JPH0816309B2 - Fabric having silk texture and method for manufacturing the same - Google Patents

Description

TECHNICAL FIELD The present invention relates to a fabric having a silk texture and a method for producing the same.

(Conventional technology) Silk fiber has a deep luster, tension, soft texture with a feeling of waist, squeaky feeling, graceful drape, high hygroscopicity, etc. Is to have
It is highly evaluated as a top material among fibers.

Therefore, many processing methods have been proposed for imparting silk characteristics to fibers other than silk. For example, polyester fiber is reduced by alkali treatment to finish the texture softly, and cellulosic fiber is reduced by cellulase enzyme to be flexible, and rayon, cotton, and polyamide fiber are used to improve resilience and softness. Various proposals have been made, such as adding a resin or silicone resin, or attaching a natural polymer such as amino acid, gelatin, or casein to give a tingling sensation, or a durable modification method by graft-reacting a monomer. ing. Regarding 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 of them are inferior in terms of appearance effect or durability.

On the other hand, treatment with an aqueous dispersion of silk fibroin protein 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 is difficult to develop the original luster, feel, repulsion and hygroscopicity of silk in ordinary fiber processing, and it has not been found yet.

(Problems to be Solved by the Invention) The present inventors have completed the present invention as a result of earnestly studying the physical properties and feel of silk, paying attention to silk fibroin, and pursuing the durability of the fibroin film.

An object of the present invention is to provide a cloth having silk luster, texture, repulsion and hygroscopicity, and excellent in durability of those properties. Another object is to provide a method for producing such a fabric industrially easily and inexpensively.

(Means for Solving the Problems) In order to achieve the above object, the present invention has the following configuration. That is, the first invention is a cloth having a film composed of silk fibroin, at least one kind selected from heterogeneous proteins having a molecular weight of 100,000 or more, and glutamic acid on the fiber surface, and the amount of the film attached is the weight of the cloth. Against 0.
The gist is a cloth having a silk texture that occupies from 05 to 7.5% by weight, and the second invention is to dissolve at least one kind of heterologous protein having a molecular weight of 100,000 or more and glutamic acid in an aqueous solution of silk fibroin. The gist of the present invention is to provide a method for producing a fabric having a silk texture, which comprises subjecting the obtained mixed aqueous solution to a fabric and subjecting the fabric to a wet heat treatment.

 The present invention will be described in detail below.

In the present invention, the cloth includes cotton, rayon, cellulose fibers such as hemp, 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. For example, a cloth using polyamide fiber such as nylon, which is difficult to be modified by a usual processing method, is particularly effective in the present invention.

The silk fibroin referred to in the present invention means a copper-ethylenediamine aqueous solution, a copper hydroxide-ammonia aqueous solution (Schweiser reagent), a copper hydroxide-alkali-glycerin aqueous solution (Lohe reagent), a lithium bromide aqueous solution, calcium or magnesium or zinc hydrochloric acid. A fibroin solution obtained by dissolving fibroin in at least one solvent selected from the group consisting of an aqueous solution of salt, nitrate or thiocyanate and an aqueous solution of sodium thiocyanate is prepared. Is prepared by dealkalization and desalting by membrane separation using a multi-layer membrane structure or a hollow fiber focusing structure satisfying the conditions, and the solvent is calcium or magnesium hydrochloride in terms of cost and use. Alternatively, nitrate is preferable.

The silk fibroin is obtained by scouring silk waste fibers by-produced at a raw silk factory or a silk spinning factory by a usual method using Marcel soap and soda ash, and applying residual sericin to 1% by weight or less.

The concentration of silk fibroin in the silk fibroin aqueous solution is usually 0.5 to 20% by weight, though it varies depending on the type of solvent and the amount of deposition.
Particularly, 1.0 to 10.0% by weight is suitable.

The heterologous protein having a molecular weight of 100,000 or more in the present invention is to improve the texture and the like by interacting with silk fibroin, and has a stabilizing action against mechanical shear stress of the fibroin aqueous solution, for example, atelocollagen, Examples thereof include gelatin and casein.

The glutamic acid used in the present invention does not stabilize the mechanical shear stress of the aqueous fibroin solution, but improves the adhesiveness by the interaction between the silk fibroin and the heterologous protein having a molecular weight of 100,000 or more.

The fabric having the silk texture of the present invention is silk fibroin-
Heterologous protein (molecular weight of 100,000 or more) -The fiber surface is covered with a glutamic acid film, but considering the flexibility and feel of the fiber, the film adhesion amount is at most 7.5% by weight of the cloth, usually 0.05 to 7.5% by weight. , Preferably 0.2-3.0% by weight
Is. The thickness of the film is usually 0.01 to 2.0μ.

Further, the ratio of the silk fibroin component of the present invention: the heterologous protein having a molecular weight of 100,000 or more and the glutamic acid component, it is necessary to mix at least 10% by weight of the silk fibroin component in consideration of the texture of the processed fabric, and particularly at least It is preferably 20% by weight, especially 30% by weight or more. The heterologous protein having a molecular weight of 100,000 or more and the glutamic acid component are preferably at least 10% by weight, particularly preferably 30% by weight or more. Silk fibroin component: The ratio of the heterologous protein having a molecular weight of 100,000 or more and the glutamic acid component can be appropriately determined depending on the desired quality such as texture or durability, but usually 20 to 80% by weight of the silk fibroin component, a heterogeneous protein having a molecular weight of 100,000 or more The glutamic acid component used is 20 to 80% by weight. Further, the ratio of the heterologous protein having a molecular weight of 100,000 or more and glutamic acid can be appropriately determined depending on the desired quality such as feeling or durability, but usually the heterologous protein having a molecular weight of 100,000 or more is 20 to 80% by weight, and the glutamic acid is 20 to 80% by weight. Used.

In the method of the present invention, the method for applying silk fibroin-a heterogeneous protein having a molecular weight of 100,000 or more-glutamic acid mixed aqueous solution to the fabric is not particularly limited, but a pad method, a spray method, a roller method, an immersion-centrifugal dehydration method, etc. may be applied. You can

The silk fibroin-a heterogeneous protein having a molecular weight of 100,000 or more-a cloth to which glutamic acid is added is dried at a temperature of 100 to 150 ° C for 5 to 30 seconds without drying or with a normal drying device, and then at a temperature of 80 ° C. Wet heat treatment is performed at ˜150 ° C. for 5 seconds to 10 minutes.

The silk fibroin-heterologous protein having a molecular weight of 100,000 or more-glutamic acid-treated cloth of the present invention has a uniform thin film encapsulating the fiber, and this film is no longer dissolved in water and is wash-resistant.

In order to further improve durability in the present invention, it acts on silk fibroin and a heterologous protein having a molecular weight of 100,000 or more,
Natural and synthetic ascorbic acid which promotes crystallization, insolubilizes and improves adhesion may be used. The amount of ascorbic acid used is preferably 5 to 15% by weight based on silk fibroin-a heterologous protein having a molecular weight of 100,000 or more-glutamic acid.

(Examples) Next, the present invention will be described 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) Adhesion rate (2) Washing test JIS L-0217 103 method (3) Water absorption test (i) Dripping method According to JIS L-1096 A method (4 layers) (ii) Bylek method JIS L-1096 B method (4) Control Electrical test (i) Friction electrification voltage Complies with JIS L-1094 B method (4 sheets stacked) (ii) Half-life according to JIS L-1094 A method (4 sheets stacked) (Measured at 20 ° C ± 40% RH (5) Contact cold temperature sensitivity Measured with a KES-F7 precision rapid thermal property measuring device manufactured by Kato Tech Co., Ltd.

(THERMO LABO II TYPE) (i) Contact cold / hot sensation: qmax The contact cold / hot sensation represents the warmth or coldness of the moment you touch it, and those that feel cold when you touch it are large numbers.
Things that feel warm are represented by small numbers.

(Ii) Thermal conductivity: K (6) Feeling The results were averaged after judgment by 5 judges according to the following.

5: Greatly changed compared to unprocessed.

4: Change compared to unprocessed.

3: Change between 2 and 4.

2: A little different from raw.

1: Same as raw.

Example 1 First, using silk spinning waste as a raw material for silk fibroin,
9 parts of 100 parts of this with a solution of 30 parts of Marcel soap and 3000 parts of water
The mixture was stirred and scoured at 5 to 98 ° C for 3 hours to reduce the residual glue to 0.1% or less, washed with water and dried at 80 ° C with hot air.

66 parts of calcium chloride (CaCl ₂ .2H ₂ O) was mixed with 34 parts of water, 100 parts of 50% calcium chloride aqueous solution was prepared, 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, 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. After sealing both ends, the salt concentration was reduced to 0.1% or less in running water for 15 to 25 hours. It was

Desalted dialysate has a silk fibroin concentration of 5.5% by weight
It is a degree. This was diluted with hot water to prepare a 5% by weight colloidal solution of silk fibroin.

On the other hand, after knitting the pantyhose below,
Staining and fixing treatment were performed by a commonly known method.

Panty hose (support type) Leg part (20 x 13 x 13 DCY) x 13d / 3f raw thread Panty part (20 x 30POY) x 30d / 8f Woolly thread Toe part (13d / 3f raw thread x 30d / 8f Woolly thread x 70d / 18f Woolly thread Next, after dipping in the treatment liquid (A) or (B) shown below,
Centrifugal dehydration was performed at a pickup rate of 15%. Then, after drying for 10 seconds at a temperature of 90 ° C, 1 ° C at 115 ° C
A steam set was carried out by placing the mold in a mold at a wet temperature for 0 seconds.

Treatment liquid (A) Treatment liquid (B) The physical properties of the obtained processed cloth are shown in Tables 1 to 3.

(Comparative Example 1) Processing was carried out in the same manner as in Example 1 without adding casein.

 The physical properties of the obtained processed cloth are shown in Tables 1 to 3.

(Comparative Example 2) In the same treatment as in Example 1, processing was performed without adding glutamic acid.

 The physical properties of the obtained processed cloth are shown in Tables 1 to 3.

As is clear from Tables 1 to 3, it is understood that the washing durability is dramatically improved by mixing silk fibroin with at least one kind selected from heterogeneous proteins having a molecular weight of 100,000 or more and glutamic acid. It can be seen that further improvement is achieved by mixing ascorbic acid.

(Effects of the Invention) As described in detail above, the silk fibroin of the present invention-a heterologous protein having a molecular weight of 100,000 or more-a glutamic acid-treated cloth has silk texture and luster, and further increases tension and luster, and silk. A peculiar squeaky feeling is also obtained, the absorption of moisture on the surface and the release of moisture are similar to silk, and the feeling of touch when touched is warm. It also exhibits excellent washing resistance. Further, the method of the present invention can efficiently process such a cloth, and its usefulness is clear.

Claims (2)

[Claims] 1. A silk fibroin having a molecular weight of 10 on the fiber surface.
A fabric having a film consisting of at least one selected from over 10,000 different proteins and glutamic acid,
The amount of the above coating is 0.05 to 7.5% by weight based on the weight of the fabric.
A fabric with a silky texture that occupies. 2. A silk wind characterized by dissolving at least one kind of a heterologous protein having a molecular weight of 100,000 or more and glutamic acid in an aqueous silk fibroin solution, applying the resulting mixed aqueous solution to a cloth, and subjecting the cloth to wet heat treatment. A method of manufacturing a fabric having a combination.