JPH04197627A - Material for cloth - Google Patents

Abstract

PURPOSE:To obtain a porous film which has a uniform void hole distribution and is superior in moisture permeability, by a method wherein starch within a polymer film containing the starch is removed by a simple method under a gentle condition by operation of an amylolytic enzyme. CONSTITUTION:Either starch is removed by performing hydrolysis-extraction by bringing a polymer/starch film into contact with an aqueous solution of an amylolytic enzyme or the starch is removed by performing the hydrolysis- extraction by bringing polymer/starch film made by mixing a polymer with starch and the amylolytic enzyme into contact with water, through which a porous polymer film is obtained. A material for cloths is comprised of processed cloth comprised by integrating the porous polymer film with the cloth. The processed clot contains not only a matter where the porous polymer film and cloth are laminated for integration but also a matter where the porous polymer film is integrated as a coating by applying the same to the cloth and a matter where the porous polymer film is integrated as an impregnated layer of the cloth and the processed cloth superior in moisture permeability and strength is obtained.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to a clothing material with excellent moisture permeability and waterproof properties, which is used as fabric for sportswear, raincoats, work clothes, surgical gowns, etc. .

[Conventional technology]

Clothing materials that have both waterproof properties that do not let water such as rain pass through, and moisture permeability that do not get stuffy even when you are wearing them, include materials that are made by laminating cloth and porous films obtained by stretching fluorocarbon resin films, and ultrafine fibers. High-density fabrics using hydrophilic polymers, fabrics coated with hydrophilic polymers, coatings formed on the surface of the base fabric, or films laminated with the base fabric that are foamed using a foaming agent to make them porous. Are known.

[Problems to be Solved by the Present Invention] Among the above-mentioned prior art, certain waterproof-transparent '12 te
Although there are some materials that are highly functional and have been put into practical use, they are generally expensive, and on the other hand, inexpensive materials do not have sufficient waterproofing and moisture permeability. It had drawbacks such as a complicated manufacturing method and variations in quality.

An object of the present invention is to provide a material for clothing that has excellent waterproofing and moisture permeability and is inexpensive.

[Means to achieve the purpose]

The present inventors have discovered that a porous film with a uniform pore distribution can be obtained by removing starch in a starch-containing polymer film using a simple method under mild conditions through the action of an amylolytic enzyme. The present invention was achieved by discovering that the film has excellent thermal permeability.

That is, the present invention is a clothing material made of a processed fabric made by integrating a porous polymer film and cloth, the porous polymer film being a polymer/starch film formed by forming a mixture of polymer and starch into a film shape. , relates to a clothing material characterized in that it is obtained by removing starch from the polymer/starch film using an amylolytic enzyme to generate pores.

In the present invention, the polymer refers to a synthetic polymer compound obtained by vinyl polymerization, polycondensation, addition condensation, or other known methods, and includes both thermoplastic resins and thermosetting resins, and the form of the polymer is as follows: Either a lump, a solution or dispersion in an organic solvent or water may be used. The production method of the present invention tends to exhibit its characteristics when applied to polymers having a hydrolyzable bond, such as an ester bond or an amide bond, in the molecule. Therefore, the polymers to which the production method of the present invention can be applied include polyurethane, polyester, polyamide, polycarbonate, fluoropolymers, vinyl ester polymers, as well as vinyl monomers mainly including acrylic esters and methacrylic esters. lump, solution,
Acrylic polymers obtained by polymerization in a suspended or emulsified state are preferred. The form of the polymer is preferably an aqueous solution or emulsion because it can be easily mixed with starch. The most preferred polymers in the present invention are acrylic emulsions and polyurethane emulsions.

The starch used in the present invention is not particularly limited, and known starches such as those obtained from rice, adlay, wheat, corn, sweet potato, potato, arrowroot, adzuki bean, lotus, buckwheat, millet, etc. can be used. Further, these starches may be processed by partial decomposition, cationization, etc. Since the pore size of the resulting porous polymer film depends on the particle size of the starch used, the starch is appropriately selected and used depending on the required performance of the porous polymer film. However, if starch does not need to be completely decomposed and removed, or if a certain amount of starch needs to remain in the porous film, starch with a particle size larger than the desired pore size is used. For example, the relationship between starch type and pore size is as follows. Potato starch:
About 15-20 microns, corn starch; 8-12 microns, rice starch; 1-10 microns, soluble starch; 1-1000 angstroms.

The ratio of polymer to starch used is determined by the number of pores required in the porous polymer film. - Numerically, the polymer/starch solids weight ratio is from 100/1 to
It is in the range of 100/200, and from the viewpoint of the strength and performance of the obtained film, it is preferably in the range of 100/10 to 100/100. Starch is in powder form,
It may be in the form of a paste, a dispersion liquid, or an aqueous solution. When used in the form of a paste or a dispersion, the solvent can be water or an organic solvent.

There are various amylases as starch degrading enzymes in the present invention, and specific examples include α-amylase, β-amylase,
-Amylase, isoamylase, pullulase, glucoamylase, etc.

Among them, it is particularly preferable to use glucoamylase because it can efficiently remove starch under mild conditions.

In the present invention, a porous polymer film is obtained by removing starch from a polymer/starch film using an amylolytic enzyme, and the following two methods are typical methods for carrying out this process. I can do it.

■ A method in which a polymer/starch film is brought into contact with an aqueous solution of an amylolytic enzyme to hydrolyze-extract and remove starch.

(2) A method in which starch and an amylolytic enzyme are mixed into a polymer to form a polymer/starch film, and the film is brought into contact with water to remove the starch by hydrolysis and extraction.

In method (2), a specific example of a method of bringing the polymer/starch film into contact with the amylolytic enzyme aqueous solution is, for example, by applying an aqueous enzyme solution to the film using a roll coater.
There are methods of applying the film using a spray, curtain coater, etc., or immersing the film in an enzyme aqueous solution bath for a certain period of time, and cleaning with a detergent solution if necessary, but the immersion method is the most effective.

Further, the concentration of the amylolytic enzyme aqueous solution is in the range of 0.1 to 100g #2, preferably 0.5g of amylolytic enzyme #2.
~10gIQ.

The temperature at which the polymer/starch film is brought into contact with the amylolytic enzyme aqueous solution can be in the range of 10 to 100°C, preferably in the range of 40 to 80°C, particularly preferably in the range of 60 to 70°C. Further, the contact time may be determined so that the degree of decomposition and extraction of starch is as desired, and is in the range of 10 minutes to 72 hours, preferably 1 to 48 hours. . −−■
When using the method, the ratio of starch and amylolytic enzyme used is starch/amylolytic enzyme = 10010.1 ~
In the range of 100/20, preferably from 100/1 to 100/
The range is 10. Polymer containing starch degrading enzyme/
Methods for bringing the starch film into contact with water include applying water to the film using a roll coater, spray, curtain coater, etc., immersing the film in water, and further bringing the film into contact with water vapor. There is a method of keeping the film in a moist state, such as by letting it dry or placing it under high humidity. The temperature and time of contact with water are the same as those in method (2). Further, after contacting with water, cleaning with a cleaning liquid may be performed.

In both (1) and (2), it is desirable to adjust the pH of the starch decomposing enzyme aqueous solution or water to a range where the starch decomposition reaction is most accelerated using a buffer solution or the like. Additionally, additives such as penetrants that improve the efficiency of decomposition and extraction may be used.

The clothing material of the present invention is a processed fabric made by integrating the porous polymer film obtained as described above and fabric. The processed fabric does not only refer to a fabric in which a porous polymer film and a cloth are laminated and integrated. It also includes those in which the polymer film is integrated as an impregnated layer of the fabric.

In the production of these processed fabrics, in the case of lamination, the step of removing starch from the polymer/starch film to form a porous polymer film may be performed before laminating the polymer/starch film and the fabric, or after lamination. You may go. In the case of a coating or an impregnated layer, the polymer/starch film is preferably formed as a coating on cloth or an impregnated layer on cloth, and then the starch is removed to form a porous polymer film.

The thickness of the porous polymer film (including in the form of a coating or impregnated layer) can range from 1 micron to 1 millimeter, more preferably from 5 microns to 100 microns.

Further, if necessary, the porous polymer film layer may contain an antifungal agent, a preservative, a bactericidal agent, an ultraviolet absorber, a deodorizing agent, an aromatic agent, and the like.

The cloth used in the present invention is not particularly limited (
The material may be appropriately selected from woven fabrics, nonwoven fabrics, and knitted fabrics such as , nylon, polyester, rayon, acrylic, cotton, and wool.

[Effect of the invention] The porous polymer film layer formed by the unique method described above has pores with a pore size set within a desired range uniformly distributed, and some residual starch. It has excellent moisture permeability due to its supposed hydrophilic properties. or,
A porous polymer film can be formed by processing under mild conditions rather than harsh conditions (temperature, chemicals used, etc.) that can degrade the fabric or the film-forming polymer, resulting in strong processed fabrics. can be obtained.Also,
It can be manufactured at low cost.

Therefore, the clothing material of the present invention can be used as a material for sportswear such as ski wear, medical clothing such as raincoats, work clothes, and surgical gowns.

(Example) The present invention will be explained in more detail in the following example.
The present invention is not limited by the examples, and
Unless otherwise specified, parts are parts by weight and percentages are percentages by weight.

Example 1 (Preparation of polymer/starch film) Acryset@
3 parts of rice starch was added to 10 parts of 204E (manufactured by Nippon Shokubai Kagaku Kogyo ■, acrylic emulsion, solid content 49%) to obtain a homogeneous mixture. Applying the mixture to release paper,
After drying at room temperature, the release paper was removed to obtain a film with a thickness of about 50 μm.

(Preparation of starch degrading enzyme aqueous solution) AM G (manufactured by NOVOINDUSTRI A/S,
Glucoamylase) 1 part with 0.1M citric acid and 0.2
The solution was dissolved in 1000 parts by volume of a buffer solution prepared by mixing M phosphorus, Ml, and sodium hydride to adjust the pH to 4.5.

(Hydrolysis of starch) The polymer/starch film was immersed in a starch degrading enzyme aqueous solution whose temperature was controlled to 60° C. for 12 hours.

(Measurement of Hydrolysis Rate) The produced glucose was measured by Somogyi's modified method, and the hydrolysis rate was calculated. 81% of the starch used was hydrolyzed.

(Confirmation of pore formation using an electron microscope) The films at each stage above were examined using an electron microscope.

No pores were observed in the film obtained by using Acryset ■204E alone without using starch. It was confirmed that the polymer/starch film before being treated with the aqueous amylolytic enzyme solution had starch particles dispersed in the acrylic resin film.

It was confirmed that in the porous polymer film obtained by immersing the polymer/starch film in an aqueous amylolytic enzyme solution for 12 hours, the starch was hydrolyzed to produce a porous polymer film. Also, the pore diameter is approximately 3
It was found to be in the range of ~6 μm.

(Creation of clothing material) Acryse Soto ■ 204E was applied to polyester taffeta in the form of dots with a coating area of 30%, and the porous polymer film obtained above was superimposed on this, brought into close contact, and heated at 100°C. After drying for 15 minutes, a clothing material (1), which is a laminate of a porous polymer film and cloth, was obtained.

Example 2 (Preparation of polymer/starch film) Acryset 0
285E (manufactured by Nippon Shokubai Chemical Co., Ltd., acrylic emulsion) and Sumitex Resin M-3 (manufactured by Sumitomo Chemical Co., Ltd., water-soluble melamine resin) in a ratio of 100/3 (solid content ratio)
3.5 parts of cornstarch was added to 10 parts of thermosetting emulsion (I) obtained by mixing to obtain a homogeneous mixture.

The mixture was applied to release paper, dried at room temperature, and then the release paper was removed to obtain a film with a thickness of 45 μm.

(Creation of clothing material) Thermosetting emulsion (I) was applied dotted onto a nylon cloth so that the coating area was 35%, and the above polymer/starch film was superimposed on this, brought into close contact, and heated at 120°C. A laminate was obtained by heat treatment for 10 minutes.

Into the same amylolytic enzyme aqueous solution used in Example 1,
The above laminate was immersed at 60° C. for 18 hours to obtain a clothing material (2). When the hydrolysis rate was measured in the same manner as in Example 1, it was found to be 73%. When the porous polymer film in the obtained clothing material (2) was examined under an electron microscope, it was found that the pores were uniformly distributed. It was observed that the pore size was 8-11 μm.

Example 3 Thermosetting acrylic emulsion (I) 10 on nylon cloth
Apply a homogeneous mixture of 1 part and 2 parts of potato starch,
After drying at 20°C for 20 molecules, heat treatment was performed at 120°C for 5 minutes to form a cured coating film with a thickness of about 30 μm on the nylon cloth.

Starch was hydrolyzed in the same manner as in Example 2. The hydrolysis rate was 83%, and when the coating film of the obtained clothing material (3) was observed using an electron microscope, uniformly distributed pores were observed, and the pore diameter was 10 to 22 μm.

Example 4 A polyester cloth was soaked in a mixture of 10 parts of Acryset ■ 204E, 5 parts of rice starch, and 0.15 parts of glucoamylase, wrung to adjust the adhesion amount to about 100 g/m'', and dried at 50°C for 30 minutes. As a result, the cloth was uniformly impregnated with the solid content of the polymer/starch mixture to obtain a polyester cloth having an impregnated layer without pinholes.

A buffer solution prepared by mixing 0.1M citric acid and 0.2M sodium monohydrogen phosphate and adjusting the pH to 4.5 was heated to 60°C, and a polyester cloth having the above-mentioned impregnated layer was added to it for 36 minutes. A material for clothing (4) was obtained by soaking for a period of time.

The hydrolysis rate was 91%, and when observed with an electron microscope, the pores were uniformly distributed in the impregnated layer, and the pore diameter was 3 to 6 μm.

Example 5 A mixture of 10 parts of Merci 585 (manufactured by Toyo Polymer ■, polyurethane emulsion, non-volatile content 33.5%) and 5 parts of rice starch was applied to a cotton cloth, dried at 60°C for 30 minutes, and a thickness was applied to the cotton cloth. A coating film of approximately 25 tLm was formed.

Starch was hydrolyzed in the same manner as in Example 2 to obtain a clothing material (5). The hydrolysis rate was 75%, and according to observation using an electron microscope, pores were uniformly distributed in the coating film, and the pore diameter was 3 to 6 μm.

Comparative Example 1 A comparative clothing material (1) was produced by repeating the same operations as in Example 1 except that AMC (glucoamylase) was not used. Starch decomposition rate is 2.3%
Met.

Comparative Example 2 The laminate of the film and cloth obtained in Example 2 was treated with a 1% aqueous hydrochloric acid solution instead of the AMC aqueous solution,
Comparative clothing material (2
) was obtained. The starch hydrolysis rate was 1.9%.

Compared to the clothing material (2) obtained in Example 2, the comparative material (2) obtained had deteriorated adhesive strength between the cloth and the film, and the strength of the film itself was also weak. It was observed that

Example 6 Moisture permeability was measured for clothing materials (1) to (5) obtained in Examples 1 to 5 and comparative materials (1) to (2) obtained in Comparative Examples 1 to 2. . The results are shown in Table 1.

The method for measuring moisture permeability is as follows.

Calcium chloride was placed in a desiccator containing a water/glycerin mixture at a ratio of 65% RH.
A cup tightly sealed with processed cloth was placed, and after 24 hours at 20°C, the increase in weight of calcium chloride was measured.

Table 1

Claims (1)

[Claims] 1. A clothing material consisting of a processed fabric made by integrating a porous polymer film and cloth, wherein the porous polymer film is a polymer/starch film formed by forming a mixture of polymer and starch into a film, and the polymer /A clothing material obtained by removing starch from a starch film using an amylolytic enzyme to generate pores.