JP2903127B2 - Manufacturing method of moisture permeable material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention is a production of a moisture-permeable material having an antibacterial, antifungal and anti-algal effect without impairing the original moisture permeability, and having excellent safety for the human body. It is about the law.

[Conventional technology]

Conventionally, waterproofing has breathable waterproofing and impervious waterproofing, but breathable waterproofing has no drawback, but has low water pressure resistance, while impervious waterproofing has a high waterproof pressure but has the drawback of `` moistness '' .
As an improvement method of these, aeration and moisture permeation processing has been performed in which water vapor is easily passed but water droplets such as sweat and rain are not passed. Examples of this processing method include a method of coating a resin having a microporous structure (Japanese Patent Application Laid-Open No. 61-68237 and others) and a method of mixing a hydrophilic polymer and a hydrophobic elastomer so as to selectively transmit only water vapor. (Japanese Patent Application Laid-Open No. 55-7483, etc.) are disclosed.

[Problems to be solved by the invention]

Conventionally, products that require moisture permeability, especially products that come into contact with the human body and easily cause stuffiness, such as footwear, hats and gloves, generate odors, rashes, and eczema due to moisture, microorganisms, skin waste products, etc. There was a problem. As a countermeasure, a resin process is used which does not allow water to pass through but has a moisture-permeable property to remove moisture. However, the moisture permeability was weak, and in particular, it was not possible to sufficiently adjust the humidity when sweating during exercise or working at high humidity. Furthermore, odor, rash, eczema, etc. caused by microorganisms and skin wastes could not be prevented only by removing moisture alone.

[Means for solving the problem]

The present inventors have sufficient moisture permeability, and prevent the growth of microorganisms, as a result of intensive research on materials having high safety to the human body, a resin composition containing a water-containing antibacterial inorganic powder and a resin When applied to the base cloth to a thickness of 5 to 150 μm, and then cured by heating the resin composition applied to the base cloth, moisture permeability, antibacterial properties, antifungal properties, anti-algal properties, and against the human body, which are the above-mentioned problems. They have found that all of the safety requirements are satisfied, and have completed the present invention.

That is, according to the method of the present invention, when the resin composition containing the water-containing antibacterial inorganic powder and the resin applied to the base cloth is cured by heating, the moisture contained in the antibacterial inorganic powder becomes steam. By opening extremely fine holes in the resin coating, it is possible to obtain a moisture-permeable material that selectively allows only water vapor to pass after curing, and it is also expected that the antibacterial substance is easily exposed to the resin surface and the antibacterial effect is increased. .

Therefore, according to the present invention, it is possible to provide a moisture-permeable material having antibacterial, antifungal and anti-algal effects without impairing the original moisture permeability, and having excellent safety for the human body.

 Hereinafter, details of the present invention will be described.

In the present invention, as the hydrous antibacterial inorganic powder, a solid,
An example is a powder or the like in which a liquid or gaseous drug is supported on an inorganic carrier and a certain amount of water is held in the powder or the like. Examples of the inorganic carrier include crystalline aluminosilicate (hereinafter referred to as zeolite) and amorphous aluminosilicate (hereinafter referred to as zeolite).
AAS), silica gel, activated alumina, diatomaceous earth, activated carbon, calcium oxide, magnesium oxide, calcium sulfate, phosphorus pentoxide, magnesium perchlorate, etc. High zeolite, AAS, silica gel, activated alumina,
It is preferable to use any of calcium sulfate.

The antimicrobial agent used when producing the water-containing antimicrobial inorganic powder in the present invention may be in any form of solid, liquid or gas, such as silver, copper, zinc, mercury, lead, tin,
Bismuth, cadmium, thallium and other metal ions and their compounds, stabilized chlorine, lead hypochlorite, chloramine,
Halogen compounds such as ethylene iodide, alcohols,
Phenols, ethers, guanidines, thiazoles, quaternary ammonium salts, thiocarbamate and the like, but strong antibacterial activity, there is also persistent,
Furthermore, silver, copper, zinc, antibacterial amorphous zeolite or antibacterial amorphous aluminosilicate holding antibacterial metals such as tin and silica gel adsorbing the antibacterial metal aqueous solution, activated alumina, It is preferable to use a powder such as calcium sulfate.

That is, the present invention relates to a zeolite (hereinafter, referred to as an antibacterial zeolite) or an AAS in which antibacterial metal ions such as silver, copper, zinc, and tin are retained by ion exchange, silica gel adsorbed with the metal salt aqueous solution, and pentoxide. Provided is a method for producing an antibacterial material by applying a resin composition comprising a powder such as phosphorus or magnesium perchlorate and a resin to a base cloth.

In the present invention, as the “zeolite”, both natural zeolites and synthetic zeolites can be used. Zeolite is generally an aluminosilicate having a three-dimensional skeleton structure, and has a general formula of XM _{2 / n} O.Al ₂ O _3.
Displayed as YSiO ₂ · ZH ₂ O. Here, M represents an ion-exchangeable ion and is usually a monovalent or divalent metal ion. n is the valence of the (metal) ion. X and Y indicate the respective metal oxides and silica coefficients, and Z indicates the number of water of crystallization. Specific examples of zeolite include, for example, A-
Type zeolite, X-type zeolite, Y-type zeolite,
Examples include T-type zeolites, high silica zeolites, sodalite, mordenite, analcyme, clinoptilolite, chabazite, erionite, and the like. However, it is not limited to these. The ion exchange capacity of these exemplified zeolites is 7 m of A-type zeolite.
eq / g, X-type zeolite 6.4meq / g, Y-type zeolite 5m
eq / g, T-type zeolite 3.4meq / g, sodalite 11.5me
q / g, mordenite 2.6meq / g, analcyme 5meq / g, clinoptilolite 2.6meq / g, chabazite 5meq / g, erionite 3.8meq / g, all of which are ion-exchanged with antibacterial metal ions. It has enough capacity.

The antibacterial zeolite used in the present invention is an ion-exchangeable ion in the zeolite, for example, a part or all of sodium ions, calcium ions, potassium ions, magnesium ions, iron ions, etc., is an antibacterial metal ion, preferably ammonium. Ion and antibacterial metal ion. Examples of antibacterial metal ions include silver, copper, zinc, mercury, tin, lead, bismuth, cadmium, chromium or thallium ions, preferably silver,
Mention may be made of copper, zinc or tin ions.

From the viewpoint of antibacterial properties, it is appropriate that the above antibacterial metal ions are contained in the zeolite in an amount of 0.1 to 15%. Antibacterial zeolites containing 0.1 to 15% silver ions and 0.1 to 18% copper, zinc or tin ions are more preferred. Further, discoloration of the antibacterial zeolite can be effectively prevented by further ion-exchanging the antibacterial zeolite with ammonium ions by 0.5 to 5%. still,
In the present specification,% means weight% on a dry basis at 110 ° C.

Hereinafter, a method for producing the antibacterial zeolite used in the present invention will be described. For example, the antimicrobial zeolite used in the present invention is prepared by bringing the zeolite into contact with a mixed aqueous solution containing antibacterial metal ions such as silver ions, copper ions, zinc ions, or tin ions, preferably ammonium ions, which are prepared in advance. The above-mentioned ions are replaced with the ion-exchangeable ions therein. The contact can be performed at 10 to 70 ° C, preferably 40 to 60 ° C, for 3 to 24 hours, preferably 10 to 24 hours by a batch system or a continuous system (for example, a column method). The pH of the mixed aqueous solution is 3 to 10, preferably 5 to 10.
It is appropriate to adjust to ~ 7. This adjustment is preferable because precipitation of silver oxide or the like on the zeolite surface or in pores can be prevented. Each ion in the mixed aqueous solution is usually supplied as a salt. For example, silver ions are silver nitrate, silver sulfate, silver perchlorate, silver acetate, diammine silver nitrate, diammine silver sulfate, etc., and copper ions are copper nitrate (I
I), copper sulfate, copper perchlorate, copper acetate, potassium tetracyanocuprate, etc., zinc ions are zinc nitrate (II), zinc sulfate,
As zinc perchlorate, zinc thiocyanate, zinc acetate and the like, tin ion as tin sulfate and the like, and as ammonium ion, ammonium nitrate, ammonium sulfate, ammonium acetate, ammonium perchlorate, ammonium thiosulfate, ammonium phosphate and the like can be used.

The content of silver ions and the like in the zeolite can be appropriately controlled by adjusting the concentration of each ion (salt) in the mixed solution. For example, when the antibacterial zeolite contains silver ions and zinc ions, the silver ion concentration in the mixed aqueous solution is 0.002 M // 0.15 M /, and the zinc ion concentration is 0.15 M / 〜2.8 M /, as appropriate. An antibacterial zeolite having a silver ion content of 0.1 to 15% and a zinc ion content of 0.1 to 18% can be obtained. 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 / ~ 2.3M /, tin ion concentration is 0.15M / ~ 2.5M /,
By setting the ammonium ion concentration to 0.2 M / ~ 2.5 M /, an antibacterial zeolite having a copper ion content of 0.1-18%, a tin ion content of 0.1-18%, and an ammonium ion content of 0.5-5% is appropriately obtained. Can be.

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

The zeolite after the ion exchange is thoroughly washed with water and then dried. Drying is preferably performed 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 obtained by substituting a part or all of ion-exchangeable ions in the amorphous aluminosilicate with an antibacterial metal can be used as the antibacterial powder. The amorphous aluminosilicate is produced by a conventionally known method and has a high water content, and any of those having a water content of 3 to 70% can be used. For example, JP-A-53-30500, JP-A-61-174111
And other methods. The method for producing the antibacterial amorphous aluminosilicate can be carried out in accordance with the method for producing the antibacterial zeolite.

The antibacterial powder used in the present invention has a water content of 3 to
It is preferable to set it to 70%, preferably 3 to 20%, from the viewpoint that the air permeability and moisture permeability of the applied resin film can be stably obtained. If the water content is less than this range, air permeability will be poor, and if it is more than this range, not only water vapor but also water will pass. In the present specification, good ventilation moisture permeability means that the air permeability is 0.2 cc / cm ² / sec or more and the moisture permeability is 4000
g / cm ^2/40 indicates that ℃ is / 24 hr or more.

Further, the particle size of the antibacterial powder is not particularly limited, but from the viewpoint of obtaining the antibacterial material with a smaller amount of powder, the particle size is preferably relatively small. The particle size of the powder can be, for example, 0.04 to 20 μm, preferably 0.5 to 2 μm.

The resin used in the present invention includes, for example, starch, tragacanth gum, pretty gum, casein, natural paste such as egg white, polyvinyl alcohol, polyacrylamide, carboxymethylcellulose, sodium alginate, synthetic paste such as polyacrylate, and the like. Other polyurethane resin, silicone resin, epoxy resin, acetal resin, ketone resin, alkyl carbamate resin, urea resin, melamine resin, vinyl acetate resin, vinyl chloride resin, nylon resin, natural rubber, nitrile rubber (NB
R), styrene butadiene rubber (SBR), chloroprene rubber (CR), and other various types of synthetic resins such as solvent type and emulsion type. Of these, polyurethane, polyacrylester, polyvinyl and their elastomer compositions are exemplified. It is preferable from the viewpoint that the obtained membrane has high permeability and moisture permeability.

In the present invention, the mixing ratio when the water-containing antibacterial inorganic powder and the resin are mixed and applied to the base fabric is such that the water-containing antibacterial inorganic powder is 0.1 to 30% with respect to the resin solid content, and preferably 1 to 30%. Ten
% Is suitable from the viewpoint of exhibiting high antibacterial activity.

In the present invention, there is no particular limitation 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 or the like. For example, application methods include spray coating (spraying), knife coating (blade coating),
Gravure coating, roll coating, impregnation coating and the like can be mentioned.

The application amount of the resin composition can be variously selected depending on the use and the like, but is, for example, 5 to 600 g / m ² , preferably 10 to 400 g / m ² . Further, it is preferable that the film thickness is 5 to 150 μm for maintaining good air permeability. When the thickness is larger than this range, the air permeability is insufficient, and when the thickness is smaller, the material is liable to be broken due to insufficient mechanical strength.

In the method for producing the resin composition of the present invention, various mixers can be used, for example, a Banbury mixer having a high shear dispersing power, a two-roll mill, a kneader and a three-roll mill having a low shear dispersing power, a colloid mill, mixer,
Dispersers, homomixers, sand mills and ball mills can also be used.

The resin composition may contain a crosslinking agent, oils, waxes, fillers, preservatives, coloring agents, stabilizers, cell conditioners (surfactants), and the like, if necessary.

In the present invention, there is no particular limitation on the type, shape, and the like of the material used as the base fabric, as long as the material does not deteriorate due to the manufacturing method step in the method of the present invention. For example, natural fibers such as cotton, wool, silk, and hemp; cellulosic fibers such as rayon and cupra; polyamide fibers such as nylon 6, nylon 66; polyester resins such as polyethylene terephthalate fibers; and polyacrylonitrile fibers. Acrylic fiber, water-insolubilized polyvinyl alcohol fiber, cellulose acetate fiber, natural leather, synthetic leather, at least one fiber selected from rubber, woven fabric, knitted fabric,
In the present invention, the coated material applied as described above can be used as a non-woven fabric and a composite thereof. Drill fine holes.
For example, by heating at a temperature of 60 to 120 ° C. for 5 to 60 minutes to cure, a moisture-permeable material having fine pores can be obtained.

The antibacterial product obtained by the present invention can be used for various products such as fibers, rubbers, and plastics that require aeration and moisture permeability. For example, footwear such as leather shoes, shoes, sneakers, and boots, hats such as helmets, baseball caps, and hoods, rubber gloves for cooking, leather gloves, work gloves, gloves such as a kendo trowel, and sheets and bedding such as pillow covers. It is suitable for clothing such as sportswear and raincoat.

〔The invention's effect〕

According to the present invention, a resin composition having a water-containing antibacterial inorganic powder and a resin is applied to a base cloth to a thickness of 5 to 150 μm, and then the resin composition applied to the base cloth is cured by heating. It is possible to provide a moisture-permeable material having antibacterial, antifungal and anti-algae effects without impairing the moisture permeability of the product and having excellent safety for the human body.

〔Example〕

 Hereinafter, the present invention will be described in more detail with reference to Examples.

Reference Example 1 (Preparation of antibacterial aluminosilicate) Commercially available A-type zeolite powder (N
a ₂ O ・ Al ₂ O ₃・ 1.9SiO ₂・ XH ₂ O: average particle size 1.5μm), mordenite powder made of Sinanen New Ceramics (Na ₂ O ・ Al ₂ O
_{3 · 9.7SiO 2 · XH 2 O} : average particle size 2.0 .mu.m), and JP 61-
Amorphous aluminosilicate powder synthesized according to 174111 (0.9Na ₂ O ・ Al ₂ O ₃・ 2.4SiO ₂・ XH ₂ O: average particle size 0.9 μm)
Was added to water to obtain a slurry of 1.3, and then stirred to degas, and an appropriate amount of 0.5N nitric acid solution and water were added to adjust the pH to pH.
Was adjusted to 5 to 7 to obtain a total volume of 1.8 slurry. Next, for ion exchange, the total volume was adjusted to 4.8 by adding to the mixed aqueous solution containing the antibacterial metal ion, and the slurry was heated to 40 to 60 ° C.
And kept in a state where it reached an equilibrium state with stirring for 24 hours. Each solution of silver nitrate, copper sulfate, zinc nitrate, tin sulfate, and ammonium nitrate was used as a solution for ion exchange. After ion exchange, the aluminosilicate phase is filtered, and excess silver, copper, zinc,
It was washed with water until tin, ammonium ions and the like disappeared. Next, the aluminosilicate phase was dried by heating at 110 ° C. to obtain antibacterial aluminosilicate powder samples shown in Table 1 as sample Nos. 1 to 8.

Reference Example 2 (Preparation of Antibacterial Active Alumina) Commercially available activated alumina powder (manufactured by Wako Pure Chemical Industries, Ltd.) was adjusted to a particle size of 0.04 to 20 μm by a jet type ultrafine pulverizer. A mixed aqueous solution 2 containing the antibacterial metal ion used in Reference Example 1 was added to 1 kg of the fine powder, stirred at room temperature for 8 hours, and then filtered to prepare an antibacterial active alumina. Then, it was dried by heating at 110 ° C. to obtain antibacterial alumina powder samples shown in Table 2 as sample Nos. 9 to 14.

Examples 1 to 14 (Production of moisture-permeable material) After adjusting the water content of each antibacterial inorganic powder prepared in Reference Examples 1 and 2 to a predetermined amount, the following resin composition was kneaded with a sand grinder for 3 hours. A warp density of 120 using nylon 30 denier / 68 filament for both commercially available warp and weft
Plain fabric (taffeta) with yarn / inch and weft density 90 yarn / inch
Then, the entire surface was printed with an automatic screening machine (made by 6 units, model 1000) through a 70 mesh screen mesh.
Thereafter, they were heat-treated at 105 ° C. for 7 minutes to obtain a moisture-permeable cloth. The production conditions of each work cloth are shown in Examples 1 to 14 in Table 3. Worked cloths containing no hydrous antibacterial inorganic powder under the same conditions were also prepared (Comparative Examples 1 to 3 in Table 3).

(Resin composition): A. Polyurethane resin (solid content: 30) 75 parts (Yulac LT-100 manufactured by Hirono Chemical Co., Ltd.) B. Isopropyl alcohol (solvent) 25 parts C. Water-containing antibacterial inorganic powder 1 to 5 parts ( Reference Examples 1 and 2) Test Example 1 (Ventilation moisture permeability test) For each of the processed cloths obtained in Examples 1 to 14 and Comparative examples 1 to 3, a permeability test (Gulley type densometer method) and a moisture permeability test (JIS)・ Z-208 method) and water resistance test (JIS L-1096 method) by low water pressure method. Table 3 shows the results.

Test Example 2 (Antibacterial test) Each of the processed cloths obtained in Examples 1 to 14 and Comparative Examples 1 to 3 was 5 ×
It was cut into 5 cm, and 5 ml of Escherichia coli (10 ⁵ cells / ml) was sprinkled on it and cultured at 37 ° C. for 18 hours. The bacterial solution was washed away with a sterilized saline solution, and the number of E. coli present in the solution was measured to evaluate the antibacterial activity. Table 3 shows the results.

Test Example 3 (Use test of sneaker using moisture-permeable material) Sneakers using the moisture-permeable material (work cloth) obtained in Example 2 and Comparative Example 3 were manufactured. Each sneaker
Fifteen feet were used continuously for 36 hours, and then the odor and the degree of “smell” were evaluated by a sensory test. Table 4 shows the results.

(Evaluation criteria) A. Smell B. Mouret 1: It smells quite strong.

2: Smell 2: Smell felt 3: Slightly smelled 3: Slightly smelled 4: Not smell at all 4: No smell at all Test example 4 (use test of a hat using a moisture-permeable material) Example 10 and Hats using the moisture-permeable material obtained in Comparative Example 3 were manufactured. Fifteen hats were used continuously for 12 hours under sunlight irradiation, and the smell and the degree of “smell” were evaluated by a sensory test in the same manner as in Test Example 3. Table 4 shows the results
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Claims (3)

(57) [Claims] An antibacterial property is obtained by applying a resin composition containing a water-containing antibacterial inorganic powder and a resin to a base cloth to a thickness of 5 to 150 μm, and then heating and curing the resin composition applied to the base cloth. The moisture contained in the inorganic powder is converted into water vapor to form an extremely fine hole in the resin coating to expose the antibacterial substance to the resin surface. A method for producing a moisture-permeable material, characterized by changing to a moisture-permeable material to be passed. 2. The water content of the water-containing antibacterial inorganic powder is 3 to 70%.
The method for producing a moisture-permeable material according to claim 1, wherein 3. The method for producing a moisture-permeable material according to claim 2, wherein the resin is any one of polyurethane, polyacrylester, polyvinyl, and an elastomer composition thereof.