JPH0359175A - Production of moisture-permeable material - Google Patents

Abstract

PURPOSE:To obtain the subject material having excellent antibacterial and mildew-proofing property and improved safety to human body without lowering the moisture permeability of the base cloth by applying a resin composition containing a hydrated antibacterial inorganic powder and a resin to a base cloth at a specific thickness and curing the coating layer with heat. CONSTITUTION:A resin composition containing (A) a hydrated antibacterial inorganic powder produced e.g. by adsorbing an antibacterial metallic ion such as ion of silver, copper or zinc to zeolite powder and adding 3-70% of water to the powder and (B) a resin (e.g. conventional natural or synthetic resin) is applied to a base cloth such as a woven or knit fabric made of natural or synthetic fiber, etc., at a thickness of 5-150mum and the coating film is cured by heating to form fine pores and obtain the objective moisture-permeable material. The resin is selected from polyurethane, polyacryl ester resin, polyvinyl resin, etc. The material is suitable for leather shoes, sneaker, sheets, sport wear, etc.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is directed to the production of a moisture permeable material that has antibacterial, antifungal, and antialgal effects without impairing its original moisture permeability, and is highly safe for the human body. It is about law.

[Conventional technology]

Conventionally, there are two types of waterproofing: breathable waterproofing and impermeable waterproofing.
Breathable waterproofs do not get stuffy, but have low water pressure resistance, while old hand breathable waterproofs have high water pressure resistance, but have the disadvantage of getting stuffy. As a method to improve these conditions, ventilation i3 wet processing, which allows water vapor to easily pass through but does not allow water droplets such as sweat and rain to pass through, has been implemented. This processing method involves coating a resin with a micropore structure (JP-A-61-68237, etc.), or mixing a hydrophilic polymer and a hydrophobic elastomer so that it is selectively permeable only to the air. A method for forming a film (Japanese Patent Laid-Open No. 55-7483, etc.) is shown.

[To be solved by the invention 118] Conventionally, products that require moisture permeability, especially products such as footwear, hats, and gloves that come into contact with the human body and are likely to cause "stuffiness," have been subject to heat, microorganisms, and skin waste products. Odor, rash, etc.
I had a problem with eczema. As a countermeasure for this, ventilation i! does not allow water to pass through, but removes moisture. ? Resin processing with W properties is performed. However, the permeability of W is weak, especially when sweating during exercise or working in high humidity. I couldn't do the jl adjustment.

Furthermore, removing only moisture cannot prevent odors, rashes, eczema, etc. caused by microorganisms and skin waste products.

[Means for solving espionage]

As a result of intensive research into materials that have sufficient moisture permeability, prevent the growth of microorganisms, and are highly safe for the human body, the present inventors have developed a resin composition containing hydrous antibacterial inorganic powder and resin. When applied to a base fabric to a film thickness of 5 to 150 μm, and then heated and cured, the resin Mi Kaimono applied to the base fabric solves the above-mentioned problems of moisture permeability, antibacterial property, anti-mold property, anti-algae property, and human body. The present invention was completed by discovering that all the safety requirements for

That is, according to the method of the present invention, when a resin composition containing a water-containing antibacterial inorganic powder and a resin, which is commonly used for base fabrics, is cured by heating, the water contained in the antibacterial inorganic powder turns into water vapor. By creating extremely fine pores in the resin coating, it is possible to obtain a moisture-permeable material that selectively allows only water vapor to pass through after curing.In addition, antibacterial substances are more likely to be exposed on the resin surface, and an increase in antibacterial effects can be expected. .

Therefore, according to the present invention, it is possible to provide a 13jIA material that has antibacterial, antifungal, and antialgal effects without impairing its original moisture permeability, and is excellent in safety for the human body.

The details of the present invention will be explained below.

In the present invention, examples of the hydrous antibacterial inorganic powder include powders in which a solid, liquid, or gaseous drug is supported on an inorganic carrier, and a certain amount of water is retained in the powder.

The inorganic carriers include crystalline aluminosilicate (hereinafter referred to as zeolite) and amorphous aluminosilicate (hereinafter referred to as AAS).
Examples include silica gel, activated alkali, diatomaceous earth, activated carbon, calcium oxide, magnesium oxide, calcium sulfate, phosphorus pentoxide, and magnesium perchlorate, which have a large water-holding capacity and high chemical stability. It is preferable to use zeolite, AAS, silica gel, activated alumina, or calcium sulfate.

The antibacterial agent used in the production of the hydrated antibacterial inorganic powder in the present invention may be in any solid, liquid or gaseous form, such as silver, copper, zinc, mercury, lead, soot, bismuth, cadmium, Ions of the genus * such as thallium and their compounds, stabilized chlorine, hypochlorite, fluorine, halogen compounds such as ethylene iodide, alcohols, phenols, ethers, guanidines, thiazoles, Examples include quaternary ammonium salts, thiocarbamates, etc., but silver, antiseptic, zinc, etc.
It is preferable to use an antibacterial zeolite or an antibacterial amorphous aluminosilicate holding an antibacterial metal such as tin, and a powder of silica gel, activated alumina, calcium sulfate, etc. on which the above antibacterial metal aqueous solution is adsorbed.

That is, the present invention uses zeolite (hereinafter referred to as antibacterial zeolite) or AAS in which antibacterial metal ions such as silver, copper, zinc, and soot are retained through ion exchange, silica gel on which an aqueous solution of the metal salt is adsorbed, and pentoxide. The present invention provides a method for producing an antibacterial material by applying a resin made of powder such as phosphorus, magnesium perchlorate, etc. and resin to a base fabric.

In the present invention, as the "zeolite", both natural zeolite and platform zeolite can be used.

Zeolite is an aluminosilicate that has a three-dimensional skeleton structure and is expressed in the following formula: Here, M represents an ion that can be exchanged, and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y represent the respective metal oxide and silica coefficients, and Z represents the number of crystal water. Specific examples of zeolites include A-type zeolide, etc. can be mentioned. However, the ion exchange capacities of these exemplary zeolites are not limited to these: 8-type zeolide 7 meq/g, X-type zeolide 6.4*eq/g, Y-type zeolite 5 meq
/g, T-type zeolide 3.4meq/g, sodalite 11.5meq/g-mordenite 2.6meq/g
g, Analcyme 5meq/g-clinoptilolite 2
．． 6 meq/g, chabasite 5 meq/g, and erionite 3.8 meq/g, all of which have sufficient capacity for ion exchange with antibacterial metal ions.

The antibacterial zeolite used in the present invention includes ion exchangeable ions in the zeolite, such as sodium ions,
Part or all of calcium ions, potassium ions, magnesium ions, iron ions, etc., are replaced with antibacterial metal ions, preferably ammonium ions and antibacterial metal ions. As examples of antimicrobial metal ions, mention may be made of ions of silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium, preferably ions of silver, copper, zinc or soot.

From the viewpoint of antibacterial properties, it is appropriate that the antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%.

Antibacterial zeolite containing 0.1 to 15% silver ions and 0.1 to 18% copper ions, zinc ions, or tin ions is more preferable, and the antibacterial zeolite further contains 0.5 to 5% ammonium ions. Effectively preventing discoloration of the antibacterial zeolite by replacing it;
I can do it. In this specification, % refers to % by weight on a dry basis at 110°C.

The method for producing the antibacterial zeolite used in the present invention will be explained below. For example, the antibacterial zeolite used in the present invention can be produced by contacting the zeolite with a mixed aqueous solution containing antibacterial metal ions such as silver ions, copper ions, zinc ions, or tin ions, preferably further containing ammonium ions, prepared in advance. The ion-exchangeable ions therein are replaced with the above ions. Contacting is carried out at 10-70°C, preferably 40-60°C for 3-24 hours, preferably 10-24 hours.
It can be carried out by a 24-hour batch method or a continuous method (for example, a column method). The pH of the above mixed aqueous solution is 3 to 1.
It is appropriate to adjust it to 0, preferably 5 to 7. This adjustment is preferable because it can prevent silver oxides and the like from being deposited on the zeolite surface or into the pores.

In addition, each ion in the mixed aqueous solution is usually supplied as a salt. For example, silver ions are supplied as silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc., and copper ions are supplied as salts. , copper nitrate (■), copper sulfate, copper perchlorate, copper acetate, potassium tetracyanostelate, etc., zinc ions include zinc nitrate (■), zinc sulfate, zinc perchlorate, zinc thiocyanate, zinc acetate, etc. The ion may be tin sulfate, and the ammonium ion may be ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium perchlorate, ammonium thiosulfate, ammonium phosphate, or the like.

The content of silver ions, etc. in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixture/8 solution. For example, when the antibacterial zeolite contains silver ions and zinc ions. , the silver ion concentration in the mixed aqueous solution was 0.002 M/l to 0.15 M/t.
, zinc ion concentration 0.15M/1~2.8? l/
1, silver ion-containing 10.1-
15% and an antibacterial zeolite with a zinc ion content of 0.1-18%. Further, when the antibacterial zeolite further contains copper ions, tin ions, and ammonium ions, the copper ion concentration in the mixed aqueous solution is 0.1M/
1-2.3M/f, tin ion concentration 0.15M/f
j1~2.5M/1, ammonium ion concentration is 0.2M/j! ~2.5M/1, copper ion content 0.1~18%, tin ion content 0.1~18%, ammonium ion content 1005~5
% antibacterial zeolite can be obtained.

In the present invention, in addition to the mixed aqueous solution as described above, ion exchange can also be performed by using an aqueous solution containing each ion individually and bringing each aqueous solution into contact with the zeolite sequentially. The concentration of each ion in each aqueous solution can be determined according to the concentration of each ion in the mixed aqueous solution.

After ion exchange, the zeolite is thoroughly washed with water and then dried. Drying is preferably carried out at 105°C to 115°C under normal pressure or at 70°C to 90°C under reduced pressure (1 to 30 torr).

In the present invention, an antibacterial amorphous aluminosilicate in which some or all of the ion-exchangeable ions in the amorphous aluminosilicate are replaced with an antibacterial metal can also be used as the antibacterial powder. Amorphous aluminosilicate is produced by a conventionally known method and has a high water-containing capacity, and any type of aluminosilicate with a water content of 3 to 70% can be used. 1986
There is a method described in, for example, No.-174111. The method for producing antibacterial amorphous aluminosilicate can be carried out in accordance with the method for producing antibacterial zeolite.

The antibacterial powder used in the present invention has a water content of 3 to 7.
0%, preferably 3 to 20% is the aeration rate of the applied resin membrane i! If the water content is less than this range, which is preferable from the viewpoint of stably obtaining tW properties, breathability will be poor, and if it is more than this range, not only water vapor but also water will pass through. In this specification, good ventilation and moisture permeability means that the air permeability is 0.2cc/ad/
Moisture permeability is 4000g/n (/40℃/24hr
This shows that the above is true.

Further, although there is no particular restriction on the particle size of the antibacterial powder, from the viewpoint of obtaining an antibacterial material with a smaller amount of powder, it is preferable that the particle size is relatively small. The particle size of the powder may be, for example, 0.04 to 20 μm, preferably 0.5 to 2 μm.

Examples of the resin used in the present invention include starch,
Natural thickening agents such as tragacanth gum, pretty gum, casein, and egg white; synthetic thickening agents such as polyvinyl alcohol, polyacrylamide, carboxymethyl cellulose, sodium alginate, and polyacrylic ester; and other polyurethane resins, silicone resins, epoxy resins, and acetal resins. , ketone resin, alkyl carbamate resin, urea resin, melamine resin, vinyl acetate resin, vinyl chloride resin, nylon resin, natural rubber, nitrile rubber (14BR
), styrene-butadiene rubber (SBR), chloroprene rubber (C12), and other synthetic resins. There are two types: agent type and emulsion type.
Among these, polyurethane, polyacrylic ester, polyvinyl, and their elastomer compositions are obtained by ventilation i! ! ! This is preferable from the viewpoint of high performance.

In the present invention, the mixing ratio when the water-containing antibacterial inorganic powder and resin are mixed to be used as a base fabric is 0.1 to 30%, preferably 0.1 to 30% of the water-containing antibacterial inorganic powder to the resin solid content. 1-
It is appropriate to prepare the content to 10% from the viewpoint of exhibiting high antibacterial activity.

In the present invention, there are no particular restrictions on the method of application to the base fabric, and any method can be used as long as it does not cause dispersion or dissolution of the antibacterial inorganic powder. Examples include spraying, knife coating (moon-shaped coating), gravure coating, roll coating, and impregnation coating.

The typical amount of the resin Mi mold can be selected depending on the purpose, for example, 5 to 600 g/nf, preferably 10 to 4 g/nf.
It is appropriate to set it to 00g/rd. In addition, it is preferable that the film thickness is 5 to 150 μm in order to maintain good air permeability. If it is thicker than this range, the air permeability will be insufficient, and if it is thin, it will not have much mechanical strength. Becomes easily damaged.

In the method for producing the resin composition of the present invention, various mixers can be used, such as a Panbury mixer with a high dispersion power, a two-roll mill, a kneader file, a three-roll mill with a weak dispersion power, a colloid mill, and a mixer. , a disper, a homomixer, a sand mill, a ball mill, etc. can also be used.

In addition, the resin composition may contain crosslinking agents, oils, waxes, fillers, preservatives, colorants, stabilizers, cell conditioners (
(surfactant) etc. may also be included.

In the present invention, the material used as the base fabric is not particularly limited in its aha, shape, etc., as long as it is not altered in quality by the manufacturing method steps in the method of the present invention. For example, natural fibers such as cotton, wool, silk, and hemp, cellulose fibers such as rayon and cupro, boria straw fibers such as nylon 6 and nylon 66, polyester fibers such as polyethylene terephthalate TA fibers, polyacrylonitrile, etc. Woven fabrics, knitted fabrics, non-woven fabrics, and composites thereof, made of at least one type of fiber selected from acrylic fibers such as fibers, water-insolubilized polyvinyl alcohol mM, cellulose acetate fibers, natural leather, synthetic leather, rubber, etc. You can use your body etc.

In the present invention, the coating material applied as described above is heated to gradually volatilize the water contained in the hydrated antibacterial inorganic powder as water vapor to form ultrafine pores in the resin coating. For example, at a temperature of 60 to 120 A moisture permeable material with fine pores is obtained by heating and curing at 5 to 60 minutes at <0>C.

The antibacterial product obtained by the present invention can be used in various products such as fibers, rubber, and brass tink that require air permeability.For example, footwear such as leather shoes, canvas shoes, sneakers, and rain boots, helmets, baseball caps, and hoods. It is suitable for hats such as rubber gloves for cooking, leather gloves, work gloves, gloves such as kendo trowels, bedclothes such as sheets and pillowcases, and clothing such as sportswear and raincoats.

(Effects of the Invention) According to the present invention, a resin composition containing a hydrous antibacterial inorganic powder and a resin is applied to a base fabric to a film thickness of 5 to 150 μm, and then a commonly used resin composition is applied to the base fabric. By heating and curing, it is possible to provide a moisture permeable material that has antibacterial, antifungal, and antialgal effects without impairing its original moisture permeability, and is highly safe for the human body.

〔Example〕

The present invention will be explained in more detail below with reference to Examples.

Reference example 1 (Preparation of antibacterial aluminosilicate) 110°C
Commercially available A-type zeolide powder (NaRO
・AltOs ・1.9SiOz ・XHJ: average particle size 1.5μ), mordenite powder manufactured by Sinanen New Ceraminck (Na*0 ・AltOs 9.7Si
Ot -XHzO: average particle size 2.0 μ-), and amorphous aluminosilicate powder (0,9Na, O・AlzOz
・2.4SiOt-XHtO (average particle size 0.9 μm) was added with water to make a slurry of 1.31, then stirred and degassed, and then an appropriate amount of 0.5N nitric acid solution and water were added. The pH was adjusted to 5 to 7, and the total volume was made into a slurry of 1.81.For zero-order ion exchange, a mixed aqueous solution containing antibacterial metal ions was added to bring the total volume to 4.81. The mixture was maintained at 60° C. and stirred for 24 hours to reach an equilibrium state. Aqueous solutions of silver nitrate, copper sulfate, zinc nitrate, tin sulfate, and ammonium nitrate were used as solutions for ion exchange. After ion exchange, the aluminosilicate phase was filtered and washed with hot water until excess silver, copper, zinc, tin, ammonium ions, etc. in the aluminosilicate phase disappeared. Next, the aluminosilicate phase was heated and dried at 110°C. Then, antibacterial aluminosilicate powder samples shown as sample numbers 1 to 8 in Table 1 were obtained.

Reference Example 2 (Antibacterial Active Aluminum Tril!) Commercially available activated alumina powder (manufactured by Wako Pure Chemical Industries, Ltd.) was made into a particle size of 0.04 to 20 μm using a jet ultrafine pulverizer.

Mixed aqueous solution 21 containing antibacterial metal ions used in Reference Example 1 was added to fine rice grains 1 and stirred at room temperature for 8 hours, and then filtered to prepare antibacterial activated alumina. Sample No. 9 to 1 is shown in Table 2.
An antibacterial alumina powder sample shown in No. 4 was obtained.

Examples 1 to 14 (Manufacture of 33 temperature material) Reference examples 1 and 2
After adjusting the water content of each antibacterial inorganic powder prepared in , the following resin composition was kneaded with a sand grinder for 3 hours, and commercially available nylon 30 denier/68 filament was used for both warp and cotton threads. 70 for plain woven fabric (tuck) with a warp density of 120 threads/inch and a weft density of 90 threads/inch.
An auto-screening machine (manufactured by Rokuki, model 1000) was used to print the entire surface through the screen mesh of the menshi.

Thereafter, they were heat treated at 105° C. for 7 minutes to obtain i3 wet processed cloth. The manufacturing conditions for each processed cloth are shown in Table 3 for Examples 1 to 1.
A processed cloth not containing a hydrous antibacterial inorganic powder was also prepared under the same conditions as shown in Table 4 (Comparative Examples 1 to 3 in Table 3).

(Resin & animals: A. Polyurethane resin (solid content 30%) 75 parts (Hirono Chemical Industry Co., Ltd. Neelak LT-100) B. Isopropyl alcohol (solvent) 25 parts C0 Hydrous antibacterial inorganic powder
1 to 5 parts (Reference Examples 1 and 2) Test Example 1 (Air permeability test) Each of the processed fabrics obtained in Examples 1-14 and Comparative Examples 1 to 3 was subjected to an air permeability test (Gulley densometer method), A yi temperature test (JIS Z-208 method) and a water pressure test using a low water pressure method (JIS-L-1096 method) were conducted. The results are shown in Table 3.

Test Example 2 (Antibacterial Test) Each processed fabric obtained in Examples 1-14 and Comparative Examples 1-3 was
Cut into 5clI pieces and add large U & bacteria (10S pieces/me) to this.
) was sprinkled with 5111 and cultured at 37°C for 18 hours. The bacterial solution was washed away with sterilized physiological saline, and the number of Escherichia coli bacteria present in this solution was measured to evaluate antibacterial properties. The results are shown in Table 3.

Test Example 3 (Test on the use of sneakers using moisture-permeable materials) Sneakers were manufactured using the moisture-permeable materials (processed fabrics) obtained in Example 2 and Comparative Example 3, respectively. 1 of each sneaker
Five pairs of shoes were used continuously for 36 hours, and the odor and degree of "stuffiness" were evaluated through a sensory test. The results are shown in Table 4.

(Evaluation criteria) A. Smell B. Stuffiness l: It smells quite strong l: It has a damp feeling.

Claims (1)

[Claims] 1. Applying a resin composition containing a hydrous antibacterial inorganic powder and a resin to a base fabric to a film thickness of 5 to 150 μm, and then heating and curing the resin composition applied to the base fabric. A method for producing a moisture permeable material characterized by: 2. The method for producing a moisture permeable material according to claim 1, wherein the moisture content of the hydrated antibacterial inorganic powder is 3 to 70%. 3. The method for producing a moisture permeable material according to claim 2, wherein the resin is any one of polyurethane, polyacrylic ester, polyvinyl, and elastomer compositions thereof.