JPH05123201A - Footwear and accessories thereof - Google Patents

Abstract

PURPOSE:To prevent the infection of an athlete's foot by the generation and propagation of microorganisms, such as bacteria and fungi by wearing of footwear, such as shoes, insoles of shoes, soches and slippers, and the generation of malodors and the rust in metallic parts consisting of iron, etc. CONSTITUTION:The footwear and the accessories thereof are constituted by using the constituting members contg. the antimicrobial/rust preventive agents prepd. by compounding the three materials; one or plural antimicrobial ion sources selected from the group consisting of silver, copper, zinc and the compds. of these metals, one or plural carriers selected from the group consisting of calcium carbonate, calcium phosphate and ceramic materials for adsorbing and carrying the antimicrobial ion sources and zinc oxide whiskers having a single crystalline tetrapot-shaped three-dimensional structure as principal components. As a result, the foot wear and accessories having the excellent antimicrobial and rust preventive functions are obtd.

Description

Detailed Description of the Invention

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to footwear such as shoes, insoles, socks, slippers and the like, which suppresses the growth of microorganisms such as mold and bacteria and the generation of odor and also has an anticorrosive effect, and its accessories. Is.

2. Description of the Related Art In recent years, with westernization of life, there are many opportunities to wear shoes for a long period of time throughout the year, and in the case where shoes are not worn, slippers are often worn. Therefore, as a matter of course, socks are often used. Wearing these shoes, socks, and other footwear for a long time often causes the feet to become stuffy, which leads to the development and breeding of Trichophyton, which easily causes athlete's foot disease and infection. On the other hand, there are also many cases of athlete's foot infections caused by slippers in public places such as hospitals and accommodations. To prevent such infections, there is no effective method, and there is no effective method. It was usual to rely on treatment such as UV irradiation.

However, it is the actual situation that there is no specific medicine method or means for the treatment after these infections, and it can be completely cured only by a long and long medicinal therapy. This is a kind of fungus that causes the athlete's foot fungus called Trichophyton. Keeping it clean and drying to prevent infection and reproduction of this fungus is the only preventive measure, but in practice footwear is often used. It is difficult to achieve unless replaced with.
Therefore, in recent years, an antibacterial agent has been knitted into socks or the like and some effects have been observed, but the antibacterial effect is lost after repeated washing, and it cannot be said that the condition is satisfactory. The present invention solves the conventional problems by keeping the antibacterial effect for preventing the development of athlete's foot in footwear such as shoes, insoles, socks, slippers, and the like for a long time, and at the same time, for shoes such as pawls. Its purpose is to combine the rust prevention effect on the metal part of

[Means for Solving the Problems] In order to solve the above-mentioned problems, the present invention means an antibacterial property (a function of inhibiting or suppressing the growth of microorganisms such as bacteria and fungi). An antibacterial agent), and one or more antibacterial ion sources selected from the group consisting of silver, copper, zinc, and compounds of these metals, and calcium carbonate adsorbing and supporting the antibacterial ion sources. , Antibacterial and rust preventive, mainly composed of one or more carriers selected from the group consisting of calcium phosphate and ceramic materials and zinc oxide whiskers having a three-dimensional structure of a single crystal tetrapot The agent is used as a component of footwear and its accessories.

According to the present invention, according to the above-mentioned constitution, silver ions, copper ions or zinc ions which are generally pollution-free and are also used in drinking water purifiers and the like are used as an antibacterial ion source having an antibacterial property and become an antibacterial ion source. Calcium carbonate, calcium phosphate as a substance that adsorbs and supports a metal or a compound of the metal (naturally Ca as hydroxyapatite
Also known as apatite, which is represented by the chemical formula of ₁₀ (PO ₄ ) ₆ (OH) ₂ , is a universally prolific phosphate mineral group, ceramic materials (naturally acidic clay, Dosenkyo, etc.) (Ceramics material) and non-polluting materials that are inexpensive and easily have a large surface area, and are mixed with zinc oxide whiskers with a single crystal tetrapot-like three-dimensional structure in this support. Since it is footwear containing it and its accessories, it prevents the infection of Trichophyton, which is a cause of skin diseases such as athlete's foot, or suppresses its growth, and also has an anticorrosive effect on metal parts such as shoe brakes. It is one that exerts in a complex way.
In addition to the features described above, (1) the zinc oxide whiskers to be blended are in a single crystal tetrapot shape, and have a unique shape that they grow in four directions, which is not found in other crystals. Therefore, (a) the activity and stability are strong, and the antibacterial performance of silver ion, copper ion, zinc ion, etc. is remarkably increased. Therefore, not only the antibacterial and anticorrosive properties of the antibacterial and anticorrosive agent are great, but the content of expensive silver or copper is remarkably small, so that it is inexpensive and the footwear excellent in antibacterial and anticorrosive properties and its It is possible to realize accessories. (B) Since the antibacterial performance of silver ions, copper ions, zinc ions, etc. can be improved by mixing zinc oxide whiskers, silver,
The contents of copper, zinc and the like can be reduced to 1/10 to 1/1000 as compared with the case where conventional zinc oxide whiskers are not mixed. As a result, of course, the amount of metal ions eluted in water can be made much smaller than the environmental emission standard. Therefore, it is possible to realize footwear and its accessories having antibacterial and anticorrosive functions that are safe for environmental protection and impact on the human body. (C) Zinc oxide whiskers have a whisker fiber length of 2 to
It ranges from 3 μm to several tens of μm and has a specific gravity of 5.7.
8 (by air permeation method), sublimation temperature 1720 ℃, tensile strength 270-280 kgf / cm ² , bending strength 440 kgf / cm ² , bending elastic modulus 20,000-21,000 kgf / cm ^2, etc. Further, when mixed with the resin member constituting the accessory, there is an advantage that the mechanical strength is enhanced by the mixture of the zinc oxide whiskers. (2) The adsorption carrier is a commonly used inexpensive non-polluting substance such as calcium carbonate, calcium phosphate, and ceramics. When a water-soluble metal salt solution such as silver nitrate, copper sulfate or zinc sulfate is used, This is a simple method that allows adsorption and support by simply immersing the support in these solutions. Each of them has a sufficiently large specific surface area.

EXAMPLE For example, 0.5 to 20 wt% of calcium phosphate supporting copper and 1 to 40 wt% of zinc oxide whisker powder
% Is mixed with a polymer such as synthetic resin or synthetic rubber using an extruder and extruded to obtain a pellet of a composite polymer. The footwear and its accessories themselves or constituent members can be produced by molding and processing this using an ordinary injection molding machine or extrusion molding machine. It is also possible to use the composite polymer as a binder, dissolve or disperse it in a solvent to prepare an adhesive, and apply the composite at the processing stage of preparing footwear and its accessories. Hereinafter, examples according to the present invention will be described in detail. Example 1 First, commercially available calcium phosphate (hydroxyapatite, BET surface area 60 m ² / g) was immersed in a copper sulfate solution and then dried to carry 0.05 wt% of copper phosphate (hereinafter abbreviated as Cu hydro). Got Zinc oxide whisker powder and polyvinyl chloride (PV
C) A resin is dry-blended, and tetrahydrofuran (THF) as a solvent is added to these to dissolve PVC to prepare an adhesive containing an antibacterial / rust preventive agent. Cardboard mount P with polyethylene (PE) film laminated on one side
A flexible foamed PVC resin layer was formed on the surface of the E film by a so-called tape casting method in which a paint-like viscous solution prepared by dissolving PVC containing a foaming agent in THF was applied by a roll coater by a conventional method and then dried. Then, a taffeta woven cotton cloth is adhered to the PVC resin layer with an adhesive containing an antibacterial / anticorrosive agent prepared in advance, the PVC resin layer is peeled off from the mount, and the coating of the desired color is applied to the peeled surface. After that, the leather-like wrinkles are attached to the artificial leather sheet by the embossing roller. In short, the antibacterial / rust preventive agent according to the present invention is interposed between the foamed PVC resin layer forming the artificial leather sheet and the lined cotton cloth. Attach a zinc-plated iron pawl for passing shoelaces to an artificial leather sheet, cut out that part and make a test piece,
The antibacterial and antirust effects were evaluated. The molds used for the evaluation of the antibacterial effect are the 1st group Aspilgillus nigel, the 2nd group Penicillium citrinum (blue mold), the 4th group Cladsporium cladsporioides, and the 4th group as described in JIS 2911 “Mold resistance test method”. There are five species of group 5, ketomium globosum and candida albicans (fungi). The test method was to use a Sabouraud agar medium, and apply the test strain to the test piece at 28 ° C. and a humidity of 70 to 75% in a weather meter after applying the test piece.
After being left for 50 hours, the state of bacterial growth and the rust preventive effect were visually examined. The antibacterial / rust prevention results are shown in (Table 1).

[Table 1] As is clear from (Table 1), the examples according to the present invention have a higher antibacterial / rust-preventing effect than the conventional examples for comparison. Also, by mixing zinc oxide whiskers,
It is also clear that the amount of Cu hydro can be reduced. In addition,
In Example 1, calcium phosphate was used as the carrier, but even if ceramics such as calcium carbonate, acid clay, and Dosen-ko were used instead, the antibacterial and antirust effects were the same. The same effect can be obtained by using silver or zinc instead of copper. FIG. 1 shows an electron micrograph of zinc oxide whiskers mixed in an antibacterial / rust preventive agent in an example according to the present invention. (Example 2) The Cu hydro prepared by immersing calcium phosphate in an aqueous solution of copper sulfate and then drying was dry-blended with zinc oxide whisker powder and soft PVC, extruded with a single-screw extruder, cut after cooling, and composited. A resin pellet was prepared. Using this composite resin pellet, a shoe sole material was produced by a general-purpose injection molding machine. In addition, this shoe sole has a structure in which a protrusion for stimulating the acupoint on the sole is formed, and the sole itself is designed to be applicable to the sole of the insole or the slipper. Town shoes using general cowhide were prototyped using the bottom material, and a monitor test was carried out in an actual use state in order to compare with a conventional example containing no antibacterial / rust preventive agent according to the present invention. Each test is 10
For 0 persons, the training was carried out for 12 months assuming that the town shoes were worn for 10 hours per day. The socks worn were all nylon. The results of occurrence of athlete's foot are shown in (Table 2).

[Table 2] As is clear from (Table 2), Example 2 according to the present invention
The number of athlete's foot is much smaller than the conventional example,
It is clear that the antibacterial performance is excellent. Although it is omitted because it is difficult to quantitatively show, another effect of wearing the town shoes according to the present invention is that the feet are less likely to smell. Probably because of the antibacterial effect. Example 1
In 2 and 2, PVC is used as an example of the applicable polymer, but not only synthetic resins such as polyethylene, polypropylene, polystyrene and polyamide, but also various synthetic rubbers widely used as binders for adhesives are widely applicable. In addition, although the examples have been described with respect to shoes, if an adhesive containing an antibacterial / anticorrosive agent according to the present invention, in which PVC of Example 1 is replaced by synthetic rubber, is printed and applied to a portion of the sock that comes into contact with the sole of the foot, etc. It should be added that a product whose antibacterial effect does not easily expire after washing is obtained.

As is apparent from the above description of the embodiments, according to the present invention, one or more metals selected from the group consisting of silver, copper, and zinc serving as an antibacterial ion source, or those metals 1 selected from the group consisting of calcium carbonate carrying a metal compound, calcium phosphate, and ceramics
By using one or a plurality of carriers and a powder or a composite polymer in which zinc oxide whiskers are mixed, it is possible to provide footwear having excellent antibacterial and anticorrosive functions and its accessories.

[Brief description of drawings]

FIG. 1 is an electron micrograph showing the shape of a zinc oxide whisker contained in an antibacterial / antirust combination agent according to an example of the present invention.

Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location // C08K 3/22 KAE 7167-4J 3/26 KAF 7167-4J 3/32 KAG 7167-4J 3/34 KAH 7167-4J 7/08 KCJ 7167-4J 9/02 KCN 7167-4J

Claims (4)

[Claims] 1. Silver which elutes ions having antibacterial properties,
Selected from the group consisting of one or more antibacterial ion sources selected from the group consisting of copper, zinc, and compounds of these metals, and a group consisting of calcium carbonate, calcium phosphate, and ceramic materials that adsorb and support the antibacterial ion sources. Footwear and its accessories containing an antibacterial / anticorrosive agent mainly composed of one or more carriers and zinc oxide whiskers having a three-dimensional structure of a single crystal tetrapot. 2. Footwear and its accessories in which the antibacterial / rust preventive agent according to claim 1 is mixed in a polymer member which is a constituent member of footwear and its accessories. 3. An antibacterial / rust preventive agent containing a single crystal three-dimensional tetrapot-shaped zinc oxide whisker incorporated in the antibacterial / rust preventive agent at a lower limit of 10% by weight. Footwear described in 1 or 2 and its accessories. 4. An antibacterial ion source comprising one or more compounds of silver, copper, zinc and a metal thereof, containing up to 1% by weight of metal as an upper limit.
Footwear listed and its accessories.