JPH0578979A - Modified silk powder-fixed cloth and its production - Google Patents

Abstract

PURPOSE:To obtain the title cloth having excellent silk touch feeling by reducing crystallinity of a natural silk yarn and fixing pulverized modified silk powder on the fiber surface at a specific amount. CONSTITUTION:Using cocoon, cocoon waste, silk spun yarn waste, etc., as a raw material, sericin is removed and silk is regenerated from a sericin removed silk fibroin solution dissolved in a solution of salts, preferably of calcium, etc., and dried and pulverized to provide finely powdered silk powder having crystallinity modified into <=1/2 of a natural silk yarn and having <=5mum volume average particle diameter. Then the silk powder is applied to the fiber surface of natural or synthetic fiber, etc., as dispersion of water or organic solvent and the applied fiber is heat-treated and fixed or a dispersion to which a synthetic resin emulsion (e.g. acrylic resin) or the resin emulsion and further a water soluble high polymer are added is applied to the applied fiber and the fiber is thermally fixed to provide the cloth having silk touch feeling. Furthermore, by the addition of the water soluble high polymer to the cloth water absorbing cloth rich in washability is provided.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a finely powdered modified silk powder processed cloth and a method for producing the same.

[0002]

2. Description of the Related Art Silk has a soft and 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, for polyester fibers, various proposals have been made such that the cross-sectional shape of the original fiber is changed from a round shape to an irregular shape, the denier is made finer, a mixed denier yarn is used, or a combination of different shrinkage yarns is used. Further, there is a method of reducing the weight by alkali treatment and finishing the texture softly. Nylon is known to be processed with organic acids for weight loss. As a post-processing method, a method of adding a urethane resin or a silicone resin to improve resilience and a soft feeling, or adding an amino acid resin to express a tingling feeling has been proposed. 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 silk fibroin solution has also been proposed, but there is a problem that the stability of the solution is particularly poor, especially with respect to shearing force, and further the texture of the processed fabric becomes hard and the durability after the treatment is increased. There is also the problem of poor sex. That is, it is difficult to express the original luster, feel, repulsion and hygroscopicity of silk in ordinary fiber processing, and no silk close to natural silk has been found.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present invention has been completed as a result of researching the physical properties of silk and paying attention to fine powder modified silk powder. The object of the present invention is to provide silk luster, texture,
It is an object of the present invention to provide a cloth which has resilience and hygroscopicity and is excellent in durability of those properties. Another object is to provide a method for producing such a fabric industrially easily and inexpensively.

[0005]

In order to achieve the above-mentioned object, the present invention has the following constitution. That is, the first aspect of the present invention is a fine powder modified silk powder having a volume average particle diameter of 5 μm or less in which the crystallinity of the fiber surface is modified to ½ or less of that of natural silk yarn, and the fine powdery modified silk powder has a volume average particle diameter of 0.5 μm or less. The gist is a specially textured fabric that is fixed by 05 to 5.0%. A second aspect of the present invention is a method for producing such a processed fabric, comprising water of finely powdered modified silk powder having a volume average particle size of 5 μm or less and having a crystallinity modified to 1/2 or less of that of natural silk or A third method of manufacturing a finely powdered modified silk powder-fixed cloth is characterized in that an organic solvent dispersion liquid or a liquid to which a synthetic resin emulsion is added is applied to the cloth, and dry heat or wet heat treatment is performed. The invention provides a water-soluble polymer in water or an organic solvent dispersion of fine powder modified silk powder having a crystallinity modified to 1/2 or less of natural silk and having a volume average particle size of 5 μm or less. A gist of the present invention is to provide a method for producing a fine powdery modified silk powder-fixed cloth, which comprises applying the added processing liquid to the cloth and subjecting it to dry heat or wet heat treatment.

The present invention will be described in detail below. In the present invention, the cloth means synthetic fibers such as polyester, nylon and acrylic, cellulose fibers such as cotton, rayon and hemp, semi-synthetic fibers such as acetate and triacetate, and mixed fibers of various fibers, woven fabrics, knitted fabrics and non-woven fabrics. Is mentioned.

The modified silk powder-fixed cloth of the present invention is a fine powder modified silk powder having a volume average particle size of 5 μm or less, which has a crystallinity modified to 1/2 or less of natural silk yarn. However, in consideration of the flexibility and feel of the fiber, the amount of the fine powder modified silk powder deposited is at most 10% by weight with respect to the cloth, and usually 0.05 to 5.
It is 0% by weight, preferably 0.1 to 5.0% by weight.

The synthetic resin emulsion applicable to the present invention is preferably an acrylic resin emulsion or a urethane resin emulsion. Examples of the acrylic resin emulsion include homo- or copolymer emulsions of acrylic acid ester, acrylic acid, methacrylic acid acrylamide, glycidyl methacrylate, and the like, or mixed emulsions of these homopolymers. The urethane resin emulsion is synthesized by a known method such as phase inversion emulsification, a method using a blocked isocyanate, a method by an interfacial polycondensation reaction and the like.

Regarding the blending ratio of the fine powder modified silk powder component and the synthetic resin emulsion of the present invention, it is necessary to mix at least 10% by weight of the fine powder modified silk powder component in consideration of the texture of the processed cloth. And at least 30% by weight, especially 50% by weight or more is preferable. The synthetic fiber emulsion component is preferably at least 10% by weight, particularly preferably 20% by weight or more. The ratio of fine powder modified silk powder and synthetic resin emulsion component is
Although it can be appropriately determined depending on the desired quality such as feeling or durability, 50 to 80% by weight of fine powder modified silk powder and 20 to 50% by weight of synthetic resin emulsion component are usually used. Further, a softening agent, an antistatic agent, an antiseptic agent, a toning agent, a water absorbing agent, a reaction catalyst and the like may be added to the fine powder modified silk powder applied to the present invention, if necessary.

The water-soluble high molecular polymer applied to the present invention is obtained by polymerizing or copolymerizing a hydrophilic monomer or chemically introducing a hydrophilic group into the high molecular polymer. A polymer having an alkylene oxide unit is preferably used. For example, polyethylene glycol-polyethylene terephthalate block copolymer, polyethylene glycol mono- or diacrylate-acrylamide copolymer, urethane polymer obtained by reacting polyol and diisocyanate, and epoxy obtained by condensing epichlorohydrin and polyol. Examples include compounds. Further, the above water-soluble high-molecular weight polymer refers to a polymer which, after being applied to a cloth, transitions to a cured state by heat treatment.

The blending ratio of the finely powdered modified silk powder component and the water-soluble polymer component of the present invention can be appropriately determined depending on the desired quality such as feeling, durability, etc. A processing liquid is prepared at a ratio of 5 to 20 parts of water-soluble polymer component to 10 parts of silk powder component.

In the method of the present invention, scouring silk raw materials to be used include eyebrows, raw silk, eyebrows scraps, raw silk scraps, screws, fried cotton, silk cloth scraps, burettes, etc. in the presence of an active agent, if necessary, in the presence of warm water In the medium or in the presence of the enzyme, the one obtained by removing sericin and drying in warm water is used. When producing a recycled silk coarse powder from a silk fibroin aqueous solution, the solvent used to dissolve the silk raw material is copper-ethylenediamine aqueous solution, silk hydroxide-
Ammonia aqueous solution (Schweiser reagent), copper hydroxide-alkali-glycerin aqueous solution (Lohe reagent), lithium bromide aqueous solution, calcium or magnesium or zinc hydrochloride or nitrate or thiocyanate aqueous solution, sodium thiocyanate aqueous solution However, from the viewpoint of cost and use, calcium or magnesium hydrochloride or nitrate is preferable. The concentration of these aqueous solutions varies depending on the type of solvent used, temperature and the like, but the concentration of metal salts and the like is usually 10 to 80% by weight, preferably 20 to 70% by weight, and particularly preferably 25 to 60% by weight. The silk raw material after scouring is added to the solvent consisting of the above-mentioned aqueous solution, and the temperature is 60-
Although it dissolves uniformly at 95 ° C, preferably 70 to 85 ° C in an apparatus such as a kneader, the liquid ratio is usually 2 to 50, preferably 3 to 30.

Silk can be regenerated from an aqueous silk fibroin solution by mixing 3 to 20% by weight of an aqueous silk fibroin solution with a coagulating salt, blowing air, isoelectric focusing, ultrasonic treatment and stirring at a high shear deformation rate. It is carried out by coagulating and depositing silk fibroin with at least one kind, and then dehydrating and drying and coarsely pulverizing. The silk fibroin aqueous solution can be used as it is when coagulating with a coagulating salt, but must be dialyzed and used in other coagulation steps. Even when using a coagulable salt, dialysis is preferred. For dialysis, a dialysis membrane typified by a cellophane membrane or a dialysis machine using hollow fibers is used to almost completely remove the salts and the like. When a coagulating salt is used, for example, silk fibroin is precipitated by mixing and stirring concentrated aqueous solutions of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, sodium nitrate, potassium nitrate and the like. (In the case of coagulation of sulfate with calcium salt solvent, calcium sulfate co-precipitates.) The concentration of the coagulating salt in the concentrated aqueous solution is adjusted so that the concentration of the mixed solution with the silk fibroin aqueous solution is usually 5 to 10% by weight.

Air is blown by an appropriate method so that the liquid does not bubble out. Usually, an air amount of 0.1 l / min or more is usually blown to 1 l of the silk fibroin aqueous solution, and the blowing time is a unit. It usually depends on the amount of air per hour, but is usually 10 minutes or more. Isoelectric point coagulation is performed by adding an inorganic acid such as hydrochloric acid and sulfuric acid or an organic acid such as acetic acid and citric acid while stirring the silk fibroin aqueous solution to adjust the pH to 4.5, and usually at room temperature for 10 minutes or more. For ultrasonic treatment, put silk fibroin aqueous solution into the ultrasonic generator and stir normally at 30K.
The silk fibroin is coagulated by passing ultrasonic waves of Hz or higher at room temperature for 1 hour or longer. Silk fibroin is precipitated only by stirring, but in this case, it must be performed at a high shear deformation rate, usually at a shear deformation rate of 50 / sec or more, preferably 100 / sec or more. The stirring time varies depending on the concentration of the aqueous solution, the shear deformation rate, etc., but the gelation is usually performed in 1 hour or more. At this time, the β structure ratio can be improved up to about 70% by mixing methanol, ethanol, isopropyl alcohol, or acetone at the time of stirring. The mixing amount of alcohol or acetone is appropriately 1 to 100% by weight with respect to the aqueous solution.

The gel body obtained is subjected to a dehydration step.
A centrifugal dehydrator is preferably used here, and the stable gel body according to the present invention is usually dehydrated to about 100 to 500% by weight based on the solid content. During the centrifugal dehydration step, the gel body is broken into a proper size and can be easily dried to a completely dried state by subsequent drying. Drying is performed at a temperature of 60 to 120 ° C. under normal pressure or reduced pressure.

The regenerated silk coarse powder obtained is subjected to moist heat treatment or salting-out treatment to change the crystal structure of silk fibroin (α → β).
And promote crystallization. Wet heat treatment is under saturated steam at a temperature of 50
It is preferable to perform the moist heat treatment at a temperature of not less than 0 ° C, especially at 80 to 120 ° C. The treatment can be performed at the powder stage after dehydration and drying. The salting-out treatment is carried out before drying with a hot aqueous solution of sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, ammonium sulfate, sodium nitrate or the like, for example, at 50 ° C. or higher.

In the method of the present invention, the embrittlement coarse powder is produced by treating the silk fiber with an acid or an alkali by immersing the silk fiber in an aqueous solution of 0.1 to 1.0 MOL / l of the acid or the alkali. .. The treatment temperature is room temperature to 90 ° C., the treatment time is 5 minutes to 60 minutes, and the liquid ratio is 5 to 30. The temperature and the treatment time can be selected appropriately, but if the treatment is excessive, the embrittlement of the silk fiber proceeds too much and it is dissolved, resulting in a poor yield. On the other hand, when the embrittlement is insufficient, it cannot be efficiently pulverized by fine pulverization in the next step, and in some cases, it may be impossible to reduce the average particle diameter to 5 μm or less.

The regenerated silk coarse powder or the embrittled silk coarse powder thus obtained is then finely pulverized by wet pulverization using water or an organic solvent as a dispersion medium. As a wet type fine pulverizer, colloid mill, medium stirring mill (trade name sand mill, pearl mill),
A ball mill or the like can be used, but a ball mill is particularly preferable in terms of handling of the crusher, performance of the powder, and the like. In the wet ball mill grinding, the dispersion concentration of the coarse powder is 3 to 30% (by weight), and the amount of balls is about 1/2 of the total volume of the ball mill. The smaller the dispersion concentration, the more quickly the average particle diameter becomes 5 μm or less, but the productivity is low and the economical limit is 3% (weight). When it is 30% (weight) or more, the flow during pulverization is poor, and the average particle size does not become 5 μ or less even after pulverizing for several tens of hours. The crushing time is appropriately determined within a range of 4 hours to 24 hours, and it is 4 hours when crushing to an average particle size of about 5μ, 8 hours when crushing to an average particle size of 4μ, and 24 hours when crushing to about 2μ. Is. However, this slightly changes before and after depending on the crystallinity of the recycled silk, the brittleness of the embrittled silk, the filling amount of the dispersion medium, the dispersion concentration, and the like. Balls crushed by a ball mill are mainly spherical ones, but rod-shaped ones may be used. Use a spherical one having a diameter of 1 m / m to 5 m / m. It is difficult to manufacture a powder having an average particle diameter of 5 μm or less with a ball having a particle diameter of 10 m / m or more.

In the method of the present invention, a recycled silk coarse powder or an embrittled silk coarse powder is wet-milled with a ball mill. That is, although water or an organic solvent is used as the dispersion medium, the organic solvent is not particularly limited, but alcohols such as ethanol, polyols such as 1,3-butanediol, ethers such as dioxane, and acetone Suitable are ketones, organic acids such as acetic acid, and aprotic polar amide solvents such as N, N-dimethylformamide.

The wet pulverized product of the silk powder thus obtained is a white emulsion-like dispersion liquid having a slight viscosity. The dispersion may be used as it is, or the solvent may be distilled off, filtered, or dried to give a powder. The powder may be used as it is, or may be used as a dispersion with the above-mentioned dispersion medium each time it is used. In either case, a fine powder modified silk powder having an average particle diameter of 5 μm or less and a water or organic solvent dispersion of the powder can be obtained. The present invention is particularly useful for producing a smooth and uniform dispersion.

In the present invention, the method of applying the finely powdered modified silk powder to the cloth with the water or the organic solvent dispersion or the synthetic resin emulsion is not particularly limited, but the pad method, the spray method, and the roller are used. The law etc. can be applied. Further, in order to exhibit good adhesiveness and uniform film forming property of the fine powder modified silk powder to the cloth, the cloth is pretreated, for example, polyester fiber is treated with alkali, nylon fiber is treated with acid, or oxygen, The low temperature plasma treatment may be performed using an inorganic gas such as nitrogen, air or argon. The cloth to which the finely powdered modified silk powder is applied is dried, and further subjected to dry heat or wet heat treatment to form a strong film. The dry heat treatment is performed at 120 ° C. or higher, preferably 150 ° C. or higher, and the wet heat treatment is performed at 90 ° C. or higher, preferably 110 ° C. or higher. Then, you may wash with warm water as needed. By washing, a proper rubbing action is added, the adhesion between the fibers is relaxed, and the soft finish is improved.

[0022]

EXAMPLES Examples of the present invention will be described below. The parts shown in the examples mean parts by weight, and% other than the crystallinity means% by weight. The test method which is the basis of the numerical values in the examples is as follows. (1)

[Equation 1] (2) Texture KES Texture tester (Kato Iron Works Co., Ltd.)
Manufactured) and displayed as a hand value based on the standard for thin outerwear for women's outerwear. (3) Water absorption JIS L-1096A Drop method JIS L-1096B Byreck method (4) Washing test JIS L-0217 103 method

Example 1 Silk fibrin was used as a raw material for silk fibroin.
00 gr. Marcel soap 30 gr. , Water 3000g
r. Stirring and scouring at 95-98 ° 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. Calcium chloride (CaCl ₂ · 2H ₂ O)
100 gr. Water 100 gr. And a 38 wt% calcium chloride aqueous solution of 200 gr. Was prepared and heated to 110 ° C. To this, 40 gr. Was added with stirring using a kneader for 5 minutes, and then stirred for 30 minutes to completely dissolve it. Next, inner diameter 200μ, film thickness 2
20 μm of regenerated cellulose hollow fiber with 0μ and length of 500 mm
Using a hollow fiber type dialysis device in which 00 bundles are bundled and fixed at both ends without sealing the hollow holes (sealing), the above-mentioned dissolution liquid is caused to flow at a rate of 0.1 l / hour to deionize water. It dialyzed using and obtained the fibroin aqueous solution. The fibroin concentration of the aqueous fibroin solution was 6.5.
%, Residual calcium chloride was 0.001%. The obtained fibroin aqueous solution 500 gr. 100 / se
The mixture was stirred at high speed with a stirring blade so as to give a shear deformation rate of c or more. When stirring is continued for 2 to 3 hours, silk fibroin particles are precipitated next, and finally the whole aggregates as small aggregates of gel particles (15% crystallinity, 58% β structure) that solidify and separate from silk fibroin. Regenerate with a yield of almost 100%. Continue high-speed stirring, and then add 30% concentrated ammonium sulfate aqueous solution at about 40 gr. As a result of mixing and further stirring for 1 hour and subjecting the silk fibroin crystal to α → β conversion, the gel body was crushed into small particles. Then, the gel body was separated by filtration, washed with water and dried at 105 ° C. for 2 hours. As a result, 32 gr. A regenerated silk crushed product was obtained (crystallinity 49%, β structure ratio 100%). The coarse powder 30 gr. Of water or an organic solvent of 270 gr. The resulting mixture was wet-milled at room temperature for 24 hours with a 1-liter hard porcelain ball mill. A ball made of hard porcelain having a diameter of 3 mm was mixed in an amount of 500 ml. The aqueous dispersion of the finely powdered modified silk powder obtained by pulverization was a white emulsion and had a very smooth feel. As a result of measurement with a centrifugal sedimentation type particle size distribution measuring device (Shimadzu SA-CP3 type), the particle size distribution is 0.33 to 4.68μ,
The average particle size was 2.13μ. This one is this one
The 0% dispersion was placed in a graduated cylinder and allowed to stand for 1 week.
The separation of the water layer and the powder layer was not observed at all, and the dispersion state was very stable. 10 parts of a 10% aqueous dispersion of the above-mentioned fine powder modified silk powder and 1 part of Bondic 1610 (containing 40% solid content) manufactured by Dainippon Ink and Chemicals Co., Ltd. as a urethane resin emulsion were dispersed in water to make 100 parts in total. The polyester fabric (thin fabric) is dipped in the treatment liquid prepared so that the pick-up rate is 80%, pre-dried at 120 ° C, and the temperature is 110 ° C with a HT steamer, and the steam amount is 0.5 kg / c.
The treatment was carried out at m ² for 10 minutes. Next, Table 1 shows the rate of increase and the feel (hand value) of Example 1.

[Table 1] As shown in Table 1, the product obtained in Example 1 had little loss of the processing agent due to washing, and had a silky feel with a feeling of stiffness, firmness and crease.

Example 2 According to the same manner as in Example 1, 20 parts of a 10% organic solvent dispersion liquid of a fine powder modified silk powder obtained by wet ball milling for 24 hours while replacing water in the dispersion medium with an organic solvent is the same. Dip nylon pantyhose in a treatment solution prepared so that the total amount becomes 100 parts with an organic solvent, and pick up rate 4
It was squeezed to 0% and subjected to steaming treatment at 115 ° C. for 60 seconds with a steam setter. Next, Table 2 shows the weight increase rate and the feel (touch) of Example 2.

[Table 2]

Example 3 According to the same manner as in Example 1, raw cotton was prepared by refining raw silk,
It was immersed in an aqueous solution of sodium hydroxide having a concentration of 0.50 Mol / l at a liquid ratio of 1:20 and treated at 80 ° C. for 30 minutes. After the treatment, the embrittlement coarse powder obtained by washing with water and drying (crystallinity 45%, β
Structure rate 98%) 30 gr. According to the same manner as in Example 1, wet ball milling was performed with an aqueous medium to produce a dispersion of fine powdery embrittled silk. 20 parts of a 5% aqueous dispersion of the above-mentioned fine powder modified silk powder, Bonncoat R-3020 manufactured by Dainippon Ink and Co., Ltd. (solid content 45) as an acrylic resin emulsion.
%) 1 part is dispersed in water, and the block type N, N, N-
Distearylmethylaminopolyethylene glycol etherified polyester quaternary ammonium salt 10% solution 5% was added so that the total amount becomes 100 parts. Was pre-dried and heat-treated at 160 ° C. for 2 minutes. Next, Table 3 shows the weight gain, feel (touch) and water absorption of Example 3.

[Table 3] From Table 3, it is possible to obtain water absorption by adding a water absorbing compound to the modified silk powder dispersion.

Example 4 15 parts of 10% aqueous dispersion of fine powder modified silk powder,
3 parts of an acrylic acid copolymer (solid content 30%) consisting of polyoxyethylene (23 mol%), methacrylate (40 mol%), methacrylic acid (40 mol%), epoxy modified methacrylate (15 mol%) and water The polyester thin fabric is soaked in the working fluid prepared by mixing so that the total amount becomes 100 parts, the pickup is squeezed to 60% and pre-dried at 120 ° C, and the temperature is 110 ° C with an HT steamer.
The treatment was performed at kg / cm ² for 10 minutes. Next, Table 4 shows the rate of increase and the feeling of Example 4.

[Table 4] From Table 4, the product obtained in Example 4 was silky with less feeling of the processing agent falling off by washing and having a feeling of firmness, firmness, firmness and crease.

Example 5 20 parts of 10% aqueous dispersion of finely powdered modified silk powder,
Acrylic acid copolymer consisting of polyoxyethylene (23 mol%), methacrylate (40 mol%), methacrylic acid (40 mol%), N-hydroxyethylacrylamide (6 mol%), acrylamide (9 mol%) (solid 30%) 3% and 3 parts of water are mixed to prepare a total amount of 100 parts, and the polyester tricot is dipped in a working fluid, squeezed to 100% of the pickup, pre-dried at 120 ° C, and dry heat treated at 160 ° C for 2 minutes. I went. Next, Example 5
Table 5 shows the texture (feeling) and water absorbency.

[Table 5]

Example 6 15 parts of 10% aqueous dispersion of finely powdered modified silk powder,
Block Copolymerization of Propylene Oxide and Ethylene Oxide Bisulfite of urethane prepolymer consisting of polyether diol and hexamethylene diisocyanate 30
% Aqueous solution (2 parts), triethylamine (0.1 part) and water to prepare a total amount of 100 parts.
Preliminary drying was carried out at 20 ° C., and dry heat treatment was carried out at 160 ° C. for 2 minutes. Further, as Comparative Example 1, 15 parts of 10% aqueous dispersion of fine powder modified silk powder and 1 part of Bondic 1610 (solid content 40%) manufactured by Dainippon Ink and Chemicals Co., Ltd. as urethane resin emulsion were dispersed in water. A polyester thin fabric was treated in the same manner as in Example 6 by using the processing liquid prepared so that the total amount became 100 parts. Next, Example 6 and Comparative Example 1
Table 6 shows the texture (feeling) and water absorbency.

[Table 6] From Tables 5 and 6, the products obtained in Examples 5 and 6 were soft and showed silky feeling and water absorption.

Example 7 10% organic solvent dispersion liquid 2 of fine powder modified silk powder
0 parts, block copolymer of propylene oxide and ethylene oxide, 4 parts of 30% aqueous solution of bisulfite of urethane prepolymer consisting of polyether diol and hexamethylene diisocyanate, 0.1 parts of triethylamine and water are mixed to make 100 parts in total. The working fluid was prepared so that Dip polyester tricot in the processing liquid, squeeze it to 80% of the pick-up and predry it at 120 ° C, then 160 ° C.
Was subjected to dry heat treatment for 2 minutes. The polyester tricot treated as described above was further washed with hot water at 40 to 50 ° C. for hot water dehydration-drying. As Comparative Example 7, 20 parts of the same fine-powdered modified silk powder as in Example 7 in an organic solvent dispersion was added with water to make the total amount 100 parts, and the processing liquid was treated with polyester tricot in the same manner as in Example 7. Table 7 shows the texture (touch) and water absorption (dropping method) of Example 7 and Comparative Example 7.
Indicates.

[Table 7]

[0030]

INDUSTRIAL APPLICABILITY The present invention improves the crystallinity of natural silk by a recrystallization method or an embrittlement method so that the crystallinity is 1/2 or less of that of natural silk. By improving the affinity with the substance and making the powder structure porous, it is effective in improving the pulverizability and reducing the apparent density. As a result, unlike the case of natural silk, it can be extremely easily finely pulverized to 5 μm or less by wet pulverization with a ball mill, and the dispersibility and dispersion stability of the obtained dispersion liquid are very good. It is applied to processing, and as a special texture processing, a product with a preferable silk touch feel is obtained. Furthermore, the present invention is applied to the fiber processing of the fine powder modified silk powder, and at the same time the effect of fixing the fine powder modified silk powder to the fabric by the addition of the water-soluble polymer is obtained. Can be given,
Moreover, it is possible to provide a fabric having both excellent adhesiveness and water absorbency and excellent wash durability.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Office reference number FI technical display location D06M 101: 16 (72) Inventor Kiyoshi Otoi 3-3-9 Aoyamadai, Suita City, Osaka Prefecture (72) ) Inventor Toshihiro Iguro 1-39 Kanebocho, Nagahama City, Shiga Prefecture

Claims (3)

[Claims] 1. The crystallinity of the fiber surface is 1/2 of that of natural silk yarn.
The finely powdered modified silk powder modified to have a volume average particle diameter of 5 μm or less is 0.05 to the cloth weight.
A specially textured fabric with 5.0% adhesion. 2. A water or organic solvent dispersion or synthetic resin emulsion of fine powder modified silk powder having a crystallinity modified to ½ or less of that of natural silk and having a volume average particle size of 5 μm or less. A method for producing a fine powdery modified silk powder-fixed cloth, which comprises applying the added liquid to the cloth and subjecting it to dry heat or wet heat treatment. 3. A water-soluble polymer polymer in a water or organic solvent dispersion of fine powder modified silk powder having a crystallinity of ½ or less that of natural silk and a volume average particle diameter of 5 μm or less. A process for producing a finely powdered modified silk powder-fixed fabric, which comprises applying a working fluid to which coalescing is added to the fabric and subjecting it to dry heat or wet heat treatment.