WO2019230214A1 - Agent ayant un effet similaire à l'effet réalisé sous irradiation avec de la lumière même lorsqu'il n'est pas irradié avec de la lumière, et procédé de préparation dudit agent - Google Patents

Agent ayant un effet similaire à l'effet réalisé sous irradiation avec de la lumière même lorsqu'il n'est pas irradié avec de la lumière, et procédé de préparation dudit agent Download PDF

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WO2019230214A1
WO2019230214A1 PCT/JP2019/016066 JP2019016066W WO2019230214A1 WO 2019230214 A1 WO2019230214 A1 WO 2019230214A1 JP 2019016066 W JP2019016066 W JP 2019016066W WO 2019230214 A1 WO2019230214 A1 WO 2019230214A1
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agent
particles
effect
silver
oxide
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PCT/JP2019/016066
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English (en)
Japanese (ja)
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司 櫻田
理 櫻田
広志 田代
臼井　清文
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株式会社信州セラミックス
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Priority to JP2020521769A priority Critical patent/JP6983442B2/ja
Priority to CN201980035995.6A priority patent/CN112218714A/zh
Priority to TW108118737A priority patent/TWI793333B/zh
Publication of WO2019230214A1 publication Critical patent/WO2019230214A1/fr
Priority to JP2021185972A priority patent/JP7425497B2/ja

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
    • A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23L—FOODS, FOODSTUFFS, OR NON-ALCOHOLIC BEVERAGES, NOT COVERED BY SUBCLASSES A21D OR A23B-A23J; THEIR PREPARATION OR TREATMENT, e.g. COOKING, MODIFICATION OF NUTRITIVE QUALITIES, PHYSICAL TREATMENT; PRESERVATION OF FOODS OR FOODSTUFFS, IN GENERAL
    • A23L3/00—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs
    • A23L3/34—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals
    • A23L3/3454—Preservation of foods or foodstuffs, in general, e.g. pasteurising, sterilising, specially adapted for foods or foodstuffs by treatment with chemicals in the form of liquids or solids
    • A23L3/358—Inorganic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/01—Deodorant compositions
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L9/00—Disinfection, sterilisation or deodorisation of air
    • A61L9/16—Disinfection, sterilisation or deodorisation of air using physical phenomena
    • A61L9/22—Ionisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/45—Oxides or hydroxides of elements of Groups 3 or 13 of the Periodic Table; Aluminates
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates

Definitions

  • the present invention by providing on the surface of a substrate such as paper, fabric, resin, metal, ceramics, or composite, there is no irradiation of light to bacteria, viruses, allergens, fungi, odorous substances, harmful substances, etc.
  • a substrate such as paper, fabric, resin, metal, ceramics, or composite
  • the present invention relates to an agent capable of producing the same effects as those obtained under continuous light irradiation for a long period of time, and a method for preparing the same.
  • bactericides and deodorizers in solid or liquid form are known. Many of the solid bactericides and deodorizers are related to photocatalyst technology utilizing the redox power of the photocatalyst.
  • a normal photocatalyst can be allowed to act for a long time because the photocatalyst itself is insoluble, but it works only when ultraviolet light is present and does not act in the dark.
  • the photocatalyst since the photocatalyst is solid, it has a bactericidal and deodorizing effect when it comes into contact with bacteria, viruses, allergens, and various organic substances that cause odors. It takes time to be played.
  • liquid disinfectants or deodorizers such as alcohol and hypochlorite usually work without the need for light and immediately have excellent disinfecting or deodorizing effects on the surrounding environment. It only works for a short time because it evaporates or evaporates. Furthermore, generally many liquid disinfectants are still toxic and therefore have the disadvantage of burdening the environment.
  • Conventional photocatalysts have a structure in which metallic silver is supported on a carrier made of, for example, titanium dioxide, and bacteria, viruses, allergens are generated by radicals generated through oxidation-reduction reactions occurring on the surface of the photocatalyst in the presence of ultraviolet light.
  • the organic substances that cause various odors are decomposed to have a sterilizing effect and a deodorizing effect.
  • this redox reaction occurs only at the interface between the silver and titanium dioxide of the photocatalyst, and the reaction is very weak under visible light, so it is considered that the photocatalyst is not useful in a dark environment. It was.
  • Patent Documents 1 and 2 disclose an invention of an agent composed of silver particles and titanium dioxide particles that exhibits a bactericidal effect and a deodorizing effect even in the absence of light. This agent is different from the one in which silver particles are supported on the surface of titanium dioxide particles, and has a physical bond such that the silver particles and the titanium dioxide particles are hard to get into each other.
  • Patent Document 3 a copper compound having a titanium oxide having a rutile-type titanium oxide content of 50 mol% or more and a monovalent copper compound and a divalent copper compound supported on the surface of the titanium oxide.
  • An invention of a supported titanium oxide photocatalyst is disclosed.
  • Patent Document 4 discloses an invention of a visible light responsive hybrid photocatalyst obtained by a mechanochemical reaction between copper ion-supported tungsten oxide particles and zeolite.
  • Patent Documents 3 and 4 do not show that silver particles or copper particles are provided, and are related to a photocatalyst that exhibits catalytic activity under room light. It cannot express catalytic activity.
  • the object of the present invention is an agent that has the same effects as those obtained under continuous light irradiation for a long period of time even without light irradiation, and can exhibit these effects in a short time. Is to provide.
  • the agent having the same effect as the effect under light irradiation without the light irradiation of the first aspect of the present invention is Composite particles in which silver particles and titanium oxide or tungsten oxide particles are physically bonded; (1) At least one kind of metal or metal oxide particles other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite, And at least one material selected from It is characterized by including.
  • the agent of the first aspect of the present invention includes not only composite particles in which silver particles and titanium oxide or tungsten oxide particles are physically bonded, (1) At least one kind of metal or metal oxide particles other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite, And at least one material selected from.
  • composite particles in which silver particles and titanium oxide or tungsten oxide particles are physically bonded are known as agents having the same effects as those obtained under light irradiation even without light irradiation. It is a component.
  • the titanium oxide includes an anatase type, a rutile type, a brookite type, and the like. Any type of titanium oxide may be used, or a mixture of two or more types may be used.
  • copper, nickel, and zinc are all metals that have a higher ionization tendency than silver, so if water is present in the surrounding area, they elute as metal ions before silver.
  • part of the surface of tungsten and molybdenum is oxidized in the air to form tungsten oxide and molybdenum oxide. If moisture is present in the surrounding area, it is eluted as tungstate ion or molybdate ion.
  • part of the surface of copper oxide hydrates and elutes as copper ions when moisture is present in the surroundings.
  • Examples of the silver salt of (2) include easily soluble silver salts such as silver nitrate, silver acetate, silver oxide, silver hydroxide, silver molybdate, silver tungstate, silver carbonate, silver phosphate, silver sulfate, and chromium. Insoluble silver salts such as acid salts, silver halides, and silver oxalates are included. In the case of a readily soluble silver salt, when water is present in the surrounding area, it immediately dissolves to produce silver ions, and in the case of a poorly soluble silver salt, if water is present in the surrounding area, the amount determined by the solubility product of each compound. Silver ions (and anions) are formed.
  • easily soluble silver salts such as silver nitrate, silver acetate, silver oxide, silver hydroxide, silver molybdate, silver tungstate, silver carbonate, silver phosphate, silver sulfate, and chromium.
  • Insoluble silver salts such as acid salts, silver halides, and silver
  • silver ions when water is present in the surroundings, silver ions are generated, so the initial bactericidal effect can be improved.
  • a readily soluble silver salt it immediately dissolves when water is present in the surroundings. Because silver ions are generated, it has high immediate effect.
  • silver nitrate for example, is designated as a deleterious substance by the Poisonous and Deleterious Substances Control Law under Japanese laws and regulations, and it should be noted that the amount used is very small.
  • the silver ion-supporting zeolite (3) is well known as a silver-based inorganic antibacterial agent, and examples thereof include Zeomic (manufactured by Sinanen Zeomic Co., Ltd.), Novalon (manufactured by Toagosei Co., Ltd.), and the like. These silver ion-carrying zeolites also elute silver ions when water is present in the surroundings.
  • the ions formed by at least one material selected from the above (1) to (3) all have an effect on the surroundings before the effect of the composite particles is exerted, the silver particles are consequently obtained.
  • a predetermined effect is achieved in a short time.
  • at least one material selected from the above (1) to (3) exhibits a predetermined effect when moisture is present in the surroundings. The above-described action is caused by the moisture in the material that comes into contact with the agent of the first aspect, for example, moisture contained in microorganisms, viruses, etc., and a predetermined effect can be obtained.
  • the effect of the agent of the first aspect of the present invention is that the composite particles and ions formed from at least one material selected from the above (1) to (3) and the resulting composite particles This is due to the radical formation in the process, but because these ions are formed slowly, the effect is obtained over a long period of time, and there is no biotoxicity, and no resistance bacteria are produced. Become.
  • the composite particles are bonded so that silver particles and titanium oxide or tungsten oxide particles are intercalated.
  • a state in which one of the silver particles and the titanium oxide or tungsten oxide particles is hard to squeeze the other, or one and the other is hard to squeeze each other, can be expressed as being fitted. Physical bonding includes these bonding modes.
  • the selected at least one material is supported on the composite particles. Further, it may be physically bonded to the composite particles.
  • the silver particles and the titanium oxide or tungsten oxide particles in the composite particles are physically bonded, even if the selected at least one material is considered to be supported on the surface of the composite particles Even if it is considered to be physically coupled, it is natural that there is light irradiation, and the same effect as that obtained when there is light irradiation even in the absence of light irradiation. There is an effect.
  • the particle size of the silver particles and the selected at least one material is 100 nm to 1 ⁇ m. It is preferable.
  • the particle size of the silver particles and the selected at least one material does not necessarily have a critical limit, but the above effect is excellent when the particle size is in the range of 100 nm to 1 ⁇ m.
  • the particle size of the silver particles and the selected at least one material is less than 100 nm, when water is present in the surroundings, the dissolution rate of the silver particles and the selected at least one material is increased.
  • the time until the predetermined effect is achieved is shortened, the long-term effect is particularly shortened because the selected at least one material disappears early.
  • the particle size of the silver particles and the selected at least one material exceeds 1 ⁇ m, the long-term effect is improved, but the time until a predetermined effect is initially obtained becomes longer.
  • the content ratio of the silver particles in the composite particles is 0 with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles.
  • the content ratio of the selected at least one material is preferably 2 to 7 parts by mass with respect to 100 parts by mass of titanium oxide or tungsten oxide particles.
  • the content ratio of the silver particles in the composite particles is less than 0.1 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles, the content of the silver particles is too small and it is difficult to achieve a predetermined effect. Moreover, even if the content ratio of silver particles exceeds 5 parts by mass with respect to 100 parts by mass of titanium oxide, the effect is saturated and silver is expensive, which is wasted.
  • a more preferable content ratio of the silver particles in the composite particles is 0.2 to 3 parts by mass with respect to 100 parts by mass of titanium oxide.
  • the content ratio of the selected at least one material is less than 0.2 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles, the content ratio of the selected at least one material is too small. The predetermined effect is not achieved. Moreover, even if the content ratio of the selected at least one material exceeds 7 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles, the effect is saturated. A more preferable content ratio of the selected at least one material is 2.5 to 4 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles.
  • the adsorbent is further contained in an amount of 5 to 50 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles.
  • the adsorbent is preferably hydroxyapatite.
  • bacteria, fungi, viruses, allergens, odorous substances regardless of the presence of the adsorbent And at least one of harmful substances.
  • the adsorbent can adsorb bacteria, fungi, viruses, allergens, odorous substances, harmful substances, and the like (hereinafter, collectively referred to as “objects to be treated”).
  • the processing object can be retained in the vicinity of the composite particles and the selected at least one kind of material, and the above-described effect is favorably achieved.
  • hydroxyapatite is used as the adsorbent, the adsorption effect of the object to be treated is good, and thus the above effect can be achieved better. Moreover, the effect with respect to bacteria, fungi, and a virus is also called a bactericidal effect.
  • the content of the adsorbent is not critical but is preferably 5 to 50 parts by mass with respect to 100 parts by mass of titanium oxide or tungsten oxide particles.
  • the content ratio of the adsorbent is less than 5 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles, the effect of adding the adsorbent is not achieved.
  • the content ratio of the adsorbent exceeds 50 parts by mass with respect to the titanium oxide or tungsten oxide particles, the content ratio of the composite particles and the at least one selected material is relatively decreased, so that the above effect is decreased.
  • a more preferable adsorbent content when hydroxyapatite is used as the adsorbent is 20 to 30 parts by mass with respect to 100 parts by mass of the titanium oxide or tungsten oxide particles.
  • the material of the second aspect of the present invention contains any agent of the first aspect, (A) Woven fabric, nonwoven fabric or paper, wood, resin, metal, ceramics, (B) a composite comprising two or more of woven fabric, non-woven fabric, paper, wood, resin, metal and ceramics, (C) one of paint, resin film, water, cleaning liquid, air filter, and printing ink, It is what was provided to.
  • the material of the second aspect of the present invention it is possible to provide a material that can exhibit the effect of any one of the first aspect.
  • the material may be any of a paint, a resin film, or wallpaper applied to the surface of a house material used indoors.
  • the surface of the housing material used indoors is also the first aspect.
  • One of the effects can be achieved.
  • the material may be a woven fabric, a nonwoven fabric, or paper, and the agent may be impregnated or coated on the material.
  • the material may be used for drinking water, rainwater, hot springs, cooling towers, hydroponics, soil improvement, vegetable washing, food storage, food preservatives.
  • the product of the third aspect of the present invention contains any agent of the first aspect, ⁇ Cloth sheets, bed sheets, pillow covers, towels, handkerchiefs, wash closes, curtains, duvet covers, blanket covers, seat covers, floor cushion covers, covers, table cloths, carpets, air purifying filters, water purifying filters, air conditioners or vehicles Selected from, -Medical supplies selected from medical materials, medical materials, medical products, or medical equipment, ⁇ Adhesive bandages, ointments, skin lotions, cosmetics and hand creams, gauze, catheters, endoscopes, bandages, lab coats, face masks, balloons, medical instrument buttons or resin products for the medical field, ⁇ Drugs, burns, pressure sores, secondary diseases of atopy, drugs provided for at least one of the following diseases: skin or epidermal wounds, Furthermore, it can also be used as one having a bactericidal effect.
  • an adsorbent for example, hydroxyapatite particles may be added.
  • the adsorbent can adsorb the object to be treated when the adsorbent coexists.
  • the object to be treated can be retained in the vicinity of the selected at least one material, and the above-described effects can be favorably achieved. If hydroxyapatite is used as the adsorbent, the adsorption effect of the object to be treated is good, and thus the above effect can be achieved better.
  • the first step (1) passing through a zone maintained at a high temperature; (2) pressurizing each other using a ball mill; and (3) A step of simultaneously performing heating and an operation of pressurizing each other using any of a ball mill, a high temperature roller and a high temperature ultrasonic pressure bonding method, A step selected from the group consisting of:
  • the temperature may be higher than the melting point of silver (962 ° C.), for example, about 1000 ° C. to 3200 ° C.
  • the desired composite particles can be produced in a very short time if the temperature of the thorn is high, but sufficient time is required to produce the desired composite particles if the temperature of the thorn is low. What is necessary is just to set time to pass suitably according to the temperature of a zone.
  • an adsorbent for example, It may be prepared by adding hydroxyapatite particles and mixing or stirring.
  • a method for preparing an agent having the same effect as that obtained under light irradiation even without light irradiation Silver particles, Titanium oxide or tungsten oxide particles; (1) At least one kind of metal or metal oxide particles other than silver selected from copper, copper oxide, nickel, zinc, tungsten, tungsten oxide, molybdenum, and molybdenum oxide, (2) Silver salt, (3) Silver ion supported zeolite, And at least one material selected from Is mixed or stirred in a ball mill to obtain an agent in which at least silver particles and titanium oxide or tungsten oxide particles are physically bonded.
  • adsorbent particles such as hydroxyapatite particles are further added to the ball mill and mixed and stirred. May be prepared.
  • the silver particles, titanium oxide or tungsten oxide particles, and metal or metal other than silver By mixing and stirring the oxide particles in the ball mill, and further mixing and stirring the hydroxyapatite particles in the ball mill, the light of the present invention can be obtained even without light irradiation in one step.
  • An agent having the same effect as that obtained under irradiation can be prepared.
  • a material having a bactericidal effect including an agent having the same effect as that obtained under light irradiation even without light irradiation has composite particles in which metal particles and titanium oxide or tungsten oxide particles are physically bonded, The metal particles are selected from gold, silver, platinum, copper, or a mixture thereof; The composite particles are formed by being adsorbed or applied to a woven fabric, a nonwoven fabric or paper in the presence of soft water having a hardness of 60 or less.
  • the composite particles are woven in the presence of soft water having a hardness of 60 or less, Since it is adsorbed or applied to a nonwoven fabric or paper, the composite particles adhere substantially uniformly without agglomeration on the fiber surface of the woven fabric, nonwoven fabric or paper, and have a good bactericidal effect.
  • a material made of paper can be obtained.
  • Soft water is not preferred when the hardness exceeds 60 because the composite particles tend to aggregate. More preferable soft water has a hardness of 40 or less. Since the composite particles are less likely to aggregate as the hardness is lowered, the adsorption or coating time can be extended so that more composite particles can be uniformly attached to the fiber surface of the woven fabric, nonwoven fabric or paper. Thus, a material made of woven fabric, non-woven fabric or paper having a better sterilizing effect can be obtained.
  • woven fabric, nonwoven fabric or paper together with adsorbent particles such as hydroxyapatite particles It may be adsorbed on or coated on.
  • the material having a bactericidal effect of this aspect when an adsorbent particle, for example, hydroxyapatite, is used as the adsorbent, the adsorbing effect of the object to be treated is improved.
  • a material made of paper can be obtained.
  • the material having the bactericidal effect of this aspect can further have an effect on at least one of allergen, odorous substance and harmful substance.
  • the composite particles can exert not only a bactericidal effect but also an effect on at least one of allergen, odorous substance and harmful substance.
  • the product includes a cloth sheet, a bed sheet, a pillow cover, a towel, a handkerchief, a wash close, a curtain, a duvet cover, and a blanket. It may be selected from a cover, a seat cover, a floor cushion cover, a cover, a table cloth, a carpet, an air purifying filter, or a water purifying filter, or selected from a gauze, bandage, lab coat, face mask. it can.
  • the method for preparing a material having a bactericidal effect including an agent having the same effect as that obtained under light irradiation even without light irradiation according to the eighth aspect of the present invention,
  • the agent has composite particles in which metal particles and titanium oxide or tungsten oxide particles are physically bonded,
  • the metal particles are selected from gold, silver, platinum, copper, or mixtures thereof;
  • the composite particles are adsorbed or applied to the woven fabric, nonwoven fabric or paper by contacting with the composite particles before drying.
  • the composite particles are combined with an adsorbent and the woven fabric, nonwoven fabric or You may prepare by adsorb
  • the composite particles can be used to produce a woven fabric or a non-woven fabric.
  • the paper may have not only a bactericidal effect but also an effect on at least one of allergens, odorous substances and harmful substances.
  • the agent having the same effect as that of the present invention even without light irradiation at least one of bacteria, fungi, viruses, allergens, odorous substances and harmful substances can be obtained.
  • FIG. 3 is a diagram illustrating a method of thermally bonding a ceramic and a metal according to the present invention.
  • FIG. 4 is a diagram illustrating how the ceramic and metal according to the present invention are pressure coupled.
  • FIG. 3 shows how to apply heat / pressure coupling to ceramic and metal according to the present invention.
  • It is a schematic conceptual diagram which shows the combined state of each component in the agent of Experimental example 2. It is a graph which shows the bactericidal effect of Staphylococcus aureus by the agent of various experimental examples. It is the graph which displayed the vertical axis
  • FIG. 2 is a diagram of the use of the agent according to the invention in various products. It is a figure of the agent of the present invention used for drinking water. It is a figure of the agent of the present invention used for preservation of drinking water.
  • FIG. 17A shows the case of using the agent of the present invention and water of hardness 85
  • FIG. 17B shows the case of using the agent of the present invention and water of hardness 60
  • FIG. 17C shows the agent of the present invention and water of hardness 30 It is an electron micrograph at the time of using.
  • FIG. 18A is a conceptual diagram showing a process of attaching the agent of the present invention and water of a predetermined hardness to a sewn garment using a processing apparatus having a drum-type washing machine
  • FIG. 18B is a diagram of the processing apparatus of FIG. 18A.
  • FIG. 18C is a top view of the processing apparatus which supplies the agent of this invention and the water of predetermined
  • FIG. 18D is a sectional side view of FIG. 18C.
  • FIG. 21A is a diagram showing an example in which the agent of the present invention and water of a predetermined hardness are supplied to a textile product by a spray can
  • FIG. 21B is a diagram showing an example in which the textile product is immersed in a container. .
  • the size of the hydroxyapatite particles in the present invention is particularly preferably from 0.3 to 50 ⁇ m in order to secure a wider surface area and to achieve good action.
  • the mixing ratio of the ceramic bonded to the metal and the hydroxyapatite as the adsorbent is 100: 1 to 50 in mass ratio, and has a desirable effect on, for example, bacteria, viruses, allergens, fungi, odorous substances or harmful substances.
  • the ratio is particularly preferably 100: 1 to 30.
  • the agent of the present invention can be prepared by mixing a metal bonded ceramic with an adsorbent.
  • ceramic (TiO 2 ) and metal (silver) particles are bonded through the hot zone shown in FIG.
  • the purity of silver used is 80 to 99.9% and the purity of titanium dioxide is about 90 to 99%.
  • a portion of the metal ingests into the interior of the ceramic particles.
  • the metal particles and the ceramic particles are bonded so that one of them is hard to squeeze the other, or so that one and the other are hard to squeeze each other (also expressed as fitting), that is, physically connected.
  • the temperature of the high temperature zone is substantially about 1000 ° C. to 3200 ° C., for example.
  • the obtained composite particles were confirmed to have a physical bond such that silver particles and titanium dioxide particles were trapped by microscopic observation.
  • the pressure bonding method (2) ceramic and metal are bonded through use of a ball mill shown in FIG.
  • the ball mill has a very hard ball made of a material such as alumina or zirconium, and the ball is, for example, about 0.1 mm and 0.004 mg.
  • the heat / pressure bonding method (3) as shown in FIG. 3, it is possible to bond ceramic and metal particles by simultaneously applying heating and pressing. Further, other methods such as a high temperature roller and a high temperature ultrasonic pressure bonding method may be used as a method for bonding the metal to the ceramic.
  • Experimental Example 1 0.5 g of silver particles having an average particle size of 300 nm, 80 g of anatase-type titanium dioxide particles having an average particle size of 250 nm, and hydroxyapatite (hereinafter simply referred to as “Hy”) having an average particle size of 1 ⁇ m. 20 g) was stirred and mixed in a laboratory ball mill using zirconia balls for 1 to 2 hours to prepare an agent consisting of silver particles-titanium dioxide particles-Hy particles of Experimental Example 1. At this time, the rotation speed of the ball mill was rotated at a low speed so that the titanium dioxide particles were not finely pulverized and the silver particles and the titanium dioxide particles were physically combined.
  • Hy hydroxyapatite
  • the time when the hydroxyapatite is introduced into the ball mill may be the same as the time when the silver particles and the titanium dioxide particles are added, or a predetermined time after the time when the silver particles and the titanium dioxide particles are added. May be.
  • an adsorbent such as hydroxyapatite can be omitted.
  • the silver content in the obtained agent of Experimental Example 1 corresponds to 0.6 parts by mass with respect to 100 parts by mass of titanium dioxide, and similarly the hydroxyapatite content corresponds to 25 parts by mass with respect to 100 parts by mass of titanium dioxide.
  • 35 g of the obtained agent of Experimental Example 1 was dispersed in 65 mL of distilled water to prepare a stock solution of the agent of Experimental Example 1 having a solid content concentration of 35%.
  • the silver content in the obtained agent of Experimental Example 2 corresponds to 0.6 parts by mass with respect to 100 parts by mass of titanium dioxide, and the copper content also corresponds to 1.8 parts by mass with respect to 100 parts by mass of titanium dioxide. Similarly, the content of hydroxyapatite corresponds to 25 parts by mass with respect to 100 parts by mass of titanium dioxide.
  • 35 g of the obtained agent of Experimental Example 2 was dispersed in 65 mL of distilled water to prepare a stock solution of the agent of Experimental Example 2 having a solid concentration of 35%, and used for various microorganism tests.
  • an agent composed of silver particles-copper particles-titanium dioxide particles-Hy particles was prepared in the same manner as in Experimental Example 2 except that the amount of copper added was 3.0 g.
  • the schematic conceptual diagram of the obtained agent of Experimental Example 3 is substantially the same as that of Experimental Example 2 shown in FIG.
  • the silver content in the obtained agent of Experimental Example 3 corresponds to 0.6 parts by mass with respect to 100 parts by mass of titanium dioxide, and the copper content also corresponds to 3.6 parts by mass with respect to 100 parts by mass of titanium dioxide.
  • the content of hydroxyapatite corresponds to 25 parts by mass with respect to 100 parts by mass of titanium dioxide.
  • 35 g of the obtained agent of Experimental Example 3 was dispersed in 65 mL of distilled water to prepare a stock solution of the agent of Experimental Example 3 having a solid content concentration of 35% and used for various microorganism tests.
  • Table 1 summarizes the compositions of the agents of Reference Example and Experimental Examples 1 to 3 prepared as described above.
  • the reference example is a water-only sample (Blank).
  • the copper content is 2 parts by mass or more with respect to 100 parts by mass of the titanium dioxide particles, a good bactericidal effect is achieved, and the amount of copper added is large. The greater the amount, the better the initial bactericidal effect, but the effect is saturated if too much, so the copper content is preferably 7 parts by mass or less with respect to 100 parts by mass of titanium dioxide particles. When these results are interpolated, it is considered that a more preferable copper content is 2.5 to 4 parts by mass with respect to 100 parts by mass of titanium dioxide.
  • FIG. 7 is a diagram showing the relationship between the contact time and the number of detected bacteria
  • FIG. 8 is a diagram showing the relationship between the contact time and log (the number of bacteria).
  • the result of the agent of Experimental Example 2 in which the amount of copper added was small was a sterilizing effect slightly inferior to the agent of Experimental Example 1 containing no copper after 2 hours. This reason is also considered to be due to the same reason as the difference in the bactericidal effect due to the difference in the copper additive with respect to Staphylococcus aureus.
  • Non-Patent Document 1 the bactericidal effect on E. coli in water is sufficient at a concentration of 5 ppm in the case of silver ions, but in the case of copper ions, the concentration of silver ions It is shown that the sterilization effect equivalent to the case where the silver ion concentration is 5 ppm at 625 ppm which is 100 times or more of the above is shown.
  • the agents of Experimental Examples 2 and 3 of the present application copper coexists with silver metal in the form of metal, and both copper metal and silver metal dissolve only in a very small amount in about 2 hours (or hardly dissolve).
  • the copper ion concentration in the test sample is several ppm to several tens of ppm at most, and the silver ion concentration is much lower than that. That is, according to the agent of the present invention, the bactericidal effect against Escherichia coli is the same as in the case of Non-Patent Document 1, while the copper ion concentration and the silver ion concentration are extremely lower than those disclosed in Non-Patent Document 1.
  • a synergistic effect that cannot be predicted from the conventional agent such as Non-Patent Document 1 is achieved.
  • the titanium dioxide particles and the silver particles are physically bonded so as to be intercalated, and the copper particles are substantially supported on the titanium dioxide.
  • the hydroxyapatite particles are bonded in a state where they are supported on titanium dioxide, silver particles, or copper particles.
  • composite particles composed of silver particles-copper particles-titanium dioxide particles are prepared by stirring or mixing titanium dioxide particles, silver particles, and copper particles in a ball mill, and then supporting hydroxyapatite particles.
  • the agent of Modification 2 consisting of silver particles-copper particles-titanium dioxide particles-Hy particles may be prepared.
  • the silver particles and the titanium dioxide particles are physically bonded so that most of them are included, but since copper is harder than silver, a part of the copper particles and the titanium dioxide particles The copper particles are physically bonded so as to be inserted, and the remaining copper particles are bonded while being supported on the surface of titanium dioxide.
  • the hydroxyapatite is couple
  • titanium dioxide particles and silver particles are stirred or mixed in a ball mill to prepare composite particles composed of silver particles-titanium dioxide particles, and then copper particles are added to form silver particles-copper particles-
  • agent of the modification 3 which consists of a titanium dioxide particle agent. That is, an adsorbent such as hydroxyapatite is not bound to the agent of Modification 3.
  • the titanium dioxide particles and the silver particles are physically bonded so that the copper particles are substantially supported on the titanium dioxide.
  • bacteria, viruses, allergens, fungi, odorous substances, harmful substances, and the like have the same effects as those obtained under continuous light irradiation for a long time without light irradiation.
  • Examples 2 and 3 above examples of using 300 nm as the particle diameter of silver particles and the average particle diameter of copper particles are shown, but these particle diameters have clear critical limits. Instead, it may be in the range of 100 nm to 1 ⁇ m. Furthermore, although the example which made content of silver particle 6 mass parts with respect to 100 mass parts of titanium dioxide was shown, the critical limit of this content is also not clear, and titanium dioxide from the point of an effect and economical efficiency.
  • the amount may be in the range of 0.1 to 5 parts by weight with respect to 100 parts by weight, and more preferably 0.2 to 2 parts by weight.
  • titanium dioxide particles were used as metal oxides that form composite particles together with silver particles.
  • titanium dioxide particles can be used.
  • hydroxyapatite is used as the adsorbent, but other known adsorbents such as zeolite, sepiolite, apatite, activated carbon, etc. can also be used.
  • the critical limit of the adsorbent particle size is not clear, for example, when hydroxyapatite is used as the adsorbent, it is particularly preferably 0.3 to 50 ⁇ m in order to secure a wider surface area and achieve good operation.
  • the content ratio of the adsorbent is not critical, but is preferably 10 to 50 parts by mass with respect to 100 parts by mass of the titanium dioxide or tungsten oxide particles.
  • the content ratio of the adsorbent is less than 10 parts by mass with respect to 100 parts by mass of the titanium dioxide or tungsten oxide particles, the effect of adding the adsorbent is not achieved.
  • the content ratio of the adsorbent exceeds 50 parts by mass with respect to the titanium dioxide or tungsten oxide particles, the content ratio of the composite particles and the at least one selected material is relatively decreased, so the above effect is decreased.
  • a more preferable adsorbent content when hydroxyapatite is used as the adsorbent is 20 to 30 parts by mass with respect to 100 parts by mass of titanium dioxide or tungsten oxide particles.
  • copper as at least one material selected from the above, when other materials are used among these materials, for example, bacteria, viruses, allergens, fungi, odorous substances, harmful substances, etc.
  • an agent that has the same effects as those obtained under continuous light irradiation for a long period of time without light irradiation, and that can exhibit these effects in a short time can be obtained.
  • the agent of the present invention can be adhered through a coating or the like for use on an object such as wood, cloth, resin, metal, ceramic, concrete, etc., and these can also be used as an inner filler. While the agent of the present invention is useful as described above, it can be a useful material by being dispersed in a dispersant such as water, an organic solvent, an adhesive or the like.
  • the agent of the present invention can take the form of printing inks and paints. These forms also aim to provide sterilization, deodorization and decorative effects.
  • the printing ink and other forms of the present invention are not limited to ceramics bonded to metal and hydroxyapatite as an adsorbent, but also include at least a coloring material and a carrier.
  • the printing ink contains other components as required.
  • coloring materials not only inorganic coloring matters (pigments) and organic coloring matters (pigments) (that is, coloring materials generally used as printing inks), but also solvent dyes (organic solvent-soluble dyes), disperse dyes, etc. Dyes.
  • examples of carriers include the following.
  • oils such as linseed oil (linseed oil), semi-dry oils such as soybean oil, non-drying oils such as castor oil, natural resins (pine resin (rosin), modified pine resin (modified rosin), gilsonite Etc.), natural resin derivatives, phenol resin, alkyd resin, xylene resin, urea resin, melamine resin, polyamide resin, acrylic resin, epoxy resin, ketone resin, petroleum resin, polyvinyl chloride resin, vinyl acetate resin, urethane resin, Examples thereof include resins such as chlorinated polypropylene, chlorinated rubber, cyclized rubber, cellulosic derivatives, reactive resins, and plasticizers.
  • Other materials include natural wax (natural wax), wax component in synthetic wax (synthetic wax), desiccant, dispersant, wetting agent, cross-linking agent, gelling agent, thickener, anti-skinning Agents, stabilizers, leveling agents, antifoaming agents, color unevenness preventing agents, antifungal agents and the like.
  • the mixing ratio of these components is not critical, but the mixing ratio of common printing inks on the market can be used.
  • the agent of the present invention is used in an amount of 3 to 80% of the total mass of the printing ink, preferably It is preferable to add so as to be 10 to 80%.
  • the form or type of printing ink is not particularly limited. Paste ink, oil-based ink, and solvent-free (solvent-free) ink may be used. It can also be used as offset printing ink, flat printing ink, gravure printing ink, screen method ink, letterpress printing ink, or special printing ink.
  • the screen method ink includes, for example, a screen method ink for paper, a screen method ink for resin, a screen method ink for glass, a screen method ink for metal, and a screen for cloth. Legal inks are preferred among the types described above.
  • the paint contains not only the agent of the present invention but also at least a film-forming component and a dispersant.
  • Film-forming components include cellulosic derivatives, phthalate resins, phenolic resins, alkyd resins, aminoalkyd resins, acrylic resins, epoxy resins, urethane resins, polyvinyl chloride resins, silicon resins, fluororesins, emulsions (emulsions) And synthetic resins such as water-soluble resins, vegetable drying oils and the like.
  • dispersant examples include petroleum solvents, aromatic solvents, alcohol solvents, ester solvents, ketone solvents, cellosolve solvents, water, and the like. In the case of powder coating, a solvent as a dispersant is not necessary.
  • dyes for example, inorganic dyes (pigments) such as titanium dioxide, lead chromate, Bengala (Indian Red), chromium oxide, carbon black, Hansa Yellow, Nova Palm Orange, Quinacridone Violet, Organic pigments such as copper phthalocyanine, precipitated calcium carbonate, barium sulfate, talc, clay, clays such as white carbon, zinc chromate, strontium chromate, zinc phosphate, aluminum phosphate And special functional dyes (pigments) represented by rust-preventing pigments.
  • inorganic dyes pigments
  • pigments such as titanium dioxide, lead chromate, Bengala (Indian Red)
  • chromium oxide carbon black
  • Hansa Yellow Hansa Yellow
  • Nova Palm Orange Quinacridone Violet
  • Organic pigments such as copper phthalocyanine, precipitated calcium carbonate, barium sulfate, talc, clay, clays such as white carbon, zinc chromate, strontium chromate, zinc phosphate, aluminum phosphate
  • auxiliary materials such as dryers (drying agents) that accelerate the drying of paint films, polymerization catalysts, wetting agents, pigment dispersants, color unevenness inhibitors, dyes (pigments)
  • drying agents drying agents
  • Non-curing agent for promoting dispersion, thickener, thixotropic agent, non-sagging agent for adjusting fluidity of pigment (pigment), leveling agent, antifoaming agent, non-crawling agent for adjusting painted surface
  • anti-floating agents, anti-skinning agents, electrostatic coating aids non-scrubbing agents, anti-blocking agents, anti-ultraviolet agents, antifouling agents, antiseptics, antifungal agents and the like.
  • the preferred content of the agent of the present invention is 3 to 3% of the total weight of the paint. 80%, especially 10 to 80% is preferable.
  • the method of coating for paint is not particularly limited. Methods such as paint brush coating, air spray coating, non-air spray coating, electrostatic spray coating, powder coating, electrodeposition coating, curtain flow coating, and roller brush coating can be used.
  • the required area of the agent of the present invention is not particularly limited, but varies depending on the use of the agent.
  • the agent of the present invention can be used by mixing with a liquid or agent that can be used on the human body or other surfaces represented by forms such as ointments and skin lotions, and is effective for sterilization and deodorization.
  • a liquid or agent that can be used on the human body or other surfaces represented by forms such as ointments and skin lotions, and is effective for sterilization and deodorization.
  • ointment for various products such as cosmetics, hand cream 11 shown in FIG. 12, ointment, therapeutic ointment (for athlete's foot, burns, pressure ulcers, secondary diseases of atopy, skin such as wounds, epidermis), mix with liquid or agent. You can also
  • the agent of the present invention can be mixed not only with a liquid solvent or agent, but also with a product such as a resin, ceramic, adhesive, etc., and can be mixed with a raw material for material production.
  • the agent of the present invention can be attached to various materials such as paper, wood, cloth, resin, metal, concrete, and is effective in sterilizing and removing odor.
  • the agent of the present invention can exert a decorative effect by printing in a desired shape or figure, and can be used for various decorations and other purposes when it is not possible to assume the use of light irradiation. Can do.
  • the agent of the present invention is adhered to, for example, ceramics, metal, and composite, purifying drinking water 12 shown in FIG. 12 (FIG. 13), storing drinking water 12, storing rainwater (FIG. 14), rainwater. Reuse, reservoir, pond, vegetable washing, hydroponics, cooling tower, bathtub, hot spring, soil improvement shown in FIG. 16, food preservation, food freshness, drain outlet, tile 13 shown in FIG.
  • the present invention can be used for various products such as the humidifier 14, the medical device, and the column filler shown in FIG. 12.
  • the agent of the present invention is attached to paper to preserve food, filter, medical material, medical product, wallpaper 15 shown in FIG. 12, shoji paper, paper, exterior material of furniture 16 shown in FIG.
  • Such materials, various wrapping papers for products, and housing materials such as bags are useful.
  • various films such as decorative films, protective films, food packaging films, resin products for medical areas such as catheters, endoscopes, balloons, instrument buttons, the personal computer shown in FIG. 30, the telephone 17 shown in FIG. 12, the product such as the jet towel 18 shown in FIG. 12, play equipment, etc., the handrail 19 shown in FIG. 12, the housing material such as the ceiling material 28 shown in FIG. It is equally useful as a material necessary to produce these products. It is also useful as a paste (bundling agent) contained in raw materials for paper, woven fabric and non-woven fabric.
  • the agent of the present invention is attached to a cloth (textile material) and a woven cloth, whereby the cloth 21 shown in FIG. 12, the food material shown in FIG. 12, the agricultural material, the medical material, the adhesive bandage 22 shown in FIG.
  • Various covers such as gauze, bandage, white coat 23 shown in FIG. 12, uniform, face mask 24 shown in FIG. 12, curtain 25 shown in FIG. 12, bed sheet shown in FIG. 12, duvet cover, blanket cover, pillow cover, etc. , Floor cushion cover, etc.), table cloth, carpet 26, towel, handkerchief and other products.
  • it can be used as a material for the air purification filter 27 shown in FIG. 12 and the water purification filter 29 shown in FIG.
  • the agent of this invention can be used also for the air conditioner 31 and the vehicle 32 which are shown in FIG.
  • it can be used for a filter of the air conditioner 31, an air conditioner of the vehicle 32, a seat, a seat cover, an interior, and the like.
  • aquatic animals such as barnacles, sarpula and mussels are driven away for painting buildings and other structures, for painting various products, and for adding low-contamination paint to ships, bridges, piers (piers), etc. Can be used for (repelling). It can also be used to prevent the generation of algae.
  • Example 4 In Experimental Example 4, the behavior when impregnating or applying to a woven fabric, non-woven fabric or paper using water having various hardnesses together with the agent prepared in Experimental Example 1 was investigated.
  • 12 kinds of water in plastic bottles such as commercially available mineral water were prepared as water of various hardnesses.
  • the hardness of these 12 types of water varied depending on the place of origin or brand, and extended from 1612 to 9.9.
  • those with a hardness of 1612 are "Courmayeur” (trade name (hereinafter the same))
  • those with a hardness of 304 are “Evian”
  • those with a hardness of 60 are “Volvic”
  • those with a hardness of 30 are "natural water of the Southern Alps”
  • Those having a hardness of 9.9 are commercially available as“ natural water of Kumano Kodo ”.
  • the pure water obtained through the ion exchange resin was used for the water of hardness 0.
  • FIG. 17A shows a case where the agent of the present invention and water having a hardness of 85 are used
  • FIG. 17B shows a case where the agent of the present invention and water having a hardness of 60 are used
  • the treatment time is as short as about 1 minute, the coexistence of water hardness will depend on it. Aggregation is unlikely to occur, but considering the time taken for the drying and heat treatment steps after treatment, aggregation may occur during this step, which may adversely affect the quality of the final product. Therefore, considering the results shown in Table 4 and FIGS. 17A to 17C comprehensively, the hardness of the coexisting water is preferably 60 or less so that the treatment time can be secured for 5 minutes or more. I understand that. The preferred water hardness is 40 or less in order to ensure a longer treatment time. Furthermore, it is more preferable that the hardness of water is 30 or less because aggregation is further reduced.
  • FIG. 18A is a conceptual diagram showing a process of attaching the agent of the present invention and water of a predetermined hardness to a sewn garment using a processing apparatus having a drum-type washing machine
  • FIG. 18B is a process diagram of FIG. 18A.
  • FIG. 19 is a schematic view of a continuous processing apparatus for adhering the agent of the present invention and predetermined soft water to a raw fabric of a textile product
  • FIG. 20 is a schematic view of a continuous processing apparatus for adhering the agent of the present invention and predetermined soft water to the original fabric of the textile product by screen printing.
  • a processing apparatus 40 shown in FIG. 18A is a drum-type washing machine used in, for example, a coin laundry, and supplies a mixed solution 42 of the agent of the present invention and predetermined soft water to an internal drum 41.
  • Means for discharging are provided.
  • a commercially available drum type washing machine is provided with a water supply pipe for supplying tap water to the inside and a drain pipe for discharging water from the inside. Therefore, a pipe for supplying a mixed solution of the agent of the present invention and a predetermined soft water in the middle of the water supply pipe and the drain pipe, and a pipe for discharging the mixed solution of the internal use agent are connected. What is necessary is just to control the inflow / outflow of each mixed solution with a solenoid valve and an electric pump, respectively.
  • the agent of the present invention and the predetermined soft water are desirably prepared and supplied before use.
  • the unprocessed clothes 43 are placed in the drum 41, and a predetermined amount of the agent of the present invention and a predetermined amount are added.
  • the wet clothes 43 may be sufficiently wetted with the mixed solution 42. Therefore, the number of rotations of the drum may be about several times, and the rotation time may be several minutes, for example, about 2 to 3 minutes.
  • the unprocessed garment 43 is sufficiently wetted by the mixed solution 42 of the agent of the present invention and the predetermined soft water, the mixed solution 42 remaining on the drum 41 is recovered, and dehydration is performed in the same manner as in ordinary washing. I do.
  • the dehydrated clothes are taken out from the processing apparatus 40, and separately subjected to a drying process at about 70 ° C. by the drying apparatus 44, whereby the clothes 45 processed by the agent of the present invention can be obtained.
  • the drying device 44 used at the time of drying is not particularly limited as long as it can be statically heated to about 70 ° C.
  • the processing apparatus 40 includes a drum-type washing machine 50 including a drum 41 and a tank 51 for storing a mixed solution of the agent of the present invention and predetermined soft water.
  • An opening 51a is formed in the upper portion of the tank 51, and the stock solution of the agent of the present invention, a predetermined soft water, an adjusted mixed solution, or another container after use is stored through the opening 51a.
  • a mixed solution or the like is injected into the tank 51.
  • the stock solution of the agent of the present invention is obtained by mixing the agent of the present invention with a predetermined soft water so as to have a predetermined concentration.
  • the drum type washing machine 50 a normal commercially available drum type can be used as it is, a water supply line 52 for supplying tap water for washing inside, and a drain line for discharging water from the inside. 53 is provided.
  • the tank 51 is provided with a mixed solution supply pipe 55 for supplying the mixed solution 42 stored in the tank 51 to the drum-type washing machine 50 from, for example, two ports of the three-way valve 54 from the bottom.
  • the mixed solution supply pipe 55 is connected to the drum type washing machine 50 via a liquid feed pump 56.
  • the remaining port of the three-way valve 54 is connected to an external drain pipe (not shown) via a drainage flow path 57. Further, the liquid feed pump 56 and the three-way valve 54 in the mixed solution supply pipe 55 are connected to the drainage tray 60 via the stop valve 58 and the drain pipe 59.
  • the drain pipe 53 of the drum type washing machine 50 is connected to the upper portion of the tank 51 through two ports of the strainer 61, the reflux pump 62, and the three-way valve 63 and the reflux channel 64.
  • the strainer 61 includes a filter (not shown) for filtering lint and the like, and a container 65 for receiving water leakage is provided at the lower part.
  • the strainer 61 and the reflux pump 62 are connected to the drainage tray 60 via a stop valve 66 and a drain pipe 67.
  • a water supply pipe 71 for supplying water having a predetermined hardness or tap water is connected to the upper portion of the tank 51. If the tap water has a predetermined hardness, the water supply pipe 71 may be connected to the tap pipe and directly supply the tap water, and the tap water and the soft water having the predetermined hardness are switched and supplied. It is good also as composition to do.
  • the operation of the processing apparatus 40 is performed as follows. First, the three-way valve 54 is switched so that the lower part of the tank 51 is connected from the drainage flow path 57 to the mixed solution supply pipe 55. Next, a predetermined amount of the stock solution of the agent of the present invention is supplied from the opening 51a provided in the upper part of the tank 51, a predetermined amount of soft water is supplied from the soft water supply pipe 71, and the mixture is stirred well to have a predetermined concentration A mixed solution 42 containing is prepared.
  • the stop valves 58, 66 and 68 are all closed, the liquid feed pump 56 and the reflux pump 62 are turned off, and the filter (not shown) of the strainer 61 is removed.
  • the drum 41 rotates and enters the drum type washing machine 50.
  • the remaining water is sufficiently discharged into the container 65 through the drain pipe 53 and the strainer 61.
  • the drum type washing machine 50 is provided with an operation panel 50a.
  • the operation panel 50a is provided with, for example, an operation mode switch (not shown). With this operation mode switch, for example, (1) Stirring (2) Thin dough Processing amount 10kg or less (3) Thin dough Processing amount 10kg to 15kg (4) Thick dough 10 kg or less (5) Thick dough 10-15 kg (6) An operation mode such as cleaning can be selected.
  • the mixed solution 42 in the drum type washing machine 50 is rotated by rotating the drum 41 while injecting the mixed solution 42 from the tank 51 to the drum type washing machine 50 by the liquid feed pump 56.
  • the processing time, the rotation speed of the drum, and the like are automatically set according to the mode of the workpiece.
  • the cleaning mode is a mode in which the interior of the drum-type washing machine 50 is cleaned with water supplied from the water supply conduit 52 after the processing is completed or before the processing is started.
  • the rotation direction of the drum is alternately switched between the normal rotation direction and the reverse rotation direction every predetermined time.
  • the operation panel 50a is provided with, for example, an operation time setting switch, a drum rotation speed setting switch, and the like, and the machining conditions set by the operation mode switch are adjusted by manual input using these switches. Is possible.
  • a filter is attached to the strainer 61, the operation mode switch is set to agitation, and the liquid feed pump 56 is turned on.
  • the mixed solution 42 that has been supplied is automatically supplied to the drum type washing machine 50 through the three-way valve 54, the mixed solution supply line 55, and the liquid feed pump 56 and is agitated.
  • the clothes 43 are put in the drum type washing machine 50, and the processing is performed by selecting the operation mode switch.
  • the clothes 43 that has been processed are taken out and dried in the dryer 44 (see FIG. 18A).
  • the next process is continuously performed, after the clothes 43 to be processed again are put in the drum 41, the same processing as described above is performed.
  • the processing for the clothing 43 is performed a predetermined number of times and the processing for the clothing 43 is finished, it is necessary to collect the mixed solution 42 so as not to be deposited inside.
  • the collection process of the mixed solution is performed by turning off the liquid feeding pump 56 and turning on the reflux pump 62.
  • the mixed solution 42 in the drum type washing machine 50 is collected by the reflux pump 62 into the tank 51 through the drain pipe 53, the strainer 61, the three-way valve 63, and the reflux path 64. Further, the mixed solution 42 in the tank 51 can be transferred to an external storage tank (not shown) for storage.
  • the connection from the piping on the outlet side of the liquid feed pump 56 to the storage tank is switched, and the mixed solution 42 is transferred from the tank 51 to the storage tank by the liquid feed pump 56.
  • the piping of the reflux pump 62 is switched, the tank 51 is connected to the inlet side piping of the reflux pump 62, and the storage tank is connected to the outlet side piping of the reflux pump 62. It is possible to transfer the mixed solution 42 from the tank 51 to the storage tank, (3) transfer the mixed solution 42 from the tank 51 to the storage tank using another pump (not shown), and the like.
  • the mixed solution 42 can be repeatedly used for a plurality of times of processing, but a predetermined limit number of times of use is determined in order to maintain the processing quality, and the mixed solution 42 exceeding the limit number of times of use is drained. 67, the water is drained to an external drainage pipe or the like through the drain pipe 69, the drain pipe 59, the drainage channel 57, or the like.
  • tap water can be supplied into the drum type washing machine 50 and the tank 51 via the water supply pipes 51 and 71 to clean the inside.
  • the washing water after washing the drum type washing machine 50 is drained to the drainage tray 60 or an external drain pipe (not shown) through the drain pipe 67, for example.
  • the wash water after washing the tank 51 is drained to an external drain pipe or the like via the drainage channel 57, for example.
  • a spray nozzle 76 is provided on the door 75 of the drum type washing machine 50, as shown in FIGS. 18C and 18D.
  • a mixed solution 77 of the agent of the present invention and predetermined soft water may be supplied by spraying from the spray nozzle 76 into the drum 41.
  • the mixed solution of the agent of the present invention and the predetermined soft water is immediately adsorbed in the clothes 43 or attached to the surface of the clothes 43. Thereby, predetermined sterilization property is provided to textiles.
  • the spray nozzle 76 is provided with a tank for storing the mixed solution 77, and the entire spray nozzle 76 or a part of the tank portion or the like is made a cartridge type so that it can be replaced.
  • the piping of the mixed solution 77 to the nozzle 76 can be omitted.
  • the unprocessed original fabric 81 supplied in a folded state is a roller. It passes through the dipping tank 83 through 82. In this dipping tank 83, a mixed solution 84 of the agent of the present invention and predetermined soft water is stored. The agent of the present invention and the predetermined soft water are absorbed or adhered in the dipping tank 83, and after the excess soft water is removed by the squeezing roller 85, the agent of the present invention passes through the drying / heat treatment section 86 to the inside or the surface of the original fabric It is fixed. As a result, the processed raw fabric 87 is imparted with a predetermined sterilization property and is folded into a predetermined shape, or is wound up in a roll shape by a roller although not shown.
  • the unprocessed raw material supplied in a folded state is provided.
  • the counter 91 is passed through a roller 92 on a base 94 of a screen printing apparatus 93.
  • the screen printing device 93 has a screen mask 95 having a predetermined pattern formed on the bottom, and a mixed solution 96 of the agent of the present invention and predetermined soft water is stored on the screen mask 95.
  • the unprocessed original fabric 91 is passed between the base 94 of the screen printing apparatus 93 and the screen mask 95.
  • a predetermined pigment (pigment or dye) can be mixed in the mixed solution 96 of the agent of the present invention and the predetermined soft water used here.
  • the unprocessed raw material is moved intermittently.
  • the unprocessed original fabric stationary on the table 94 of the screen printing device 93 is sandwiched between the table 94 and the screen mask 95 by the screen printing device 93, and in this state, the squeegee 96 is driven and unprocessed. It is printed on the original fabric in a predetermined pattern by a mixed solution 95 of the agent of the present invention and a predetermined soft water. This operation is the same as in the case of normal screen printing.
  • the raw material on which the mixed solution 66 of the agent of the present invention and the predetermined soft water is printed in a predetermined pattern by the screen printing apparatus 93 is intermittently passed through the drying / heat treatment section 97, so that the agent of the present invention is converted into the original material. It is fixed on the inside or surface.
  • the processed raw fabric 98 having a predetermined pattern with bactericidal properties is folded into a predetermined shape or is wound into a roll by a roller although not shown.
  • this continuous processing apparatus 90 by mixing a predetermined pigment in the mixed solution 66 of the agent of the present invention and a predetermined soft water, not only a bactericidal property but also a pattern of a predetermined pattern is formed on the unprocessed raw fabric. Therefore, it is useful to use a plain one as an untreated raw fabric.
  • the structure for mechanically imparting bactericidal properties to the fiber product or the raw material is shown.
  • the present invention is not limited to this. Is possible.
  • the agent of the present invention, the predetermined soft water, and the spray agent are injected into a spray can, and the agent of the present invention and the predetermined soft water are directed toward the surface of the fiber product or the raw fabric. After spraying in the form of a spray, it is possible to impart bactericidal properties to a predetermined textile or raw material by drying.
  • FIG. 21A the agent of the present invention, the predetermined soft water, and the spray agent are injected into a spray can, and the agent of the present invention and the predetermined soft water are directed toward the surface of the fiber product or the raw fabric. After spraying in the form of a spray, it is possible to impart bactericidal properties to a predetermined textile or raw material by drying.
  • FIG. 21A the agent of the present invention, the predetermined soft water, and the spray agent are injected into a spray can, and
  • the agent prepared in Experimental Example 1 has been described as an example, but the same applies to the use of the agent prepared in Experimental Example 2, Experimental Example 3, or Modified Examples 1 to 3. Further, the agent can be adsorbed or adhered to a fiber such as woven fabric, nonwoven fabric or paper, for example, impregnated or applied.
  • the agent of the present invention adsorbs bacteria, fungi, and viruses, as well as odorous substances and toxic substances. Following or simultaneously with the adsorption, bacteria, fungi, viruses, etc. are degraded. Furthermore, the effect of the agent of the present invention can stop or prevent its growth even if it is not decomposed. In addition, the agent of the present invention has the same effect as that obtained under irradiation of light at room temperature where a human lives on the earth without irradiation of light. Furthermore, since the bacteria, fungi, viruses, etc. which consist of protein are decomposed
  • Bacteria and fungi prefer high temperature and high humidity conditions for growth.
  • the agents of the present invention are particularly effective under high temperature and high humidity conditions and are therefore effective in killing bacteria and fungi.
  • the bactericidal component in the agent of the present invention is insoluble, and the agent of the present invention can be used for a very wide range of uses that kill and suppress unwanted microorganisms such as bacteria and fungi.
  • places where public health, bacteria management, odor management, etc. are required, such as housing, hospitals, nursing homes, public places, food factories, water plants, etc.
  • the agent of the present invention has immediate effect and continuity by using (combining) both existing drugs and various products or systems used. It can be used as a new sterilization system (sterilization technique). For example, after first sterilizing with alcohol, the agent of the present invention can maintain a sterilized state for a long time.
  • the agent of the present invention does not substantially dissolve, it does not give a load to the environment.
  • various pharmaceuticals for the purpose of sterilizing, inactivating viruses, decomposing allergens, and deodorizing.
  • the more effective such medicines have the fact that they are more intrinsically destructive to the human body and nature.
  • the agent of the present invention does not dissolve in water and is effective for a long time, it does not adversely affect the environment.
  • even if there is no light irradiation it has a long-term effect under continuous light irradiation and a similar effect under natural light, and has a wide application range and contributes to industry.

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Abstract

L'invention concerne un agent ayant un effet similaire à un effet réalisé sous une irradiation intermittente avec de la lumière sur une longue période de temps même lorsqu'il n'est pas irradié avec de la lumière, l'agent permettant en outre d'accomplir cet effet en une courte période de temps. L'agent ayant un effet similaire à un effet réalisé sous irradiation avec de la lumière même lorsqu'il n'est pas irradié avec de la lumière selon un mode de réalisation de la présente invention est caractérisé en ce qu'il comprend: des particules composites dans lesquelles des particules d'argent et des particules d'oxyde de titane ou d'oxyde de tungstène sont physiquement combinées; (1) des particules d'au moins un métal autre que l'argent ou un oxyde métallique choisi parmi le cuivre, l'oxyde de cuivre, le nickel, le zinc, le tungstène, l'oxyde de tungstène, du molybdène et de l'oxyde de molybdène; (2) un halogénure d'argent; et (3) au moins un matériau choisi parmi les zéolites supportées par des ions argent.
PCT/JP2019/016066 2018-05-30 2019-04-12 Agent ayant un effet similaire à l'effet réalisé sous irradiation avec de la lumière même lorsqu'il n'est pas irradié avec de la lumière, et procédé de préparation dudit agent WO2019230214A1 (fr)

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JP2020521769A JP6983442B2 (ja) 2018-05-30 2019-04-12 光の照射がなくても光の照射下で有する効果と同様の効果を有する剤を含む殺菌効果を有する材料の製造方法及び殺菌効果を有する製品の製造方法
CN201980035995.6A CN112218714A (zh) 2018-05-30 2019-04-12 无光照射也与光照射下同样有效的制剂及其制备方法
TW108118737A TWI793333B (zh) 2018-05-30 2019-05-30 包含無需光照射仍具有與於光照射下所具有之效果相同之效果的製劑之具有殺菌效果之材料之製造方法及具有殺菌效果之製品之製造方法
JP2021185972A JP7425497B2 (ja) 2018-05-30 2021-11-15 殺菌効果を有する材料の製造方法、殺菌効果を有する製品の製造方法、並びに、殺菌効果及び脱臭効果を有する剤

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CN110747641A (zh) * 2019-11-29 2020-02-04 武汉纺织大学 一种基于无机材料的光致变色碳纤维及其制备方法
CN111359001A (zh) * 2020-03-17 2020-07-03 南京乐康健康科技发展有限公司 一种纳米复合负离子杀菌速粘膜的制备方法
JP2021164640A (ja) * 2020-04-07 2021-10-14 ハーツリッチ株式会社 感染防止方法及び薬剤
EP3895540A1 (fr) * 2020-04-16 2021-10-20 Centrum Badan i Rozwoju Technologii dla Przemyslu S.A. Composition de remplissage pour plastiques et procede de fabrication d'un article en plastique le contenant
JP2022031736A (ja) * 2018-05-30 2022-02-22 株式会社信州セラミックス 光の照射がなくても光の照射下で有する効果と同様の効果を有する剤及びその調製方法
JP2022176091A (ja) * 2021-05-12 2022-11-25 浩河未来実業有限公司 抗微生物組成物及びその製造方法
JP7239122B1 (ja) 2022-08-12 2023-03-14 株式会社進め 殺菌剤、抗感染性繊維材、抗感染性繊維製品、製造方法、及び製造装置
JP7301431B1 (ja) 2022-09-15 2023-07-03 泰陽株式会社 機能性成分放出体粒子の製造方法
US12064850B2 (en) 2021-12-30 2024-08-20 Saint-Gobain Abrasives, Inc. Abrasive articles and methods for forming same

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JP2022031736A (ja) * 2018-05-30 2022-02-22 株式会社信州セラミックス 光の照射がなくても光の照射下で有する効果と同様の効果を有する剤及びその調製方法
JP7425497B2 (ja) 2018-05-30 2024-01-31 株式会社信州セラミックス 殺菌効果を有する材料の製造方法、殺菌効果を有する製品の製造方法、並びに、殺菌効果及び脱臭効果を有する剤
CN110747641A (zh) * 2019-11-29 2020-02-04 武汉纺织大学 一种基于无机材料的光致变色碳纤维及其制备方法
CN111359001A (zh) * 2020-03-17 2020-07-03 南京乐康健康科技发展有限公司 一种纳米复合负离子杀菌速粘膜的制备方法
CN111359001B (zh) * 2020-03-17 2021-04-27 南京乐康健康科技发展有限公司 一种纳米复合负离子杀菌速粘膜的制备方法
JP2021164640A (ja) * 2020-04-07 2021-10-14 ハーツリッチ株式会社 感染防止方法及び薬剤
JP7029132B2 (ja) 2020-04-07 2022-03-03 ハーツリッチ株式会社 感染防止方法
JP7550394B2 (ja) 2020-04-07 2024-09-13 ハーツリッチ株式会社 感染防止用の薬剤
EP3895540A1 (fr) * 2020-04-16 2021-10-20 Centrum Badan i Rozwoju Technologii dla Przemyslu S.A. Composition de remplissage pour plastiques et procede de fabrication d'un article en plastique le contenant
JP2022176091A (ja) * 2021-05-12 2022-11-25 浩河未来実業有限公司 抗微生物組成物及びその製造方法
JP7336157B2 (ja) 2021-05-12 2023-08-31 浩河未来実業有限公司 抗微生物組成物及びその製造方法
US12064850B2 (en) 2021-12-30 2024-08-20 Saint-Gobain Abrasives, Inc. Abrasive articles and methods for forming same
JP7239122B1 (ja) 2022-08-12 2023-03-14 株式会社進め 殺菌剤、抗感染性繊維材、抗感染性繊維製品、製造方法、及び製造装置
JP2024025437A (ja) * 2022-08-12 2024-02-26 株式会社進め 殺菌剤、抗感染性繊維材、抗感染性繊維製品、製造方法、及び製造装置
WO2024034147A1 (fr) * 2022-08-12 2024-02-15 株式会社進め Désinfectant, matériau textile anti-infectieux, produit textile anti-infectieux, procédé de production et dispositif de production
WO2024058238A1 (fr) * 2022-09-15 2024-03-21 泰陽株式会社 Particule de libération de composant fonctionnel, filtre la liant, fibre et méthode de production de particule de libération
JP2024042232A (ja) * 2022-09-15 2024-03-28 泰陽株式会社 機能性成分放出体粒子の製造方法
JP7301431B1 (ja) 2022-09-15 2023-07-03 泰陽株式会社 機能性成分放出体粒子の製造方法

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