JPH0571073A - Silk fibroin-high water absorbing resin processed fabric and its production - Google Patents

Abstract

PURPOSE:To easily and efficiently obtain processed fabric with scroopy feeling specified to silk, exhibiting moisture absorption and releasing properties close to silk and having increased tension and resilience feeling by forming a specified amount of film composed of silk fibroin and high water absorbing resin on the surface of the fabric. CONSTITUTION:A mixed solution obtained by dissolving a high water absorbing resin in an aqueous solution of silk fibroin is applied to the surface of fabric composed of natural fiber, semi-synthetic fiber or synthetic fiber, etc., by Pad method or spraying, etc., then dried and thermally treated in moisture to form 0.1-10wt.%, preferably 0.2-5.0wt.% film based on the fabric weight. Performance close to silk such as moisture absorption and releasing of fiber surface, hand and gloss are exhibited and these properties lead to excellent washing resistance. An acrylic graft copolymer of silk fibroin is preferable as the high water absorbing resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silk fibroin-superabsorbent resin processed cloth which has silk luster, texture, repulsion and hygroscopicity and is excellent in durability of those properties, and a method for producing the same.

[0002]

2. Description of the Related Art Silk has a quiet deep luster, a soft texture,
It has a unique lofty, elegant dignity that is unmatched by other fibers, such as graceful drape, and is highly regarded as the top material among fibers. Therefore, many processing methods for imparting silk characteristics to fibers other than silk have been proposed. For example, polyester fibers are treated with an alkali to reduce the weight to give a softer feel, and cellulosic fibers are reduced with an enzyme to give a softer finish.For rayon and cotton, urethane resin and silicone are used to improve resilience and softness. Methods such as applying a resin or adding an amino acid-based resin in order to express a tingling sensation have 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 dispersion of silk fibroin powder has been proposed, but there is a problem that the stability of the solution and the durability after the treatment are poor. That is, it has been difficult to develop the original luster, feel, repulsion and hygroscopicity of silk in ordinary fiber processing, and it has not been found yet.

[0003]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention The present inventors have completed the present invention as a result of diligent research on the physical properties and feel of silk and focusing on silk fibroin. The object of the present invention is to use a silk fibroin in combination with a highly water-absorbent resin, whereby a fabric having excellent moisture absorption and moisture release properties on the surface and having a texture and luster close to that of silk and excellent durability of those properties. To provide. Another object is to provide a method for producing such a fabric industrially easily and inexpensively.

[0004]

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 silk fibroin-superabsorbent resin on the fiber surface, and the amount of the film deposited is 0.1 to 10% by weight based on the weight of the cloth. The gist of the present invention is silk fibroin-superabsorbent resin-treated cloth, and the second invention is to dissolve the superabsorbent resin in an aqueous silk fibroin solution, apply the resulting mixed aqueous solution to the cloth, and then dry and wet heat treat it. The gist is a method for producing a silk-fibroin-superabsorbent resin-processed fabric, which is characterized in that

The present invention will be described in detail below. In the present invention, cloth means cotton, rayon, cellulose fiber such as hemp,
Examples include semi-synthetic fibers such as acetate and triacetate, synthetic fibers such as polyester, nylon and acrylic, and mixed fibers of various fibers, woven fabrics, knitted fabrics and non-woven fabrics, and polyamide fibers such as nylon that are difficult to modify by ordinary processing methods. The effect of the present invention is particularly great in the fabric using.

In the present invention, the super absorbent polymer is roughly classified into starch type, protein type, cellulose type and synthetic polymer type, and starch type, protein type and cellulose type are respectively graft polymerization type and carboxymethylation type. (CM
Divide into the system. The synthetic polymer type is acrylic type,
Examples include Poval type, acrylamide type, and polyoxyethylene (PEO) type. In the super absorbent polymer, an acrylic acid graft polymer of fibroin is particularly preferable.

The silk-fibroin-superabsorbent resin processed fabric of the present invention covers the fiber surface with a silk-fibroin-superabsorbent resin film. However, considering the flexibility and the feel of the fiber, the silk-fibroin-superabsorbent resin The adhered amount is at most 10% by weight, usually 0.1 to 10.0% by weight, and preferably 0.2 to 5.0% by weight with respect to the cloth. The thickness of the film is usually 0.01 to 10 μm. The ratio of the silk fibroin component to the super absorbent polymer component of the present invention is at least 1 in consideration of the texture of the processed fabric.
It is necessary to mix 0% by weight, especially at least 3
It is preferably 0% by weight, especially 50% by weight or more. The super absorbent polymer component is preferably at least 10% by weight, particularly preferably 20% by weight or more. The ratio of the silk fibroin component and the superabsorbent resin component can be appropriately determined depending on the desired quality such as feeling or durability, but usually the silk fibroin component is 50 to 80.
Those having a weight percentage of 20% to 50% by weight and a super absorbent polymer component are used.

The solvent of silk fibroin applied to the present invention is the solvent described in Japanese Patent Publication No. 58-38449.
For example, copper-ethylenediamine aqueous solution, copper 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 Examples thereof include an aqueous solution and an aqueous solution of sodium thiocyanate, but calcium or magnesium hydrochloride or nitrate is preferable from the viewpoint of cost and use. In addition, silk fibroin is obtained by refining silk waste fibers by-produced in a raw silk factory or a silk spinning factory with Marcel soap and soda ash by a usual method to obtain 1% by weight of residual sericin.
The following applies. The concentration of silk fibroin in the silk fibroin aqueous solution is usually 0.5 to 20% by weight, and particularly preferably 1.0 to 10.0% by weight, although it varies depending on the kind of solvent and the amount of the solvent.

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

In the method of the present invention, the method of applying the silk fibroin and the aqueous superabsorbent resin solution to the cloth is not particularly limited, but a pad method, a spray method, a roller method and the like can be applied.

Further, in order to develop good adhesion and uniform film-forming property of silk fibroin and super absorbent resin to the cloth, the cloth is pretreated, for example, polyester fiber is treated with alkali, nylon fiber is treated with acid or oxygen, nitrogen,
The low temperature plasma treatment may be performed in a system such as air or argon.

The cloth to which the silk fibroin-superabsorbent resin is applied can be dried and subjected to wet heat treatment to form a strong film. And the moist heat treatment is 90
C. or higher, preferably 110.degree. C. or higher. For this reason, it is preferable to use superheated steam for the moist heat treatment.
Treatment at 120 to 180 ° C. for 10 seconds to 30 minutes is preferable.

The silk-fibroin-superabsorbent resin-processed fabric of the present invention has a uniform thin film enclosing the fibers, and the silk-fibroin-superabsorbent resin film is no longer soluble in water and has washing resistance. Is. The silk fibroin-superabsorbent resin aqueous solution applied to the present invention stabilizes the silk fibroin solution, that is, heterologous proteins such as atelocollagen and hydrolyzed collagen in order to prevent gum up.
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-forming property is poor and the texture becomes coarse and hard. Furthermore, the silk fibroin-superabsorbent resin aqueous solution applied to the present invention is a softener, an antistatic agent,
Preservatives, toning agents, stabilizers, reaction catalysts and the like may be contained as necessary.

[0014]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, all parts are parts by weight. The test method which is the basis of the numerical values in the examples is as follows. (2) Texture KES (manufactured by Kato Iron Works Co., Ltd.) measured with a texture tester. (Displayed as a hand value on the basis of thin fabric for women's outerwear) (3) Water absorption test (I) Drop method JIS L-1096 A method (II) Bayrek method JIS L-1096 B method (4) Antistatic property Test (I) Friction electrification voltage JIS L-1094 B method (II) Half-life JIS L-1094 A method (measured at 20 ° C. ± 40% RH) (5) Contact cold temperature sensation KES-F7 manufactured by Kato Tech Co., Ltd. Measured with a precision rapid thermal measurement device. (THERMO LABO II TYPE) (I) Contact cold / hot sensation: qmax The contact cold / hot sensation indicates the warmth or coldness of the moment you touch it. It is represented by. (II) Thermal conductivity: K (6) Whiteness Measured with a Macbeth II type colorimeter and measured by reflectance at 450 nm. (7) Sensitivity test of feeling According to the following, averaged after judgment by 5 judges. 5: Significant change compared to unprocessed. 4: It changed compared with unprocessed. 3: Intermediate change between 2 and 4. 2: Slight change from unprocessed. 1: No change from raw.

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

The acrylic acid graft polymer of fibroin, which is one of the super absorbent resins used in this example, was prepared by the following method shown in Example 1 of JP-B-58-57974. That is, 1 kg of raw silk waste was immersed in 30 l of a 1% by weight aqueous solution of Marcel soap and treated at 98 ° C. for 3 hours to substantially remove sericin and oil. 65% by weight
2 kg of calcium nitrate aqueous solution and ethyl alcohol of 0.
0.5 kg of raw silk scraps after the scouring was added to 5 kg, and
The mixture was stirred and dissolved at 0 to 75 ° C for 1 hour. Then, 2 kg of hot water at 70 ° C. was mixed and diluted, and after cooling, desalted by a hollow fiber type dialysis device. A reaction solution was prepared so that the ratio of fibroin and acrylic acid was 5:95 in terms of solid content and the total amount of both solid content was 10% by weight. 100 g of the reaction solution was charged into a reaction vessel equipped with a stir bar, a nitrogen blowing tube, and a thermometer, 20 mg of ammonium persulfate was added under a nitrogen stream, and the temperature was raised from 25 ° C to 80 ° C over 1 hour and then 80 ° C.
The reaction was allowed to continue for 1 hour. After neutralizing the obtained viscous reaction solution with an aqueous sodium hydroxide solution,
It was dried under reduced pressure for an hour and then ground to obtain a powder having a particle size of 5 to 30 μm.

Examples 1-A, 1-B The following pantyhose were knitted, and then dyed and fixed by a commonly known method. Panty hose (support type) Leg part (20 x 13 x 13 DCY) x 13d / 3f raw yarn Panty part (20 x 30 POY) x 30d / 8f Woolly yarn Toe part 13d / 3f raw yarn x 30d / 8f Woolly yarn x
70d / 18f Woolly yarn Next, it was dipped in the treatment aqueous solution (A) or (B) shown below, and centrifugally dehydrated at a pickup rate of 15%. Then, after drying at a temperature of 90 ° C. for 10 seconds, 115
A steam set was performed by moist heat at 10 ° C. for 10 seconds in a mold. Treatment liquid (A) 5.0 wt% fibroin solution 25 wt% 4.0 wt% Acrylic acid graft polymer aqueous solution of fibroin 2.5 wt% Treatment liquid (B) 5.0 wt% fibroin solution 25 wt% 4. Acrylic acid graft polymer aqueous solution of 0% by weight fibroin 5% by weight

Comparative Examples 1-A and 1-B The same processing as in Example 1 was carried out without adding the acrylic acid graft polymer of fibroin. Comparative Examples 2-A, 2-B In the same treatment as in Example 1, processing was performed without adding the fibroin solution. Table 1 shows the durability, water absorption, antistatic property, and thermophysical property values of the products obtained in Example 1 and Comparative Examples 1 and 2.
~ Shown in Table 3.

[0019]

[Table 1]

[0020]

[Table 2]

[0021]

[Table 3]

As is clear from Tables 1 to 3, by blending silk fibroin with a highly water-absorbent resin, the washing durability is improved, the water absorbency and the antistatic property are good, and the touch feeling is closer to that of silk. I understand.

Examples 2-A and 2-B 36 denier / 18 filaments of bright cross section of triangular filament 6 nylon fibers were knitted in half gauge in 36 gauge. This is usually scoured / bleached by a known method.
After heat setting and dyeing with an acid dye, a fixing treatment with tannic acid was performed to obtain a nylon half tricot for inner use. Next, after padding with the treatment liquids (A) and (B) shown below at a pick-up rate of 80%, and drying at a temperature of 130 ° C. for 45 seconds
At a temperature of 150 ° C., a heat treatment was performed with superheated steam for 8 minutes using a high ten parachar, steamer manufactured by Arioli Co., Ltd., and a final set was performed at a temperature of 160 ° C. for 1 minute. Treatment liquid (A) 5.0% by weight fibroin solution 20% by weight 4.0% by weight Fibroin acrylic acid graft polymer 2.5% by weight Treatment liquid (B) 5.0% by weight fibroin solution 30% by weight 4.0 % By weight Fibroin acrylic acid graft polymer 3.0% by weight

Comparative Examples 3-A and 3-B In the same manner as in Example 2, processing was carried out without adding the acrylic acid graft polymer of fibroin. Comparative Example 4-A, 4-B In the same treatment as in Example 2, the acrylic urethane graft polymer of fibroin was not added, but the reactive urethane shown below was added for processing. Elastron MF-9 3% by weight (urethane prepolymer of end-blocked isocyanate manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) Elastron Catharis 64 0.25% by weight (fatty acid metal salt urethane of Dai-ichi Kogyo Seiyaku Co., Ltd.) Catalyst) Tables 4 to 7 show the durability, water absorption, antistatic property, thermophysical property, and feel of the products obtained in Example 2 and Comparative Examples 3 to 4.

[0025]

[Table 4]

[0026]

[Table 5]

[0027]

[Table 6]

[0028]

[Table 7]

[0029]

INDUSTRIAL APPLICABILITY The silk fibroin-superabsorbent resin-processed fabric of the present invention has a low moisture-adsorption ratio and moisture-releasing property on the surface, even though it has a low adhesion rate, and feels warm to the touch. It has a texture and luster closer to silk. Furthermore, the tension and waist are increased, and the squeaky feeling peculiar to silk is obtained, the performance is close to that of silk, more than silk is obtained in terms of antistatic property, and these physical properties are excellent in washing durability. There is. The production method of the present invention can industrially easily and efficiently process such a fabric, and its usefulness is clear.

Claims (2)

[Claims] 1. A silk fibroin-a cloth having a film made of a highly water-absorbent resin on a fiber surface, wherein the amount of the film adhered is 0.1 to 10% by weight based on the weight of the cloth. Super absorbent resin processed fabric. 2. A superabsorbent resin is dissolved in an aqueous silk fibroin solution, and the resulting mixed aqueous solution is applied to a cloth and then dried.
A method for producing a silk fibroin-superabsorbent resin-processed cloth, which is characterized by performing a wet heat treatment.