples 1 to 3) of the present invention were
Compared with the processed fabrics obtained in Comparative Examples 1 to 6, it has a silk texture and luster, further increases tension and waist feeling, and a squeaky feeling peculiar to silk is also obtained, and moisture absorption of surface moisture, It can be seen that the moisture release is similar to silk. Further, the processed fabrics obtained in Examples 1 to 3 have a warm feeling when touched, exhibit a performance closer to that of silk in spite of 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 wt% Silk fibroin dispersion 20.0% Compound of structural formula (2) 3.0% Methacrylic acid 2.5% Compound of structural formula (12) (Nippon Shokubai Co., Ltd., PAZ-33) 1.5% V-50 (manufactured by Wako Pure Chemical Industries, Ltd., azo-based polymerization catalyst) 0.3% The above treatment liquid was applied to a polyester faille woven fabric (weight: 110).
g / m ² ) and after squeezing the impregnation rate to 70% with mangle, steam heat treatment is performed at 110 ° C. for 10 minutes, followed by washing with hot water.
It was dried and set. The obtained processed cloth showed a sticking ratio of 4.0% as compared with that before the processing.

Example 5 A treatment liquid having the following composition was prepared. 5.0 wt% 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% Treat the treatment liquid with polyester cashmere fabric
g / m ² ) and after squeezing the impregnation rate to 70% with a mangle, a microwave treatment device APOLOTEX (manufactured by Ichigane Kogyo Co., Ltd.) was used to obtain a microwave frequency of 2450 MHz and an output of 6.0.
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 . Then, it was washed with hot water, dried and set. The obtained processed cloth showed a fixing rate of 4.5% as compared with that before the processing.

Example 6 A treatment liquid having the following composition was prepared. 5.0 wt% 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 is a polyester Habutae fabric (weight: 87 g /
m ² ), squeeze with a mangle to a squeezing ratio of 40%, and then 1.5 in a nitrogen atmosphere with a Handegraph electrostatic accelerator
An electron beam of MeV and 50 μA was irradiated at 3 Mrad. Then, it was washed with hot water at 90 ° C. for 1 minute, dried and set at 180 ° C. for 30 seconds, and the sticking ratio was calculated 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 Nos. 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 of Tables 3 and 4 above, the silk fibroin-polymer processed fabrics (Examples 4 to 6) of the present invention were
Compared with the processed fabrics obtained in Comparative Examples 1, 3 and 5, the texture and luster of silk are further increased, and the tension and waist feeling are further increased, and a squeaky feeling peculiar to silk is also obtained. It can be seen that moisture absorption and desorption are similar to silk. In addition, the processed fabrics obtained in Examples 4 to 6 have a warm feeling when touched, exhibit a performance closer to that of silk in spite of the low adhesion rate, and have excellent washing resistance. I understood.

[0059]

As described above in detail, the silk-fibroin-polymer-processed fabric of the present invention has silk texture and luster, and further increases tension and luster, and gives a squeaky feeling peculiar to silk. Also, the surface absorbs moisture and releases moisture close to that of silk. In addition, it feels warm to the touch and exhibits a performance closer to that of silk in spite of a low adhesion rate. Moreover, since it is fixed by graft polymerization, it has excellent washing resistance. Further, by using the method of the present invention (solution method and powder method), a fabric having such excellent characteristics can be efficiently processed.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Atsushi Yamamoto 515-39 Kiyosaki-cho, Hikone City, Shiga Prefecture (72) Inventor Junji Sano 3-39-28 Tomimatsu-cho, Amagasaki City, Hyogo Prefecture (72) Inventor Isamu Nakamura 1-5-9-603, Tomobuchi-cho, Miyakojima-ku, Osaka-shi, Osaka (72) Inventor Hideo Yoshidome 3-6-115, Tenjinyama-cho, Kishiwada-shi, Osaka (72) Yasunao Shimano 5-63, Honmachi, Komatsu-shi, Ishikawa Honcho House 10 (72) Inventor Shuichi Murakami 7-3-6 Chiyono Nishi, Matsuto-shi, Ishikawa Prefecture (72) Yoshihiro Umezawa 2-152 Yagi-cho, Kanazawa-shi, Ishikawa Prefecture

Claims (3)

[Claims] 1. A cloth having a film made of a silk fibroin-graft polymer on the fiber surface, wherein the amount of silk fibroin deposited is 0.1 to 5.0% by weight based on the weight of the cloth, and A silk-fibroin-graft polymer-processed fabric, characterized in that a coating amount is 0.2 to 10.0% by weight based on the weight of the fabric. 2. A silk fibroin aqueous solution containing the following components: a bifunctional monomer represented by the following general formula: A monomer containing a hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group or a phosphoric acid group, and a monomer containing an aziridine group or an aziridine group are used.
A process for producing a silk-fibroin-graft polymer-processed fabric, which comprises applying a treatment liquid obtained by adding a polyfunctional compound containing one or more of them to the fabric, and then polymerizing the treatment liquid on the fabric. 3. A dispersion liquid of silk fibroin powder containing the following components: a bifunctional monomer represented by the following general formula: embedded image A hydroxyl group, a carboxyl group, an amino group, a sulfonic acid group or a phosphoric acid group. Monomers containing, and monomers containing aziridine groups or aziridine groups
A process for producing a silk-fibroin-graft polymer-processed fabric, which comprises applying a treatment liquid obtained by adding a polyfunctional compound containing one or more of them to the fabric, and then polymerizing the treatment liquid on the fabric.