JP2000000103A - Shoe insole and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To make moisture absorbing and discharging, antibacterial, deodorizing, and heat insulating properties superior, to enhance the effect of treating athlete's foot and preventing its recurrence, and to maintain its performance over a long period by coating an air-permeable base material with a liquid composition containing silver and particulates and forming a film with large surface area. SOLUTION: A liquid composition with main components of 0.02-2 wt.% of silver on a silver atom basis, 10-70 wt.% of colloidal inorganic matter and/or inorganic particles on a solids basis, 1.5-20 wt.% of at least one type selected from a group of resin, silicate, metal alkoxide, and metal hydroxide as a binding agent, and 8-80 wt.% of water and/or a hydraulic organic solvent is prepared. The main components total to 100 wt.%. The liquid composition is applied to a base material for a shoe insole, and the liquid composition is hardened by ordinary temperature or low temperature heating to form a coating layer. After forming the coating layer on the base material, it is cut and/or shaped into the shape of a shoe insole to produce a shoe insole.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a shoe insole and a method for producing the same, and more particularly to a shoe insole (drying property), an antibacterial property, a deodorizing property, and a heat retaining property. The present invention relates to a shoe insole which is effective in treatment and has a large effect of preventing its recurrence, and can maintain its performance for a long period of time, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, shoe insoles have been added with activated carbon, silica gel or zeolite, or blended with cotton, hemp, etc. in order to impart drying or deodorizing properties. Antimicrobial agents are added for the purpose. On the other hand, a number of athlete's foot drugs are commercially available for the treatment of athlete's foot. However, inside shoes, conventional shoe insoles are all problematic in their effectiveness, and on the other hand,
Although drugs have therapeutic effects, they have problems in preventing recurrence. Normally, shoes are apt to generate odors and athlete's foot in the summer due to high temperature and high humidity, and are apt to cool down in the winter because heat is lost due to evaporation of moisture. In order to solve such a problem, it is preferable that the inside of the shoe is always dry, but this has not been solved.

[0003]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art. In this invention, a gas-permeable base material is coated with a liquid composition containing silver and fine particles, and a large surface area is obtained. By forming a film having
Excellent moisture absorption and drying properties (drying properties), antibacterial properties, deodorizing properties, excellent heat retention,
In particular, it is an object of the present invention to provide a shoe insole which is effective in treating athlete's foot, has a large effect of preventing its recurrence, and can maintain its performance for a long period of time.

[0004]

According to the present invention, (A) 0.02 to 2% by weight of silver in terms of silver atom and (B) 10 to 70% in terms of solid content of colloidal inorganic substance and / or inorganic fine particles.
(C) 1.5 to 20% by weight of (C) at least one selected from the group consisting of resin, silicate, metal alkoxide and metal hydroxide as a binder; and (D) water and / or a hydrophilic organic compound. 8 to 80% by weight of solvent [however,
(A) + (B) + (C) + (D) = 100% by weight] is applied to a shoe insole base material, and the liquid composition is heated at room temperature or at a low temperature. The present invention provides a shoe insole having a cured coating layer. Further, the present invention provides (A) silver in an amount of 0.02 to 2% by weight in terms of silver atom,
(B) 10 to 70% by weight of a colloidal inorganic substance and / or inorganic fine particles in terms of solid content, and (C) at least one selected from the group consisting of a resin, a silicate, a metal alkoxide and a metal hydroxide as a binder. 1.5 to 20% by weight, and (D) water and / or a hydrophilic organic solvent 8
~ 80% by weight [(A) + (B) + (C) +
(D) = 100% by weight].
The present invention provides a method for producing a shoe insole, which is applied to a shoe insole base material, and the liquid composition is cured by heating at room temperature or low temperature to form a coating layer. Here, the silver is selected from the group consisting of silver, silica gel, alumina, titanium oxide, zinc oxide and other metal compounds which are ion-exchanged and carried on a carrier of an aluminosilicate and / or a phosphoric acid compound. It is preferred that the silver is adsorbed or fixed to at least one kind and / or colloidal silver.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The shoe insole according to the present invention contains silver and a colloidal inorganic substance and / or inorganic fine particles in a base material for a shoe insole, and as a binder, a resin, a silicate or a metal alkoxide. And a liquid composition containing at least one selected from the group consisting of a metal hydroxide and a metal hydroxide, and the applied liquid composition is cured by heating at room temperature or low temperature.

The silver (A) used in the present invention has an antibacterial property, a deodorizing property, and particularly an effect of treating athlete's foot and preventing its recurrence in the shoe insole of the present invention. The silver (A) used in the present invention includes silver, silica gel, alumina, titanium oxide, zinc oxide and the like, which are ion-exchanged and supported on at least one carrier selected from aluminosilicates and phosphate compounds. Silver adsorbed or fixed on at least one selected from the group consisting of the metal compounds described above, and colloidal silver. As silver to be carried, adsorbed or fixed, at least one selected from silver nitrate, silver sulfate, silver chloride, and other silver salts,
Alternatively, colloidal silver having an average particle size of 0.01 μm or less can be used. Here, examples of the aluminosilicate serving as a carrier include natural or synthetic zeolites, kaolinite, high alumina clay, and sillimanite. Also,
Examples of the phosphate compound include calcium phosphate, zinc phosphate, zirconium phosphate, and the like. others,
Examples of the metal compound serving as a carrier include silica gel, alumina, titanium oxide, zinc oxide, calcium carbonate, and potassium titanate whisker. The shape of the carrier is
It may be granular, fibrous, or any other material. In the case of granular, the average particle size is 0.01 to 10 μm, preferably 0.01 to 5 μm. The aqueous solution obtained by dissolving one or two or more of the above silver salts can be ion-exchanged, adsorbed or fixed to the carrier to give the component (A). The silver concentration in the component (A) after the loading was 0.02 to
It is about 2% by weight, preferably 0.05 to 1.5% by weight.

[0007] Colloidal silver has an average particle size of 0.01 µm.
m, preferably particles having a particle size of 0.002 to 0.007 μm dispersed in a dispersion medium. Water is usually used as the dispersion medium. The pH is 9.0-1.
At 1.0, the concentration of dispersed silver particles is usually on the order of 0.1 to 2% by weight. The amount of the component (A) used in the present invention is 0.02 to 2% by weight, preferably 0.05 to 1% by weight in terms of silver atom in the liquid composition. If the amount is less than 0.02% by weight, the antibacterial and deodorizing powers are insufficiently expressed, while if it exceeds 2% by weight, the antibacterial and deodorizing powers hardly increase, but instead discolor and decrease the proportion of other components. Therefore, the desired effect cannot be obtained or the cost increases, which is not preferable.

[0008] Next, the component (B) of the present invention functions to absorb and discharge moisture (dry), deodorize, and keep warm in the insole of the present invention. In the component (B), the colloidal inorganic substance is an average particle size of about 5 to 50 mμ, preferably 7 to 50 mμ.
A particle having a particle size of ２０20 μm is dispersed in a dispersion medium, and various known particles can be used. As a dispersion medium,
Usually, the following lower alcohols, hydrocarbon ether alcohols, organic solvents such as acetic acid esters thereof, and water are used alone or in combination, and the solid concentration of the dispersed particles is usually 10 to 50% by weight. It is about. In the present invention, any of such colloidal inorganic substances can be used. Specific examples of the colloidal inorganic substance include colloidal silica, colloidal alumina, colloidal titanium oxide, colloidal zirconium oxide, colloidal cerium oxide, colloidal zinc oxide, colloidal iron oxide, colloidal manganese oxide, and colloidal water. Aluminum oxide and the like can be given. Among them, colloidal silica,
Colloidal alumina is preferred. Colloidal silica is
It is a single-particle polymer silica sol having a silanol group on the surface of the siloxane bond, and when this is gelled, the single particle of this polymer causes condensation and dehydration of the silanol group,
A siloxane bond chain is formed to form a three-dimensional siloxane bond network while multimerizing into pure silica gel. Specific examples of the colloidal silica include a Snowtex series manufactured by Nissan Chemical Industry Co., Ltd., a cataloid series manufactured by Catalyst Chemical Industry Co., Ltd., and an Adelite series manufactured by Asahi Denka Kogyo Co., Ltd. The colloidal alumina is an alumina sol having a pH of 2.5 to 6 using water as a dispersion medium, containing 5 to 25% by weight of alumina,
An acid such as nitric acid, hydrochloric acid, or acetic acid is used as a stabilizer.

In the component (B), the inorganic fine particles have an average particle diameter of about 0.01 to 50 μm, preferably 0.1 to 50 μm.
Those having a thickness of 1 to 10 μm are suitable, and coloring pigments, extender pigments, functional pigments and the like can be used. As the coloring pigment, titanium oxide white, yellow or black, iron / copper / manganese synthetic oxide black, iron oxide brown, yellow or black, carbon,
Strontium chromate, molybdenum red or white, cobalt blue or green (cobalt aluminum synthetic oxide), chromium oxide green, nickel oxide gray, and the like. Examples of the extender include kaolin, silicon dioxide, aluminum oxide (alumina), aluminum hydroxide, calcium carbonate, magnesium carbonate, silicon nitride, silicon carbide, zirconium silicate, and the like. Further, examples of the functional pigment include potassium titanate whisker, fibrous aluminum oxide, silicon carbide whisker, zeolite, silica gel, and natural mineral powder.

The component (B) of the present invention also contains a carrier which may be used for the component (A), and the amount of the carrier used is 10 to 70% by weight, preferably 1 to 70% by weight in terms of solid content in the liquid composition.
5 to 60% by weight. If it is less than 10% by weight, the properties such as moisture absorption / exhaustability and deodorizing properties are insufficient. On the other hand, if it exceeds 70% by weight, the viscosity increases and the proportion of other components is too small, which is not preferable.

Next, the component (C) of the present invention functions as a binder in the formed film. (C)
Among the components, examples of the resin include a synthetic resin emulsion and a water-soluble synthetic resin. As synthetic resin emulsions and water-soluble synthetic resins, for example, acrylic resin, alkyd resin, melamine resin, phenol resin, epoxy resin,
Polybutadiene, styrene-butadiene copolymer, acrylic-styrene copolymer, acrylic-modified urethane resin,
Examples include, but are not limited to, emulsion types and water-soluble types such as silicone resins. The above synthetic resin is mixed well with water and dried to form a water-insoluble transparent or translucent film.

[0012] Specific examples of the emulsion type of the synthetic resin include vinyl acetate resin emulsion, acrylic resin emulsion, acryl-styrene copolymer emulsion, styrene-butadiene copolymer emulsion,
Acrylic-modified urethane resin emulsions, silicone resin emulsions and the like can be mentioned. Specific examples of the water-soluble synthetic resin include a water-soluble melamine resin, a water-soluble phenol resin, a water-soluble polybutadiene, and a water-soluble acrylic resin. The above synthetic resins can be used singly or as a mixture of two or more.

[0013] Of the component (C) used as a binder, silicate is dehydrated to form a silanol group (Si-
OH) has the property of condensing into three dimensions. Taking lithium silicate as an example, the structural formula of a silicate is as follows.

Taking a specific example of a silicate as an anhydrous salt,
Lithium silicate, sodium silicate, potassium silicate,
Cesium silicate, amine silicate and the like can be mentioned. Among them, examples of the amine silicate include liquid silicates such as dimethylethanol ammonium silicate, monomethyl tripropanol ammonium silicate, dimethyl dipropanol ammonium silicate, and monoethyl tripropanol ammonium silicate. These silicate amines are prepared by adding a quaternary ammonium hydroxide to an activated silica solution obtained by contacting a diluted water glass with a hydrogen-type cation exchange resin and concentrating the solution to a predetermined concentration, or It can be easily obtained by a method of reacting an ammonium hydroxide with a silica hydrosol. Here, the quaternary ammonium hydroxide is usually obtained by a method of adding an alkylene oxide to ammonia or amines, or a method of deionizing a quaternary amine salt with an anion exchange resin.
Products containing a small amount of tertiary, secondary or primary amines in the product can also be used, and silicate amines obtained using the same can also be used in the composition of the present invention. can do. Note that in the silicic acid amine, it is preferred that SiO ₂ is contained in the range of 5 to 70 wt%.

Specific examples of the above-mentioned amine silicate include amine silicate CAS 25 manufactured by Nissan Chemical Industries, Ltd.
[SiO ₂ content = 25 to 26% by weight, specific gravity (20 ° C.)
= 1.19, viscosity (cps) = 3.0, pH = 11.
0], the same cast 40 [SiO ₂ content = 40 to 41% by weight, specific gravity (20 ° C.) = 1.32, viscosity (cps) = 1
0.0, pH = 11.2], NS manufactured by Nippon Laboratories Co., Ltd.
-20 (SiO ₂ concentration = about 20% by weight). These silicates can be used alone or in combination of two or more.

Further, among the component (C), known metal alkoxides and metal hydroxides can be used, and examples thereof include the following. R ¹ _i M ¹ (OR ² ) _j (wherein, R ¹ has 1 to 3 carbon atoms)
Alkyl group or a vinyl group, R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M ¹ is calcium or barium, i is 0 or 1, j is 1 or the compound represented by showing a 2 integer) . R ³ _k M ² (OR ⁴ ) _l (wherein R ³ has 1 to ³ carbon atoms)
R ⁴ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M ² is aluminum, yttrium or lanthanum, k is 0 or 1, and l is an integer of 1, 2 or 3.) The compound represented. R ⁵ _mM ³ (OR ⁶ ) _n (wherein R ⁵ has 1 to 3 carbon atoms)
R ⁶ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, M ³ is titanium, zirconium, manganese, tin, silicon or strontium, m
Is 0 or 1, and n is an integer of 3 or 4.) These compounds can be used alone or in combination of two or more.

The above metal alkoxides and metal hydroxides
Is a specific example of Ca (OCH_Three)_Two, Ca (OC_Two
H_Five)_Two, Ca (OC_ThreeH₇)_Two, Ca (OC_FourH₉)
_Two, Ba (OCH_Three)_Two, Ba (OC_TwoH_Five)_Two, Ba
(OC_ThreeH₇)_Two, Ba (OC_FourH₉)_Two, Al (OC
H_Three)_Three, Al (OC_TwoH_Five)_Three, Al (OC_ThreeH₇)
_Three, Al (OC_FourH₉)_Three, CH_ThreeAl (OC
H_Three)_Two, CH_ThreeAl (OC_TwoH_Five)_Two, CH_ThreeAl
(OC_ThreeH₇)_Two, CH_ThreeAl (OC_FourH₉)_Two, Ti
(OCH_Three)_Four, Ti (OC_TwoH_Five)_Four, Ti (OC_Three
H₇)_Four, Ti (OC_FourH ₉)_Four, CH_ThreeTi (OCH
_Three)_Three, CH_ThreeTi (OC_TwoH_Five)_Three, CH_ThreeTi (O
C_ThreeH₇)_Three, CH_ThreeTi (OC_FourH₉)_Three, C_TwoH_Five
Ti (OCH_Three)_Three, C_TwoH_FiveTi (OC_TwoH_Five)_Three,
C_TwoH_FiveTi (OC_ThreeH₇)_Three, C_TwoH_FiveTi (OC_Four
H₉)_Three, Si (OCH_Three)_Four, Si (OC
_TwoH_Five)_Four, Si (OC _ThreeH₇)_Four, Si (OC
_FourH₉)_Four, CH_ThreeSi (OCH_Three)_Three, CH_ThreeSi
(OC_TwoH_Five)_Three, CH_ThreeSi (OC_ThreeH₇)_Three, CH
_ThreeSi (OC_FourH₉)_Three, C_TwoH_FiveSi (OC
H_Three)_Three, C_TwoH_FiveSi (OC_TwoH_Five)_Three, C_TwoH_FiveS
i (OC_ThreeH₇)_Three, C_TwoH_FiveSi (OC_FourH₉)_Three,
Zr (OCH_Three)_Four, Zr (OC_TwoH_Five)_Four, Zr (O
C_ThreeH₇)_Four, Zr (OC_FourH₉)_Four, CH_ThreeZr (O
CH_Three)_Three, CH_ThreeZr (OC_TwoH_Five)_Three, CH_ThreeZr
(OC_ThreeH₇)_Three, CH_ThreeZr (OC_FourH₉)_Three, C_Two
H_FiveZr (OCH_Three)_Three, C_TwoH_FiveZr (OC _TwoH_Five)
_Three, C_TwoH_FiveZr (OC_ThreeH₇)_Three, C_TwoH_FiveZr (O
C_FourH₉)_Three, Sn (OCH_Three)_Four, Sn (OC
_TwoH_Five)_Four, Sn (OC_ThreeH₇)_Four, Sn (OC
_FourH₉)_Four, Ca (OH)_Two, Ba (OH)_Two, Al
(OH)_Three, CH_ThreeAl (OH)_Two, Ti (OH)_Four,
CH_ThreeTi (OH)_Three, C_TwoH_FiveTi (OH)_Three, Si
(OH)_Four, CH_ThreeSi (OH)_Three, C_TwoH_FiveSi (O
H)_Three, Zr (OH)_Four, CH_ThreeZr (OH)_Three, C_Two
H_FiveZr (OH)_Three, Sn (OH)_FourEtc.
You. These compounds may be used alone or
Alternatively, two or more kinds may be used as a mixture.

Further, as the binder of the present invention, a co-condensation compound in which these compounds are combined in advance can also be used. Examples of the co-condensation compound include ZrOSi (OC ₂ H ₅ ) ₆ and AlOSi (OC _{2
H 5) 6, TiOSi (OC} 2 H 5) 6, (C 3 H
₇ O) ₃ ZrOSi (OC ₂ H ₅ ) ₃ , (C ₃ H ₇ O)
₃ TiOSi (OC ₂ H ₅ ) ₃ , (C ₄ H ₉ O) ₃ Zr
OSi (OC ₂ H ₅ ) ₃ , (C ₄ H ₉ O) ₃ TiOSi
(OC ₂ H ₅ ) ₃ , (C ₃ H ₇ O) ₂ AlOSi (OC
_{2 H 5) 3, (C} 4 H 9 O) 2 AlOSi (OC
₂ H ₅ ) _{3 and the} like.

The amount of the binder used as the component (C) is 1.5 to 20% by weight, preferably 3 to 15% by weight, in the liquid composition. If the amount is less than 1.5% by weight, the bonding force is insufficient and powder is dropped. On the other hand, when the content exceeds 20% by weight, the covering power is too large, so that the antibacterial power and the deodorizing power cannot be exhibited, or the moisture absorption / exhaustability is impaired. The amount of the component (C) used is a solid content conversion when the use form is an emulsion or an aqueous solution.

Next, the component (D) (water and / or hydrophilic organic solvent) used in the present invention is used as a dispersion medium for the components (A) and (B), and as a viscosity modifier or a component (C). Is an essential component as a solvent or dispersion medium. Here, distilled water, ion-exchanged water, tap water, industrial water, or the like can be used as the water. Further, as the hydrophilic organic solvent, for example, methanol, ethanol,
n- or i-propanol, n-, sec- or t
-Lower alcohols such as butanol, ethylene glycol monoalkyl ether, diethylene glycol monoalkyl ether, propylene glycol monoalkyl ether, methyl group as an alkyl group such as dipropylene glycol monoalkyl ether, methyl, ethyl, propyl,
Hydrocarbon ether alcohols having butyl, etc., ethylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate,
Acetates such as the above hydrocarbon ether alcohols such as propylene glycol monoalkyl ether acetate and dipropylene glycol monoalkyl ether acetate; acetates of alcohols such as ethoxyethyl acetate; methyl acetate; ethyl acetate; propyl acetate; butyl acetate Acetates, such as acetone, etc. can be used. Here, the water and the hydrophilic organic solvent include the colloidal silver, the colloidal inorganic substance,
Water and hydrophilic organic solvents contained in silicate, emulsion-type or water-soluble type synthetic resin colloids are also included. The above-mentioned water and hydrophilic organic solvent can be used alone or as a mixture of two or more.

(D) The amount of water and / or hydrophilic organic solvent used is 8 to 8 in the liquid composition used in the present invention.
0% by weight, preferably 20-75% by weight. If it is less than 8% by weight, the viscosity of the liquid composition becomes high, so that the workability is deteriorated. On the other hand, if it exceeds 80% by weight, other components, in particular, the component (B) are insufficient, and the expression of the intended performance is reduced. It is not preferable.

The liquid composition used in the present invention is used after adjusting its solid concentration to preferably 15 to 80% by weight, more preferably 25 to 65% by weight. If the content is less than 15% by weight, the moisture absorption / desorption property becomes insufficient, while 8
If it exceeds 0% by weight, the viscosity is too high, so that the processability is deteriorated and the powder is dropped, which is not preferable.

In the liquid composition used in the present invention, in addition to the above-mentioned components, as component (E), if necessary, an inorganic or organic acid, various surfactants, a dispersant, a thickener, a curing control agent Agents, chelating agents, organic dyes and pigments, and the like. The above additives can be added in any amount as long as the object of the present invention is not impaired. The liquid composition is obtained by mixing the components (A) to (D), blending the component (E) as needed, and adjusting the total solid content concentration. At this time, the liquid composition is a high-speed stirrer, a roll mill,
By dispersing and filtering with a ball mill or other dispersing machine, a uniform and stable dispersion can be obtained.

The base material for the insole used in the present invention is preferably air-permeable. Fabrics such as woven fabric, knitted fabric and nonwoven fabric, cellulose-based natural paper, synthetic paper, and natural / artificial Organic substrates such as leather and plastic are exemplified. These base materials may be a material in which a pattern is printed in advance, a material containing fibers or wood chips, or a material which is stamped by a press die.

In the present invention, the above-mentioned liquid composition is applied to a shoe insole base material, and a coating layer is formed by a dehydration, a solvent removal reaction or a polycondensation reaction. Furthermore, a pattern can be provided by printing. The application method is not particularly limited, and for example, a spray method, a roll coating method, a dipping method, a curtain flow method, gravure printing, a screen printing method, and the like can be adopted.

When the component (C) is a resin or a silicate, the curing of the liquid composition after application is a desolvation or dehydration reaction, and proceeds even at room temperature. And the polymerization density is increased, and the coating layer becomes more dense. Heating is carried out at 50 to 200 ° C., preferably about 70 to 120 ° C., and the time is suitably 2 to 60 minutes, preferably about 5 to 20 minutes. If less than 50 ° C,
The curing time is hardly shortened. On the other hand, when the curing temperature exceeds 200 ° C., the substrate or the coating film is changed, which is not preferable.
The curing of the liquid composition after application is polymerization and gelation when the component (C) is a metal alkoxide or metal hydroxide, and proceeds even at room temperature. And the polymerization density is increased, and the coating layer becomes more dense. Heating is 60-200 ° C,
Preferably at about 80 to 150 ° C. for a time of 2 to 60 minutes,
Preferably, about 5 to 45 minutes is appropriate. If the temperature is lower than 60 ° C., the curing time is hardly shortened, while
If it exceeds, the substrate is undesirably changed.

Further, in order to improve the performance of the shoe insole such as moisture absorption / discharge (drying), antibacterial property, deodorizing property, heat retaining property, etc., after applying, drying or curing the liquid composition of the present invention, One or more layers of the liquid composition of the present invention can be applied to form a multi-layer coating layer. After applying the liquid composition to which the pigment is added, after drying or curing, the liquid composition to which the pigment is not added may be applied one to several times. Furthermore, after applying the liquid composition to which the pigment is added, after drying, or after curing, it is possible to print a pattern with a liquid composition of a different color, and then apply the liquid composition without the pigment thereon. it can. The coating amount of the coating layer to be formed, in terms of solid content, typically, 10 to 100 g / m ^2, preferably 20 to 80 g / m ^2.

After the coating layer is formed on the base material, if necessary, the laminate is laminated with a reinforcing material, and the laminate is fixed or adhered by sewing or hot spotting, and cut and / or formed into a shoe insole. Then make a shoe insole. The order of the manufacturing operation steps may be appropriately changed as necessary, or printing and other processing steps may be added.

[0029]

The present invention will now be described more specifically with reference to examples. In the examples, parts and% are by weight unless otherwise specified.

The components and base materials used in the examples are as follows. (A) Silver component; a-1: silver-supported zeolite (average particle size 1.5 μm, 6.5% in terms of silver atom) a-2: Silver-supported titanium oxide (average particle size 0.2 μm, 5% in terms of silver atom) A-3: Colloidal silver (average particle size 0.005 μm, silver atom equivalent 1.5%) (b) Colloidal inorganic substances and inorganic fine particles; b-1: Colloidal alumina (pH 4.5, alumina content 20%) B-2: Titanium oxide (average particle size 0.4 μm) b-3: Kaolin (average particle size 0.5 μm) b-4: Alumina (average particle size 3.0 μm) b-5: Magnesium carbonate (average particle size) B-6: Potassium titanate whisker (diameter 0.2 to 0.1)
5 μm, length 10-20 μm)

(C) Binder; c-1: acrylic resin emulsion (pH 5.0, solid content 45%) c-2: methyltrimethoxysilane [CH ₃ Si (OC
H ₃ ) ₃ ] c-3: amine silicate CAS 25 (manufactured by Nissan Chemical Industries, Ltd.) [SiO ₂ content = 25%, specific gravity (20 ° C.)
= 1.19, viscosity (cps) = 3.0, pH = 11.
0] c-4: acrylic resin emulsion (pH 8.0, solid content 50%)

(D) Water, hydrophilic organic solvent d-1: ion-exchanged water d-2: i-propanol (e) additive; e-1: nonionic surfactant e-2: aluminum tris (acetylacetate) Nate)

Base nonwoven fabric for shoe insoles (polyester) Nonwoven fabric (nylon) Woven fabric (cotton / hemp blend) Reinforcement mesh polypropylene (mesh 60 mesh)

Preparation of Worked Cloth The liquid composition prepared according to the composition shown in Table 1 was applied to a substrate by the coating method shown in Table 2 to obtain a worked cloth. The curing time after the first application was 10 minutes and the temperature was 100 ° C. The curing time after the second application was 20 minutes and the temperature was 100 ° C.

[0035]

[Table 1]

[0036]

[Table 2]

Examples 1 to 6 Production of shoe insole test pieces As shown in Table 3, shoe insole test pieces T-1 to T-6 were produced using the obtained work cloths 1 to 6.

[0038]

[Table 3]

Control Examples 1-2 Preparation of shoe insole test piece As a commercial product, an odoeater manufactured by Kobayashi Pharmaceutical Co., Ltd. was used. As a commercially available product, Piesante 2 manufactured by Morito Co., Ltd. was used.

Evaluation Test Moisture absorption / discharge property (drying property): To examine the moisture absorption / discharge property (drying property), test pieces T-1 to T-6 shown in Table 3 were used at a temperature of 25.
The sample was left for 1 hour in an environmental test room adjusted to 95 ° C. and a humidity of 95%, the weight after moisture absorption was measured, and the difference from the weight before moisture absorption was defined as the moisture absorption. Next, the moisture-absorbed sample was subjected to a temperature of 25 ° C and a humidity of 5 ° C.
It was left in an environmental test room adjusted to 5% to drain moisture, the weight after 1 hour and 2 hours was measured, and the difference from the weight before draining was defined as the amount of draining. The shoe insole weight was measured after being left for one day in an environmental test room adjusted to a temperature of 25 ° C. and a humidity of 55%. Note that commercially available products were used as controls. Table 4 shows the results.

[0041]

[Table 4]

Antibacterial activity test: To examine the antibacterial activity, an antibacterial activity test against Trichophyton was performed using test pieces T-1 to T-6 shown in Table 3. The test method was as follows. A fixed amount (0.75 g) of a sample cut into about 10 mm × 10 mm was added to 5 ml of Trichophyton suspension and shaken, before adding the test piece, and 1 hour and 6 hours after shaking. After 24 hours, the viable cell count in the Trichophyton suspension was measured. Measurement of viable count
It was performed by a pour plate culture method using a medium for measuring the number of bacteria. A commercially available product was used as a control. Table 5 shows the results.

[0043]

[Table 5]

*) The indication "10 or less" is due to the measurement limit in the bacterial count method used in this test, and means that no bacteria were detected.

Deodorizing property test: In order to examine the deodorizing property, a deodorizing power test for ammonia was performed using test pieces T-1 to T-6 shown in Table 3. In the test method, gaseous ammonia was added to an odor bag (3 liters)
It was injected so as to be 0 ppm, and the change with time of the amount of ammonia (0, 1, 3, 6 hours) was examined. In addition, two nonwoven fabrics (unprocessed) were used as a control. Table 6 shows the results.

[0046]

[Table 6]

Sensory test for athlete's foot (Trichophyton): To examine the therapeutic effect on athlete's foot (Trichophyton), six patients (male) requiring treatment for athlete's foot (Trichophyton) were selected and subjected to a sensory test. However, the patient had used a commercial athlete's foot patch before the start of the sensory test, and had not used any athlete's foot drug after the start of the test. In the test method, two test pieces were given to one patient at a time and worn on shoes to be used. Between the start of the test and the end of the test, 14
We conducted two observations and interviews. Evaluation criteria are
The state of athlete's foot at the start of the test was 100, and the completely cured state of athlete's foot was 0. The results are shown in Tables 7 and 8.

[0048]

[Table 7]

[0049]

[Table 8]

As can be seen from the above results, the shoe insole of the present invention (Examples 1 to 6) shows a large amount of absorbed moisture and quick moisture removal, is excellent in antibacterial properties and deodorizing properties, and particularly is athlete's foot (Trichophyton). Was effective in the treatment of On the other hand, the commercial product or the two non-woven fabrics (unprocessed) used as the control exhibited better moisture absorption / discharge (drying), antibacterial properties, deodorizing properties and the like than the test pieces T-1 to T-6 of Examples 1 to 6. It was inferior.

[0051]

According to the present invention, moisture absorption / discharge (drying),
An insole with excellent antibacterial properties, deodorization properties and heat retention properties, which is particularly effective in treating athlete's foot, has a large effect of preventing its recurrence, and can maintain its performance for a long period of time is obtained.

Claims (4)

[Claims] 1. (A) 0.02 to 2% by weight of silver in terms of silver atom, (B) 10 to 70% by weight of colloidal inorganic substance and / or inorganic fine particles in terms of solid content, (C) as a binder At least one selected from the group consisting of resins, silicates, metal alkoxides and metal hydroxides in the range of 1.5 to 20
% And (D) 8 to 80% by weight of water and / or a hydrophilic organic solvent (provided that (A) + (B) + (C) +
(D) = 100% by weight].
An insole in which a coating layer is formed by applying the liquid composition to a base material for shoe insole and curing the liquid composition by heating at room temperature or low temperature. 2. Silver is selected from the group consisting of silver, silica gel, alumina, titanium oxide, zinc oxide and other metal compounds which are carried on aluminosilicate and / or phosphate compound carriers by ion exchange. The shoe insole according to claim 1, which is silver adsorbed or fixed on at least one kind, and / or colloidal silver. (A) 0.02 to 2% by weight of silver in terms of silver atom, (B) 10 to 70% by weight of colloidal inorganic substance and / or inorganic fine particles in terms of solid content, (C) as a binder At least one selected from the group consisting of resins, silicates, metal alkoxides and metal hydroxides in the range of 1.5 to 20
% And (D) 8 to 80% by weight of water and / or a hydrophilic organic solvent (provided that (A) + (B) + (C) +
(D) = 100% by weight].
A method for producing a shoe insole, wherein the method is applied to a shoe insole substrate, and the liquid composition is cured by heating at room temperature or low temperature to form a coating layer. 4. Silver is selected from the group consisting of silver, silica gel, alumina, titanium oxide, zinc oxide and other metal compounds which are supported on aluminosilicate and / or phosphate compound carriers by ion exchange. 4. The method for producing a shoe insole according to claim 3, which is silver adsorbed or fixed to at least one kind and / or colloidal silver.