WO2019198482A1 - 消臭性・抗菌性の表面層を有する内装材及びその製造方法 - Google Patents
消臭性・抗菌性の表面層を有する内装材及びその製造方法 Download PDFInfo
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- WO2019198482A1 WO2019198482A1 PCT/JP2019/012716 JP2019012716W WO2019198482A1 WO 2019198482 A1 WO2019198482 A1 WO 2019198482A1 JP 2019012716 W JP2019012716 W JP 2019012716W WO 2019198482 A1 WO2019198482 A1 WO 2019198482A1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
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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
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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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
- 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
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- 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
- A61L9/01—Deodorant compositions
- A61L9/012—Deodorant compositions characterised by being in a special form, e.g. gels, emulsions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60R—VEHICLES, VEHICLE FITTINGS, OR VEHICLE PARTS, NOT OTHERWISE PROVIDED FOR
- B60R13/00—Elements for body-finishing, identifying, or decorating; Arrangements or adaptations for advertising purposes
- B60R13/02—Internal Trim mouldings ; Internal Ledges; Wall liners for passenger compartments; Roof liners
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- E—FIXED CONSTRUCTIONS
- E04—BUILDING
- E04F—FINISHING WORK ON BUILDINGS, e.g. STAIRS, FLOORS
- E04F13/00—Coverings or linings, e.g. for walls or ceilings
- E04F13/07—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor
- E04F13/08—Coverings or linings, e.g. for walls or ceilings composed of covering or lining elements; Sub-structures therefor; Fastening means therefor composed of a plurality of similar covering or lining elements
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- 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
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/12—Inorganic materials containing silicon
-
- 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
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/26—Inorganic materials containing copper
-
- 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
- A61L2101/00—Chemical composition of materials used in disinfecting, sterilising or deodorising
- A61L2101/02—Inorganic materials
- A61L2101/30—Inorganic materials containing zinc
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Definitions
- the present invention relates to an interior material having a deodorant / antibacterial surface layer, and more specifically, to an interior material having a deodorant / antibacterial property and a highly transparent surface layer, and a method for producing the same.
- the chemical deodorization method a malodor-causing substance is made non-brominated by chemically reacting with a deodorizing component, and deodorization with high selectivity to a specific malodor-causing substance is possible.
- the physical deodorization method removes malodor-causing substances from the air by physical adsorption, and it is relatively easy to simultaneously adsorb a plurality of malodor-causing substances with one adsorbent.
- activated carbon, zeolite, silica gel, alumina, titania, cyclodextrin and the like are used.
- the sensory deodorization method is a deodorization method in which a bad odor is masked or paired with an aromatic component so as not to feel it.
- This deodorization method unlike other deodorization methods, does not remove the malodor-causing substance from the space, so it can be said that the effect cannot be obtained from the viewpoint of health.
- the biological deodorization method is a method of suppressing the generation of malodor itself by suppressing the growth of microorganisms that are the source of malodor.
- the physical deodorization method is preferable to cope with the deodorization of various odors existing in the living space, and other deodorization methods may be added to the physical deodorization method depending on the situation and location. More preferably, the methods are combined.
- sweat odor is generated when bacteria propagate through sweat and the bacteria decompose sebum mixed with sweat.
- Toilet odor is mainly composed of ammonia that is generated by urine adhering to and around the toilet, which is generated by the decomposition of the urine. Therefore, since the suppression of the growth of these bacteria is effective in suppressing the generation of odors, combining the physical deodorization method with the biological deodorization method can suppress the generation of odor and suppress the generation of odor more. It is effective.
- antibacterial agents added to the adsorbents used in the physical deodorization method have been commercialized as antibacterial and deodorant agents.
- these antibacterial / deodorant agents often do not have sufficient deodorant / antibacterial effects, and antifungal effects do not appear in most products.
- these adsorbents are often granular or powdery and cannot be sprayed or sprayed in the air, so it takes time until the odor comes into contact with the adsorbent and is immediately effective. It is difficult.
- adsorbents are attached to building materials and furniture for interior and exterior of buildings, textile products such as clothing and curtains, and electrical appliances while maintaining their design properties to provide deodorant and antibacterial effects. It was also difficult.
- Antibacterial and antifungal agents can be broadly classified into organic materials and inorganic materials.
- organic synthetic antibacterial and antifungal agents that have been widely used are inexpensive and effective even in small amounts.
- these organic synthetic antibacterial and antifungal agents can often exert their effects only on specific microorganisms (the antibacterial spectrum is narrow), and there is a big difference in their effects on gram-negative bacteria, gram-positive bacteria, molds, etc. There may be.
- these organic synthetic antibacterial and antifungal agents have problems such as resistance bacteria are easily generated, heat resistance is poor, immediate effect is excellent but sustainability is low.
- inorganic antibacterial / antifungal agents materials in which metal ions such as silver, copper and zinc are supported on carriers are mainly used.
- carriers include zeolite, silica gel, calcium phosphate, and zirconium phosphate.
- Inorganic antibacterial and antifungal agents are characterized by their ability to exert effects on a wide range of microorganisms (wide antibacterial spectrum) and high thermal stability compared to organic ones.
- inorganic antifungal agents have a weak antifungal effect, organic antifungal agents are still mainstream as antifungal agents.
- Related prior art documents include the following patent documents 1 to 6.
- an object of the present invention is to provide an interior material having a highly transparent thin film surface layer exhibiting deodorant properties and antibacterial properties, and a method for producing the same.
- the inventors of the present invention have a high deodorant / antibacterial property when the particles containing deodorant titanium oxide particles and alloy particles containing an antibacterial metal are used.
- the present invention has been completed.
- the interior material of the present invention has a surface layer containing deodorant titanium oxide particles and alloy particles containing an antibacterial metal, thereby exhibiting a higher deodorant / antibacterial property than ever.
- this invention provides the interior material which has the surface layer which has the following deodorant and antibacterial property, and its manufacturing method.
- antibacterial may refer to growth inhibition of microorganisms including bacteria and fungi.
- An interior material having a surface layer containing i) titanium oxide particles and ii) alloy particles containing an antibacterial metal [2] The interior material according to [1], wherein the antibacterial metal contained in the alloy particles containing the antibacterial metal of ii) is at least one metal selected from the group consisting of silver, copper and zinc. [3] The interior material according to [2], wherein the alloy particles containing the antibacterial metal of ii) contain at least silver. [4] The interior material according to any one of [1] to [3], wherein the antibacterial metal contained in the alloy particles containing the antibacterial metal of ii) is 1 to 100% by mass relative to the total mass of the alloy particles. .
- the dispersion particle diameter of a particle mixture of the titanium oxide particles of i) and the alloy particles containing the antibacterial metal of ii) is a volume-based 50% cumulative distribution diameter measured by a dynamic scattering method using laser light.
- D 50 interior material according to any one of a 5 ⁇ 100 nm [1] to [4].
- the interior material according to any one of [1] to [5] wherein the surface layer contains a binder.
- the binder is a silicon compound binder.
- the interior material according to any one of [1] to [7] which is a member selected from the group consisting of indoor building materials, interior materials for vehicles, furniture, and electrical appliances.
- the dispersion coating method including i) titanium oxide particles and ii) alloy particles containing an antibacterial metal includes spray coating, flow coating, dip coating, spin coating, Mayer bar coating, gravure coating, knife coating, and kiss coating.
- the method for producing an interior material according to [9] which is die coating and / or film transfer.
- a highly transparent thin film (surface layer) showing deodorant and antibacterial properties can be easily formed, and released from life-related products and buildings without impairing the design of the article. Harmful volatile organic compounds (VOC), sweat odors, aging odors, tobacco odors, garbage odors and other unpleasant odors in daily life, and prevention of microbial contamination such as bacteria and fungi Such effects can be obtained.
- VOC volatile organic compounds
- the deodorant / antibacterial agent contained in the surface layer of the interior material of the present invention comprises a mixture of at least two kinds of particles of i) titanium oxide particles and ii) alloy particles containing an antibacterial metal.
- a mixture of at least two kinds of particles of i) titanium oxide particles and ii) alloy particles containing an antibacterial metal are dispersed in an aqueous dispersion medium.
- this can be produced by mixing at least two types of particle dispersions of titanium oxide particle dispersions prepared separately and alloy particle dispersions containing antibacterial metals.
- Titanium oxide particle dispersion As the crystal phase of titanium oxide particles, three types of rutile type, anatase type, and brookite type are generally known, but it is mainly preferable to use anatase type or rutile type.
- the term “mainly” as used herein refers to generally 50% by mass or more of the entire titanium oxide particle crystal, preferably 70% by mass or more, more preferably 90% by mass or more, and 100% by mass. Also good.
- titanium oxide particles in order to improve the deodorizing performance, titanium oxide particles supported by a metal compound such as platinum, gold, palladium, iron, copper, nickel, tin, nitrogen, sulfur, carbon, What doped elements, such as a transition metal, can also be used, and also titanium oxide used as a photocatalyst can be used.
- a metal compound such as platinum, gold, palladium, iron, copper, nickel, tin, nitrogen, sulfur, carbon, What doped elements, such as a transition metal, can also be used, and also titanium oxide used as a photocatalyst can be used.
- the use of titanium oxide for photocatalysts is more preferable because the deodorizing and antibacterial effects are more strongly obtained when irradiated with light.
- the titanium oxide used as the photocatalyst may be a general photocatalytic titanium oxide or a visible light responsive photocatalytic titanium oxide designed to respond to visible light of 400 to 800 nm.
- an aqueous solvent is usually used, and water is preferably used, but a water-soluble organic solvent that can be mixed with water, water and a water-soluble organic solvent at an arbitrary ratio. You may use the mixed solvent which mixed.
- water for example, deionized water, distilled water, pure water and the like are preferable.
- the water-soluble organic solvent include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and propylene glycol-n-propyl ether. Are preferred.
- the aqueous dispersion medium may be used alone or in combination of two or more thereof.
- the proportion of the water-soluble organic solvent in the mixed solvent is preferably more than 0% by mass and 50% by mass or less, more preferably 20% by mass or less, and still more preferably 10% by mass or less. It is.
- the dispersion particle diameter of the titanium oxide particles in the titanium oxide particle dispersion is a volume-based 50% cumulative distribution diameter D 50 (hereinafter referred to as “average particle diameter”) measured by a dynamic light scattering method using laser light. Is preferably 5 to 30 nm, more preferably 5 to 20 nm. This is because the deodorizing performance may be insufficient when the average particle size is less than 5 nm, and the dispersion may become opaque when it exceeds 30 nm.
- ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd.
- Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
- LA-910 manufactured by Horiba Seisakusho
- the concentration of the titanium oxide particles in the titanium oxide particle dispersion is preferably 0.01 to 30% by mass, particularly 0.5% from the viewpoint of easy production of a titanium oxide / alloy thin film having a required thickness described later. ⁇ 20% by weight is preferred.
- the alloy particle is composed of two or more metal components including at least one antibacterial metal.
- An “antibacterial metal” refers to a metal that is harmful to microorganisms such as bacteria and fungi, but is relatively harmless to the human body.
- a film is coated with metal component particles, and JIS When the standard test of Z 2801 antibacterial processed product is performed, the decrease in the viable count of Staphylococcus aureus and Escherichia coli is confirmed.
- Silver, copper, zinc, platinum, palladium, nickel, aluminum, titanium, cobalt, zirconium, molybdenum And tungsten (the following references 1 and 2).
- the alloy particles used in the interior material of the present invention are preferably alloy particles containing at least one of these metals, and in particular, alloy particles containing at least one metal of silver, copper, and zinc. It is preferable. More specifically, the alloy particles used in the interior material of the present invention are, for example, silver copper, silver palladium, silver platinum, silver tin, gold copper, silver nickel, silver antimony, silver copper tin, gold copper tin, silver nickel tin. And alloy particles containing a combination of metal components such as silver antimony tin, platinum manganese, silver titanium, copper tin, cobalt copper, zinc magnesium, silver zinc, copper zinc, and silver copper zinc.
- Components other than the antibacterial metal in the alloy particles are not particularly limited, but for example, gold, antimony, tin, sodium, magnesium, silicon, phosphorus, sulfur, potassium, calcium, scandium, vanadium, chromium, manganese, iron, gallium , Germanium, arsenic, selenium, yttrium, niobium, technetium, ruthenium, rhodium, indium, tellurium, cesium, barium, hafnium, tantalum, rhenium, osmium, iridium, mercury, thallium, lead, bismuth, polonium, radium, lanthanum, cerium , Praseodymium, neodymium, promethium, samarium, europium, gadolinium, actinium and thorium. These may be used alone or in combination of two or more.
- the content of the antibacterial metal in the alloy particles is 1 to 100% by mass, preferably 10 to 100% by mass, more preferably 50 to 100% by mass with respect to the total mass of the alloy particles. This is because the antibacterial performance may not be sufficiently exhibited when the antibacterial metal is less than 1% by mass with respect to the total mass of the alloy particles.
- an aqueous solvent is usually used, and water, a water-soluble organic solvent that can be mixed with water, or a mixed solvent in which water and a water-soluble organic solvent are mixed at an arbitrary ratio is used. Is preferred.
- water for example, deionized water, distilled water, pure water and the like are preferable.
- water-soluble organic solvent examples include alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol, diethylene glycol, and polyethylene glycol; ethylene glycol monomethyl Glycol ethers such as ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether; ketones such as acetone and methyl ethyl ketone; 2-pyrrolidone Water-soluble nitrogen-containing compounds such as N-methylpyrrolidone; It is may be used singly or in combination of two or more kinds thereof.
- alcohols such as methanol, ethanol, n-propanol, 2-propanol, n-butanol, 2-but
- the dispersed particle diameter of the alloy particles in the alloy particle dispersion may be referred to as a volume-based 50% cumulative distribution diameter D 50 (hereinafter referred to as “average particle diameter”) measured by a dynamic light scattering method using laser light. ) Is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 70 nm or less.
- the lower limit value of the average particle diameter is not particularly limited, and although it is theoretically possible to use a particle having the smallest particle diameter that can have antibacterial properties, it is preferably 1 nm or more in practice. In addition, when the average particle diameter exceeds 200 nm, the dispersion may become opaque, which is not preferable.
- ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd.
- Nanotrack UPA-EX150 manufactured by Nikkiso Co., Ltd.
- LA-910 manufactured by Horiba Seisakusho
- the concentration of the alloy particles in the alloy particle dispersion is not particularly limited, but generally the lower the concentration, the better the dispersion stability, so 0.0001 to 10% by mass is preferable, more preferably 0.001 to 5% by mass, and further Preferably, the content is 0.01 to 1% by mass. If it is less than 0.0001% by mass, the productivity of the interior material is remarkably lowered, which is not preferable.
- Titanium oxide / alloy particle mixed dispersion used in the production of the interior material of the present invention contains a titanium oxide particle dispersion and an antibacterial metal, which are separately configured as described above. It is obtained by mixing the alloy particle dispersion liquid.
- the dispersion particle diameter of the mixture of the titanium oxide particles and the alloy particles containing the antibacterial metal in the titanium oxide / alloy particle mixed dispersion is a volume standard measured by a dynamic light scattering method using laser light.
- 50% cumulative distribution diameter D 50 (hereinafter sometimes referred to as “average particle diameter”) is 5 to 100 nm, preferably 5 to 30 nm, more preferably 5 to 20 nm.
- the average particle size is less than 5 nm, the deodorizing performance may be insufficient, and when it exceeds 100 nm, the dispersion may become opaque.
- the apparatus for measuring the average particle size of the particle mixture of titanium oxide particles and alloy particles is as described above.
- the titanium oxide / alloy particle mixed dispersion used in the interior material of the present invention may contain a binder described later.
- a binder may be added to the titanium oxide / alloy particle mixed dispersion for the purpose of facilitating application of the dispersion to the surfaces of various members described later and adhesion of the particles.
- the binder include metal compound binders containing silicon, aluminum, titanium, zirconium, etc .; organic resin binders containing fluorine resins, acrylic resins, urethane resins and the like.
- the mass ratio of binder to titanium oxide / alloy particles is 0.01 to 99, preferably 0.05 to 20, more preferably 0.1 to 9, and still more preferably. Is in the range of 0.4 to 2.5, and it is preferable to add and use within these ranges. This is because when the mass ratio is less than 0.01, the adhesion of the titanium oxide particles to the surface of various members may be insufficient, and when it exceeds 99, the deodorizing performance and antibacterial performance are insufficient. Because there are things.
- titanium oxide / alloy thin film with high deodorant performance, antibacterial performance and high transparency especially a compound ratio of silicon compound binder (mass ratio of silicon compound: (titanium oxide particles + alloy particles)) It is preferably added to the titanium oxide / alloy particle mixed dispersion in the range of 1:99 to 99: 1, more preferably 10:90 to 90:10, and still more preferably 30:70 to 70:30.
- the “silicon compound-based binder” is a colloidal dispersion, solution or emulsion of a silicon compound containing a solid or liquid silicon compound in an aqueous dispersion medium, specifically, Colloidal silica (preferably particle size 1 to 150 nm); silicate solution such as silicate; silane, siloxane hydrolyzate emulsion; silicone resin emulsion; silicone resin such as silicone-acrylic resin copolymer, silicone-urethane resin copolymer And emulsions of copolymers with other resins.
- colloidal silica preferably particle size 1 to 150 nm
- silicate solution such as silicate
- silane siloxane hydrolyzate emulsion
- silicone resin emulsion silicone resin such as silicone-acrylic resin copolymer, silicone-urethane resin copolymer And emulsions of copolymers with other resins.
- the titanium oxide / alloy particle mixed dispersion liquid in which the concentration is adjusted as described above so that the desired concentration is obtained. It is preferable to add the aqueous binder solution.
- a water-soluble organic solvent, a surfactant, or the like may be added to the titanium oxide / alloy particle mixed dispersion liquid and the coating liquid obtained by adding a binder to the dispersion liquid in order to improve the coating property to the interior material.
- the water-soluble organic solvent examples include alcohols such as methanol, ethanol and isopropanol; glycols such as ethylene glycol; glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether and propylene glycol-n-propyl ether. preferable.
- the proportion of the water-soluble organic solvent in the dispersion or coating liquid is preferably more than 0 and 50% by mass or less, more preferably 20% by mass or less, and still more preferably 10%. It is below mass%.
- surfactants include anionic surfactants such as fatty acid sodium salts, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethyls.
- anionic surfactants such as fatty acid sodium salts, alkylbenzene sulfonates, higher alcohol sulfates, polyoxyethylene alkyl ether sulfates; alkyltrimethylammonium salts, dialkyldimethylammonium salts, alkyldimethyls.
- Cationic surfactants such as benzylammonium salts and quaternary ammonium salts; amphoteric surfactants such as alkylamino fatty acid salts, alkylbetaines and alkylamine oxides; polyoxyethylene alkyl ethers, polyoxyethylene alkylphenol ethers, alkyl glucosides, Polyoxyethylene fatty acid ester, sucrose fatty acid ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid alkanolamine And the like polymeric surfactant; nonionic surfactants, such as. Among these, nonionic surfactants are preferable from the viewpoint of the stability of the dispersion.
- a surfactant When a surfactant is used, a total of 100 parts by mass of the total composition in the titanium oxide / alloy particle mixed dispersion or coating liquid (that is, the above-described titanium oxide particles, alloy particles, nonvolatile impurities, binder, solvent and
- the surfactant concentration is more than 0, preferably 0.001 to 5.0 parts by mass, and 0.01 to 1.0 parts by mass with respect to 100 parts by mass of the surfactants in total. Is more preferably 0.05 to 0.5 parts by mass.
- the method for producing a deodorant / antibacterial agent used in the interior material of the present invention includes the following steps (1) to (6), and the deodorant / antibacterial agent is finally added to an aqueous dispersion medium by adding i It is obtained in a form (mixed solution) in which titanium oxide particles and ii) alloy particles containing an antibacterial metal are dispersed.
- the peroxotitanic acid solution produced in the step (1) is subjected to pressure control. Step of heating at 80 to 250 ° C.
- Step (3) Step of producing a solution containing a raw material antibacterial metal compound and a solution containing a reducing agent for reducing the metal compound (4) Step (5) for producing an alloy particle dispersion by mixing a solution containing the raw material antibacterial metal compound produced in the step (3) and a solution containing a reducing agent for reducing the metal compound (5) (6) Steps (6), (2) and titanium oxide particle dispersions obtained in steps (5) and (5) Step of mixing with liquid
- Steps (1) and (2) are steps for producing a titanium oxide particle dispersion.
- Steps (3) to (5) are steps for producing an alloy particle dispersion.
- the liquid phase reduction method which is one of the superior chemical methods, is used.
- alloy particles are precipitated by mixing a reducing agent in a solution containing two or more kinds of metal ions that are used as raw materials for the alloy.
- the dispersibility of the alloy particles in the solvent can be further improved by coexisting a protective agent for the alloy particles in the reaction system.
- step (6) the titanium oxide particle dispersion obtained in the step (2) and the alloy particle dispersion obtained in the step (5) are mixed, and finally the oxidation having deodorizing and antibacterial properties is performed. It is a manufacturing process of a titanium / alloy particle mixed dispersion. Details of each step will be described below.
- step (1) a peroxotitanic acid solution is produced by reacting a raw material titanium compound, a basic substance, and hydrogen peroxide in an aqueous dispersion medium.
- a basic substance is added to a raw material titanium compound in an aqueous dispersion medium to form titanium hydroxide, impurity ions other than the contained metal ions are removed, and hydrogen peroxide is added.
- hydrogen peroxide is added to the raw material titanium compound, and then a basic substance is added to form peroxotitanium hydrate, impurities other than the contained metal ions are removed, and hydrogen peroxide is further added.
- a method of adding peroxotitanic acid may be used.
- the raw material titanium compound for example, inorganic acid salts such as titanium chloride, nitrate and sulfate; organic acid salts such as formic acid, citric acid, succinic acid, lactic acid and glycolic acid; and alkalis are added to these aqueous solutions And titanium hydroxide deposited by hydrolysis, and one or two or more of these may be used in combination.
- inorganic acid salts such as titanium chloride, nitrate and sulfate
- organic acid salts such as formic acid, citric acid, succinic acid, lactic acid and glycolic acid
- alkalis alkalis
- titanium hydroxide deposited by hydrolysis it is preferable to use titanium chloride (TiCl 3 , TiCl 4 ) as the raw material titanium compound.
- the aqueous dispersion medium those similar to the aqueous dispersion medium in the above-mentioned titanium oxide particle dispersion are used so as to have the above-mentioned composition.
- concentration of the raw material titanium compound aqueous solution formed from a raw material titanium compound and an aqueous dispersion medium is 60 mass% or less, especially 30 mass% or less.
- concentration is selected suitably, it is preferable that it is 1 mass% or more normally.
- the basic substance is for making the raw material titanium compound into titanium hydroxide smoothly.
- hydroxide of alkali metal or alkaline earth metal such as sodium hydroxide or potassium hydroxide; ammonia, alkanolamine, alkyl Examples include amine compounds such as amines.
- the basic substance is used after being added in such an amount that the pH of the raw material titanium compound aqueous solution becomes 7 or more, particularly pH 7-10.
- the basic substance may be used in the form of an aqueous solution having an appropriate concentration together with the aqueous dispersion medium.
- Hydrogen peroxide is used to convert the above raw material titanium compound or titanium hydroxide into peroxotitanium, that is, a titanium oxide compound containing a Ti—O—O—Ti bond, and is usually used in the form of hydrogen peroxide water. Is done.
- the amount of hydrogen peroxide added is preferably 1.5 to 20 times the molar amount of titanium.
- the reaction temperature is preferably 5 to 80 ° C., and the reaction time is 30 minutes to 24 hours. preferable.
- the peroxotitanic acid solution thus obtained may contain an alkaline substance or an acidic substance for pH adjustment or the like.
- examples of the alkaline substance include ammonia, sodium hydroxide, calcium hydroxide, and alkylamine.
- examples of the acidic substance include sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, phosphoric acid, and hydrogen peroxide.
- the obtained peroxotitanic acid solution is preferably pH 1 to 9, particularly pH 4 to 7, from the viewpoint of handling safety.
- step (2) the peroxotitanic acid solution obtained in step (1) is subjected to a hydrothermal reaction for 0.01 to 24 hours at a temperature of 80 to 250 ° C., preferably 100 to 250 ° C. under pressure control. .
- the reaction temperature is appropriately 80 to 250 ° C. from the viewpoint of reaction efficiency and reaction controllability, and as a result, peroxotitanic acid is converted into titanium oxide particles.
- under pressure control means that when the reaction temperature exceeds the boiling point of the dispersion medium, the reaction temperature is appropriately maintained to maintain the reaction temperature so that the reaction temperature can be maintained. This includes the case of controlling at atmospheric pressure when the temperature is lower than the boiling point.
- the pressure is usually about 0.12 to 4.5 MPa, preferably about 0.15 to 4.5 MPa, more preferably 0.20 to 4.5 MPa.
- the reaction time is preferably 1 minute to 24 hours.
- the particle diameter of the titanium oxide particles obtained here is preferably in the range as already described, but it is possible to control the particle diameter by adjusting the reaction conditions, for example, the reaction time and the temperature raising time. It is possible to reduce the particle diameter by shortening.
- step (3) a solution in which the raw material antibacterial metal compound is dissolved in an aqueous dispersion medium and a solution in which a reducing agent for reducing the raw material antibacterial metal compound is dissolved in the aqueous dispersion medium are produced. .
- the method for producing these solutions may be a method in which a raw material antibacterial metal compound and a reducing agent for reducing the raw material antibacterial metal compound are separately added to an aqueous dispersion medium and dissolved by stirring.
- the stirring method is not particularly limited as long as it can be uniformly dissolved in the aqueous dispersion medium, and a generally available stirrer can be used.
- various antibacterial metal compounds can be used.
- inorganic acid salts such as chlorides, nitrates and sulfates of antibacterial metals; formic acid, citric acid, oxalic acid, lactic acid, Organic acid salts such as glycolic acid; complex salts such as ammine complexes, cyano complexes, halogeno complexes, and hydroxy complexes may be used, and one or more of these may be used in combination.
- inorganic acid salts such as chlorides, nitrates and sulfates.
- the reducing agent is not particularly limited, and any of various reducing agents capable of reducing metal ions constituting the raw material antibacterial metal compound can be used.
- the reducing agent include hydrazines such as hydrazine, hydrazine monohydrate, phenylhydrazine and hydrazinium sulfate; amines such as dimethylaminoethanol, triethylamine, octylamine and dimethylaminoborane; citric acid, ascorbic acid, tartaric acid, Organic acids such as malic acid, malonic acid, formic acid; alcohols such as methanol, ethanol, isopropyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, benzotriazole; sodium borohydride, lithium borohydride, hydrogen Lithium triethylborohydride, lithium aluminum hydride, diisobutylaluminum hydride, tributyltin hydride, lithium tri
- a protective agent may be added to a solution obtained by dissolving a reducing agent in an aqueous dispersion medium.
- the protective agent is not particularly limited as long as it can prevent the reduction-precipitated alloy particles from aggregating, and a surfactant or an organic compound having the ability as a dispersant can be used.
- the protective agent include surfactants such as anionic surfactants, cationic surfactants and nonionic surfactants; polyvinylpyrrolidone, polyvinyl alcohol, polyethyleneimine, polyethylene oxide, polyacrylic acid, Water-soluble polymer compounds such as methylcellulose; aliphatic amine compounds such as ethanolamine, diethanolamine, triethanolamine, propanolamine; butylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3-butoxypropylamine, octylamine, Primary amine compounds such as nonylamine, decylamine, dodecylamine, hexadecylamine, oleylamine, octadecylamine; N, N-dimethylethylenediamine, NN-diethylethylenedi Diamine compounds such as amine; and a carboxylic acid compound such as oleic acid.
- surfactants such as anionic
- aqueous dispersion medium aqueous solvent
- water a water-soluble organic solvent that can be mixed with water, or a mixed solvent in which water and a water-soluble organic solvent are mixed at an arbitrary ratio.
- water for example, deionized water, distilled water, pure water and the like are preferable.
- water-soluble organic solvent examples include alcohols such as methanol, ethanol, isopropanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol and diethylene glycol; ethylene glycol monomethyl ether Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether; ketones such as acetone and methyl ethyl ketone; 2-pyrrolidone, Water-soluble nitrogen-containing compounds such as N-methylpyrrolidone; and ethyl acetate .
- the aqueous dispersion medium may be used alone or in combination of two or more thereof.
- Basic substances include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; alkali metal hydrogen carbonates such as sodium hydrogen carbonate and potassium hydrogen carbonate; tert- Alkali metal alkoxides such as butoxy potassium, sodium methoxide and sodium ethoxide; alkali metal salts of aliphatic hydrocarbons such as butyl lithium; amines such as triethylamine, diethylaminoethanol and diethylamine.
- the acidic substance examples include inorganic acids such as aqua regia, hydrochloric acid, nitric acid, and sulfuric acid; organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid, and trichloroacetic acid.
- inorganic acids such as aqua regia, hydrochloric acid, nitric acid, and sulfuric acid
- organic acids such as formic acid, acetic acid, chloroacetic acid, dichloroacetic acid, oxalic acid, trifluoroacetic acid, and trichloroacetic acid.
- the concentration of the solution in which the raw material antibacterial metal compound is dissolved in the aqueous dispersion medium and the concentration of the solution in which the reducing agent for reducing the raw material antibacterial metal compound is dissolved in the aqueous dispersion medium is not particularly limited, In general, the lower the concentration, the smaller the primary particle size of the individual alloy particles formed. Therefore, it is preferable to set a suitable concentration range according to the intended primary particle size range.
- the pH of the solution in which the raw material antibacterial metal compound is dissolved in the aqueous dispersion medium and the pH of the solution in which the reducing agent for reducing the raw material antibacterial metal compound is dissolved in the aqueous dispersion medium are not particularly limited.
- the solution is preferably adjusted to a suitable pH according to the molar ratio of metals in the target alloy particles, the primary particle diameter, and the like.
- step (4) the solution prepared in step (3) in which the raw material antibacterial metal compound is dissolved in the aqueous dispersion medium and the reducing agent for reducing the raw material antibacterial metal compound are contained in the aqueous dispersion medium.
- the dissolved solution is mixed to produce an alloy particle dispersion.
- the method of mixing these two solutions is not particularly limited as long as these two solutions can be mixed uniformly.
- a method of stirring and mixing a metal compound solution and a reducing agent solution in a reaction vessel For example, a method of stirring and mixing a metal compound solution and a reducing agent solution in a reaction vessel. , A method in which a reducing agent solution is dropped while stirring a metal compound solution placed in a reaction vessel, and agitation and mixing, a method in which a metal compound solution is dropped and stirred and agitation is performed in a reaction vessel, a metal Examples thereof include a method in which a compound solution and a reducing agent solution are continuously supplied in a fixed amount and mixed in a reaction vessel or a microreactor.
- the temperature at the time of mixing is not particularly limited, and is preferably adjusted to a suitable temperature according to the molar ratio of the metal in the target alloy particles, the primary particle diameter, and the like.
- step (5) the alloy particle dispersion produced in step (4) is washed with an aqueous dispersion medium by a membrane filtration method.
- aqueous dispersion medium it is preferable to use water, a water-soluble organic solvent that can be mixed with water, or a mixed solvent in which water and a water-soluble organic solvent are mixed at an arbitrary ratio.
- water for example, deionized water, distilled water, pure water and the like are preferable.
- water-soluble organic solvent examples include alcohols such as methanol, ethanol, isopropanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol and diethylene glycol; ethylene glycol monomethyl ether Glycol ethers such as ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol-n-propyl ether; ketones such as acetone and methyl ethyl ketone; 2-pyrrolidone, Water-soluble nitrogen-containing compounds such as N-methylpyrrolidone; and ethyl acetate . You may use a water-soluble organic solvent combining these 1 type (s) or 2 or more types.
- non-volatile impurities other than alloy particles for example, components other than metal in the raw metal compound, reducing agent, protective agent, from the alloy particle dispersion by the membrane filtration method produced in step (4) Wash / separate etc. Washing is preferably performed until the mass ratio of alloy particles to nonvolatile impurities (alloy particles / nonvolatile impurities) in the alloy particle dispersion becomes 0.01 to 10, more preferably 0.05 to 5, and even more. Preferably it is 0.1-1. If the mass ratio is less than 0.01, the amount of impurities to the alloy particles is large, and the resulting antibacterial / antifungal properties and deodorizing performance may not be fully exhibited. This is not preferable because the properties may be lowered.
- Nonvolatile impurity concentration (%) [nonvolatile content mass (g) / mass of alloy particle dispersion before heating (g)] ⁇ 100—metal component concentration in alloy particle dispersion (%)
- the membrane used in the membrane filtration method is not particularly limited as long as it can separate the alloy particles and non-volatile impurities other than the alloy particles from the alloy particle dispersion, but, for example, a microfiltration membrane, an ultrafiltration membrane, or the like. And nanofiltration membranes. Of these, filtration can be performed using a membrane having an appropriate pore size.
- any method such as centrifugal filtration, pressure filtration, or cross flow filtration can be employed.
- the shape of the filtration membrane those having an appropriate form such as a hollow fiber type, a spiral type, a tubular type, and a flat membrane type can be used.
- the material of the filtration membrane is not particularly limited as long as it is durable to the alloy particle dispersion, and is made of polyethylene, tetrafluoroethylene, difluoroethylene, polypropylene, cellulose acetate, polyacrylonitrile, polyimide, polysulfone.
- Organic membranes such as polyethersulfone; inorganic membranes such as silica, alumina, zirconia, and titania can be appropriately selected and used.
- filtration membrane as described above include Microza (Asahi Kasei Chemicals Corporation), Amicon Ultra (Merck Millipore Corporation), Ultra Filter (Advantech Toyo Corporation), MEMBRALOX (Nihon Pole ( Co.)).
- step (6) the titanium oxide particle dispersion obtained in the step (2) and the alloy particle dispersion obtained in the step (5) are mixed to deodorize and have antibacterial titanium oxide / alloy particles. A mixed dispersion is obtained.
- the mixing method is not particularly limited as long as each dispersion is uniformly mixed.
- mixing can be performed by stirring using a generally available stirrer.
- the mixing ratio of the titanium oxide particle dispersion and the alloy particle dispersion is 1 to 100,000, preferably the mass ratio of the titanium oxide particles to the alloy particles in each dispersion (titanium oxide particles / alloy particles). Is 10 to 10,000, more preferably 20 to 1,000. When the mass ratio is less than 1, it is not preferable because the deodorizing performance is not sufficiently exhibited, and when it exceeds 100,000, the antibacterial performance is not sufficiently exhibited, which is not preferable.
- average particle diameter 50% cumulative distribution diameter D 50 on a volume basis measured by a dynamic light scattering method using a laser beam related to the dispersed particle diameter of the mixture of titanium oxide particles and alloy particles in the titanium oxide / alloy particle mixed dispersion , Sometimes referred to as “average particle diameter”) is as described above.
- the apparatus for measuring the average particle diameter is also as described above.
- the total concentration of titanium oxide particles, alloy particles and non-volatile impurities in the titanium oxide / alloy particle mixed dispersion prepared in this way is, as described above, from the viewpoint of easy production of a titanium oxide / alloy thin film having a required thickness. 0.01 to 20% by mass is preferable, and 0.5 to 10% by mass is particularly preferable.
- the total concentration when the total concentration is higher than the desired concentration, the total concentration can be lowered by adding and diluting the aqueous dispersion medium. When the total concentration is lower than the desired total concentration, The total concentration can be increased by volatilizing or filtering the dispersion medium.
- the titanium oxide / alloy particle mixed dispersion can be used for the purpose of forming a deodorant / antibacterial thin film (surface layer) on the surface of the interior material.
- the interior material can have various shapes according to each purpose and application.
- the interior material in the present specification refers to indoor building materials such as, for example, building wall materials, wallpaper, ceiling materials, floor materials, tiles, bricks, wooden boards, resin boards, metal boards, tatami mats, bathroom materials, etc.
- Interior materials such as automobiles and trains, wall materials, ceiling materials, floor materials, seats, handrails, straps, curtains, blinds, rugs, dividers, glass, mirrors, films, desks, chairs, beds, storage
- furniture such as shelves and life-related products
- home appliances such as air purifiers, air conditioners, refrigerators, washing machines, personal computers, printers, tablets, touch panels, and telephones.
- examples of materials for various interior materials include organic materials and inorganic materials.
- organic materials examples include vinyl chloride resin (PVC), polyethylene (PE), polypropylene (PP), polycarbonate (PC), acrylic resin, polyacetal, fluororesin, silicone resin, and ethylene-vinyl acetate copolymer (EVA).
- PVC vinyl chloride resin
- PE polyethylene
- PP polypropylene
- PC polycarbonate
- acrylic resin acrylic resin
- polyacetal polyacetal
- fluororesin silicone resin
- silicone resin ethylene-vinyl acetate copolymer
- EVA ethylene-vinyl acetate copolymer
- inorganic materials include non-metallic inorganic materials and metallic inorganic materials.
- nonmetallic inorganic material include glass, ceramic, stone, and gypsum. These may be processed into various shapes such as tiles, glass, mirrors, walls, and design materials.
- metal inorganic material include cast iron, steel material, iron, iron alloy, stainless steel, aluminum, aluminum alloy, nickel, nickel alloy, and zinc die cast. These may be plated with the metal inorganic material, may be coated with the organic material, or may be plated on the surface of the organic material or non-metallic inorganic material.
- a titanium oxide / alloy particle mixed dispersion or a coating liquid in which a binder is added to the titanium oxide / alloy particle mixed dispersion is used.
- spray coating, flow coating, dip coating, spin coating, Mayer bar coating, reverse roll coating, gravure coating, knife coating, kiss coating, die coating, and the like is used.
- spray coating, flow coating, dip coating, spin coating, Mayer bar coating, reverse roll coating, gravure coating, knife coating, kiss coating, die coating, and the like and then dried.
- a film transfer method for example, spray coating, flow coating, dip coating, spin coating, Mayer bar coating, reverse roll coating, gravure coating, knife coating, kiss coating, die coating, and the like.
- the drying temperature after coating can be variously selected depending on the substrate to be coated, but is preferably 0 to 500 ° C, more preferably 5 to 200 ° C, and still more preferably 10 to 150 ° C. This is because when the temperature is lower than 0 ° C., the dispersion and / or coating solution may be frozen and cannot be used, and when the temperature exceeds 500 ° C., the deodorization / antibacterial properties may be decreased.
- the drying time after coating can be appropriately selected depending on the coating method and the drying temperature, but is preferably 10 seconds to 72 hours, more preferably 20 seconds to 48 hours. This is because if it is less than 10 seconds, the deodorant / antibacterial thin film may not be sufficiently fixed on the surface of the member, and if it exceeds 3 days, the economical efficiency in the production of the interior material is not preferable.
- the thickness of the above surface layer can be appropriately selected, but is preferably 10 nm to 10 ⁇ m, more preferably 20 nm to 5 ⁇ m, still more preferably 50 nm to 1 ⁇ m. This is because if the layer thickness is less than 10 nm, the deodorant and antibacterial properties obtained may be insufficient, and if it exceeds 10 ⁇ m, the surface layer may be easily peeled off from the surface of the interior material. is there.
- the surface layer (deodorant / antibacterial thin film) formed in this way is transparent, and a good deodorant / antibacterial effect can be obtained without impairing the design of the article.
- the interior material formed with can exhibit the effects of cleaning, deodorizing, antibacterial and the like of the interior material by deodorizing and antibacterial action of titanium oxide / alloy particles.
- raw material antibacterial metal compound may be simply referred to as “raw material metal compound”.
- Various performance tests in the present invention were performed as follows.
- test target odor components were 10 types of ammonia, acetic acid, hydrogen sulfide, methyl mercaptan, trimethylamine, acetaldehyde, pyridine, isovaleric acid, nonenal, and indole that are defined in the standard.
- Defect (displayed as C): 3 or more types of gases with an odor component reduction rate of 30% or more
- the titanium oxide / alloy thin film has a thickness of 100 nm on the surface of the 50 mm square interior material. It applied so that it might become, and the test piece was produced. The test piece was tested by a method based on Japanese Industrial Standard JIS Z 2801: 2012 “Antimicrobial Processed Product—Antimicrobial Test Method / Antimicrobial Effect” and evaluated according to the following criteria (Table 6).
- Mold resistance test of titanium oxide / alloy thin film In order to evaluate the anti-mold performance of the titanium oxide / alloy thin film, the titanium oxide / alloy thin film was applied to the surface of a 50 mm square interior material to a thickness of 100 nm. A test piece was prepared. The test piece was evaluated by a method based on Japanese Industrial Standard JIS Z 2911: 2010 “Fung resistance test method” until 8 weeks later. The evaluation was carried out based on the evaluation of the mold growth state stipulated in Appendix A (Table 6). ⁇ Very good (indicated as A) ... Mold growth state is 0-1 ⁇ Good (indicated as B): Mold growth is 2 to 3 ⁇ Defect (displayed as C): Mold growth state is 4-5
- the crystal phase of the titanium oxide particles is obtained by powder X-ray diffraction of the titanium oxide particle powder recovered by drying the obtained dispersion of titanium oxide particles at 105 ° C. for 3 hours (product)
- the name “desktop X-ray diffractometer D2 PHASER” (Bruker AXS Co., Ltd.) was measured (Table 1).
- Average particle diameter D 50 The average particle diameter D 50 of the titanium oxide particle dispersion, the alloy particle dispersion, and the two types of particle mixture of titanium oxide particles and alloy particles is determined by laser light using ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.). Was calculated as a volume-based 50% cumulative distribution diameter measured by a dynamic light scattering method.
- Example 1 ⁇ Preparation of titanium oxide particle dispersion> A 36 mass% titanium chloride (IV) aqueous solution was diluted 10-fold with pure water, and then 10 mass% ammonia water was gradually added to neutralize and hydrolyze to obtain a precipitate of titanium hydroxide. It was. The solution at this time was pH9. The resulting precipitate was subjected to deionization treatment by repeatedly adding pure water and decanting. After this deionization treatment, 35% by mass hydrogen peroxide solution is added to the titanium hydroxide precipitate so that H 2 O 2 / Ti (molar ratio) is 5, and then the mixture is stirred at room temperature for a whole day and night to sufficiently react. To obtain a yellow transparent peroxotitanic acid solution (a).
- Titanium oxide particle dispersion (A) (non-volatile content concentration of 1.0% by mass) was obtained (Table 1).
- a solution (i) containing a reducing agent was obtained by mixing 10% by mass of polyvinylpyrrolidone as a reducing agent / protective agent.
- the alloy particle dispersion ( ⁇ ) was obtained by concentrating and washing with pure water using a 000 ultrafiltration membrane (Microza, Asahi Kasei Co., Ltd.) (Table 3).
- Titanium oxide particle dispersion (A) and alloy particle dispersion ( ⁇ ) are mixed so that the mass ratio of particles in each dispersion (titanium oxide particles / alloy particles) is 100, and titanium oxide / alloy particles are mixed.
- Dispersion liquid (e-1) was obtained.
- Titanium oxide / alloy particle mixed dispersion (e-1) and silica-based binder (colloidal silica, trade name: Snowtex 20, manufactured by Nissan Chemical Industries, Ltd., average particle size 10-20 nm, SiO 2 concentration 20 mass% Aqueous solution) was added so that the TiO 2 / SiO 2 (mass ratio) was 1.5 to prepare an evaluation coating solution (E-1) (Table 4).
- Example 2 ⁇ Preparation of titanium oxide particle dispersion> Yellow transparent peroxotitanium in the same manner as in Example 1 except that tin (IV) chloride was added and dissolved in a 36 mass% titanium chloride (IV) aqueous solution so that the Ti / Sn (molar ratio) was 20. An acid solution (b) was obtained.
- ⁇ Preparation of silver palladium alloy particle mixed dispersion> Contains a raw metal compound in which pure water is used as a solvent, silver nitrate is dissolved so that the concentration as Ag is 4.50 mmol / L, and palladium nitrate dihydrate is dissolved so that the concentration as Pd is 0.50 mmol / L
- An alloy particle dispersion ( ⁇ ) was obtained in the same manner as in Example 1 except that the solution (II) (Table 2) was used (Table 3).
- Titanium oxide particle dispersion (B) and alloy particle dispersion ( ⁇ ) are mixed so that the mass ratio of particles in each dispersion (titanium oxide particles / alloy particles) is 200, and titanium oxide / alloy particles are mixed.
- a dispersion (e-2) was obtained.
- a coating solution for evaluation (E-2) was prepared in the same manner as in Example 1 except that the titanium oxide / alloy particle mixed dispersion (e-2) was used (Table 4).
- Example 3 ⁇ Preparation of silver-zinc alloy particle mixed dispersion> Contains a raw material metal compound in which ethylene glycol is used as a solvent and silver nitrate is dissolved so that the concentration as Ag is 3.75 mmol / L, and zinc nitrate hexahydrate is dissolved so that the concentration as Zn is 1.25 mmol / L An alloy particle dispersion ( ⁇ ) was obtained in the same manner as in Example 1 except that the solution (III) (Table 2) was used (Table 3).
- Titanium oxide particle dispersion (B) and alloy particle dispersion ( ⁇ ) are mixed so that the mass ratio of particles in each dispersion (titanium oxide particles / alloy particles) is 1,000, and titanium oxide / alloy is mixed.
- a particle mixed dispersion (e-3) was obtained.
- a coating solution for evaluation (E-3) was prepared in the same manner as in Example 1 except that the titanium oxide / alloy particle mixed dispersion (e-3) was used (Table 4).
- Example 4 ⁇ Preparation of copper-zinc alloy particle mixed dispersion> Using ethylene glycol as a solvent, copper nitrate trihydrate was dissolved so that the concentration as Cu was 3.75 mmol / L, and zinc nitrate hexahydrate was dissolved so that the concentration as Zn was 1.25 mmol / L.
- An alloy particle dispersion ( ⁇ ) was obtained in the same manner as in Example 1 except that the solution (IV) (Table 2) containing the starting metal compound was used (Table 3).
- Titanium oxide particle dispersion (B) and alloy particle dispersion ( ⁇ ) are mixed so that the mass ratio of particles in each dispersion (titanium oxide particles / alloy particles) is 300, and titanium oxide / alloy particles are mixed.
- a dispersion (e-4) was obtained.
- a coating solution for evaluation (E-4) was prepared in the same manner as in Example 1 except that the titanium oxide / alloy particle mixed dispersion (e-4) was used (Table 4).
- a PET film (product model number “Lumirror T60”, Toray Industries, Inc.) that has been subjected to corona surface treatment is cut into various test sizes, and the coating liquid for evaluation (E-4) is applied to the film surface that has been subjected to corona surface treatment.
- the interior material of the present invention was obtained by coating with a coater and drying in an oven set at 80 ° C. for 30 minutes. Although the surface was observed at a location 20 cm away by visual observation under visible light, there was no abnormality in appearance and the surface layer had high transparency.
- the results of the deodorization test are summarized in Table 5, and the results of the antibacterial test and antifungal test are summarized in Table 6.
- Example 5 ⁇ Preparation of silver-copper alloy particle mixed dispersion>
- concentration concentration with an ultrafiltration membrane having a molecular weight cut off of 10,000 (Microza, Asahi Kasei Co., Ltd.) and washing with pure water
- the amount of washing water used is 1 with respect to the amount of alloy particle dispersion finally obtained.
- An alloy particle dispersion ( ⁇ ) was obtained in the same manner as in Example 1 except that the amount was reduced to 1 ⁇ 2 (from 10 times to 5 times) (Table 3).
- Titanium oxide particle dispersion (B) and alloy particle dispersion ( ⁇ ) are mixed so that the mass ratio of particles in each dispersion (titanium oxide particles / alloy particles) is 100, and titanium oxide / alloy particles are mixed.
- a dispersion (e-5) was obtained.
- a coating solution for evaluation (E-5) was prepared in the same manner as in Example 1 except that the titanium oxide / alloy particle mixed dispersion (e-5) was used (Table 4).
- Example 6 ⁇ Preparation of zinc-magnesium alloy particle mixed dispersion> Using ethylene glycol as a solvent, zinc nitrate hexahydrate was dissolved so that the concentration as Zn was 3.75 mmol / L, and magnesium nitrate hexahydrate was dissolved so that the concentration as Mg was 1.25 mmol / L.
- An alloy particle dispersion ( ⁇ ) was obtained in the same manner as in Example 1 except that the solution (V) containing the starting metal compound (Table 2) was used (Table 3).
- the titanium oxide particle dispersion (A) and the alloy particle dispersion ( ⁇ ) are mixed so that the mass ratio of the particles in each dispersion (titanium oxide particles / alloy particles) is 300.
- An alloy particle mixed dispersion (e-6) was obtained.
- a coating solution for evaluation (E-6) was prepared in the same manner as in Example 1 except that the titanium oxide / alloy particle dispersion (e-6) was used (Table 4).
- Wall tiles made of porcelain used as wall materials were cut into various test sizes, and the coating liquid for evaluation (E-6) was applied with an air spray gun in the same manner as in Example 1 and set to 90 ° C.
- the interior material of the present invention was obtained by drying in an oven for 2 hours. Although the surface was observed at a location 20 cm away by visual observation under visible light, there was no abnormality in appearance and the surface layer had high transparency.
- the results of the deodorization test are summarized in Table 5, and the results of the antibacterial test and antifungal test are summarized in Table 6.
- a titanium oxide particle dispersion (c-1) was obtained only from the dispersion of titanium oxide particles (A).
- a coating solution for evaluation (C-1) was prepared in the same manner as in Example 1 except that the titanium oxide particle dispersion (c-1) was used (Table 4).
- An evaluation coating solution (C-2) was prepared in the same manner as in Example 1 except that the alloy particle dispersion (c-2) was used (Table 4).
- a performance evaluation sample was prepared in the same manner as in Example 2 except that the evaluation coating liquid (C-2) was used. Although the surface was observed at a location 20 cm away by visual observation under visible light, there was no abnormality in appearance and the surface layer had high transparency.
- the results of the deodorization test are summarized in Table 5, and the results of the antibacterial test and antifungal test are summarized in Table 6.
- a silver particle dispersion ( ⁇ ) was obtained in the same manner as in Example 1 except that the solution (VI) containing the starting metal compound was used (Table 3).
- Titanium oxide particle dispersion (A) and silver particle dispersion ( ⁇ ) are mixed so that the mass ratio of particles in each dispersion (titanium oxide particles / silver particles) is 1,000, and titanium oxide / silver is mixed.
- a particle dispersion (c-3) was obtained.
- a coating solution for evaluation (C-3) was prepared in the same manner as in Example 1 except that the titanium oxide / silver particle dispersion (c-3) was used (Table 4).
- the titanium oxide particle dispersion (A) is mixed with a solution (VII) containing a raw material silver compound so that the mass ratio of particles in the dispersion (titanium oxide particles / silver component) is 300, and the titanium oxide / silver particles are dispersed.
- a liquid (c-4) was obtained.
- the titanium oxide particles in the titanium oxide / silver particle dispersion were agglomerated.
- a coating solution for evaluation (C-4) was prepared in the same manner as in Example 1 except that the titanium oxide / silver particle dispersion (c-4) was used (Table 4).
- the two types of particle mixture of titanium oxide particles and alloy particles containing an antibacterial metal showed deodorant, antibacterial and antifungal properties.
- the interior material of the present invention can suppress unpleasant odors and prevent microbial contamination such as bacteria and fungi, and can keep the living space clean.
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Abstract
Description
なお、関連する先行技術文献としては、以下の特許文献1~6が挙げられる。
なお、本明細書において、「抗菌性」とは、細菌、真菌(カビ)を含む微生物の増殖抑制をいう場合がある。
i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とを含有する表面層を有する内装材。
〔2〕
ii)の抗菌性金属を含有する合金粒子に含有される抗菌性金属が、銀、銅及び亜鉛からなる群から選ばれる少なくとも1種類の金属である〔1〕に記載の内装材。
〔3〕
ii)の抗菌性金属を含有する合金粒子が、少なくとも銀を含有するものである〔2〕に記載の内装材。
〔4〕
ii)の抗菌性金属を含有する合金粒子に含有される抗菌性金属が、合金粒子の全質量に対して1~100質量%である〔1〕~〔3〕のいずれかに記載の内装材。
〔5〕
i)の酸化チタン粒子と、ii)の抗菌性金属を含有する合金粒子との粒子混合物の分散粒子径が、レーザー光を用いた動的散乱法により測定される体積基準の50%累積分布径D50で、5~100nmである〔1〕~〔4〕のいずれかに記載の内装材。
〔6〕
さらに、表面層がバインダーを含有するものである〔1〕~〔5〕のいずれかに記載の内装材。
〔7〕
前記バインダーがケイ素化合物系バインダーである〔6〕に記載の内装材。
〔8〕
室内の建築材、車内の内装材、家具及び電化製品からなる群から選ばれる部材である〔1〕~〔7〕のいずれかに記載の内装材。
〔9〕
内装材の表面に、i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とを含む分散液を塗布する工程を有する、〔1〕に記載の内装材の製造方法。
〔10〕
i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とを含む分散液の塗布方法が、スプレーコート、フローコート、ディップコート、スピンコート、メイヤーバーコート、グラビアコート、ナイフコート、キスコート、ダイコート及び/又はフィルム転写である〔9〕に記載の内装材の製造方法。
本発明の内装材の表面層に含まれる消臭・抗菌剤は、i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子との少なくとも2種類の粒子混合物からなるものである。これらを塗布するにあたっては、まず、水性分散媒中に、i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子との少なくとも2種類の粒子が分散された形態とすることが好ましい。後述するように、これは、それぞれ別々に調製した、酸化チタン粒子分散液と、抗菌性金属を含有する合金粒子分散液との少なくとも2種類の粒子分散液を混合して製造することができる。
酸化チタン粒子の結晶相としては、通常、ルチル型、アナターゼ型、ブルッカイト型の3つが知られているが、主として、アナターゼ型又はルチル型のものを使用することが好ましい。なお、ここでいう「主として」とは、酸化チタン粒子結晶全体のうち、通常50質量%以上をいい、好ましくは70質量%以上、更に好ましくは90質量%以上であり、100質量%であってもよい。
光触媒用酸化チタンを使用すると、光が照射された時に消臭・抗菌効果がより強く得られるため、より好ましい。
光触媒として使用される酸化チタンは一般的な光触媒酸化チタンであっても、400~800nmの可視光に応答するように設計された可視光応答型光触媒酸化チタンであってもよい。
酸化チタン粒子分散液の濃度(%)=〔不揮発分質量(g)/加熱前の酸化チタン粒子分散液質量(g)〕×100
本発明において、合金粒子は、抗菌性金属を少なくとも1種含んだ、2種以上の金属成分からなるものである。
「抗菌性金属」とは、細菌や真菌(カビ)などの微生物には有害であるが、人体には比較的害の少ない金属のことを指し、例えば、フィルムに金属成分粒子をコーティングし、JIS Z 2801 抗菌加工製品の規格試験を行った場合、黄色ブドウ球菌や大腸菌の生菌数の減少が確認される、銀、銅、亜鉛、白金、パラジウム、ニッケル、アルミニウム、チタン、コバルト、ジルコニウム、モリブデン、タングステンなどが挙げられる(下記参考文献1、2)。
参考文献2:H.Kawakami、ISIJ Intern.,48(2008)9, 1299-1304
本発明の内装材の製造に用いられる酸化チタン・合金粒子混合分散液は、上述の通り、別々に構成された、酸化チタン粒子分散液と、抗菌性金属を含有する合金粒子分散液とを混合することによって得られるものである。
ここで、酸化チタン・合金粒子混合分散液中の酸化チタン粒子及び抗菌性金属を含有する合金粒子との混合物の分散粒子径は、レーザー光を用いた動的光散乱法により測定される体積基準の50%累積分布径D50(以下、「平均粒子径」ということがある。)が、5~100nm、好ましくは5~30nm、より好ましくは5~20nmである。これは、平均粒子径が、5nm未満の場合、消臭性能が不十分になることがあり、100nm超過の場合、分散液が不透明となることがあるためである。
なお、酸化チタン粒子及び合金粒子の粒子混合物の平均粒子径を測定する装置は、上述の通りである。
また、本発明の内装材に用いられる酸化チタン・合金粒子混合分散液には、後述するバインダーを含有してもよい。
本発明の内装材に用いられる消臭・抗菌剤の製造方法は、以下の工程(1)~(6)を含み、該消臭・抗菌剤は、最終的に、水性分散媒中に、i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とが分散された形態(混合液)で得られる。
(1)原料チタン化合物、塩基性物質、過酸化水素及び水性分散媒から、ペルオキソチタン酸溶液を製造する工程
(2)上記(1)の工程で製造したペルオキソチタン酸溶液を、圧力制御下、80~250℃で加熱し、酸化チタン粒子分散液を得る工程
(3)原料抗菌性金属化合物を含む溶液と、該金属化合物を還元するための還元剤を含む溶液とを製造する工程
(4)上記(3)の工程で製造した原料抗菌性金属化合物を含む溶液と、該金属化合物を還元するための還元剤を含む溶液とを混合して合金粒子分散液を製造する工程
(5)上記(4)の工程で製造した合金粒子分散液を膜ろ過法により水性分散媒で洗浄する工程
(6)(2)の工程と(5)の工程で得られた酸化チタン粒子分散液と合金粒子分散液とを混合する工程
工程(3)~(5)は、合金粒子分散液の製造工程である。該製造工程は、物理的方法や化学的方法がある中、特に、合成条件の調整が容易で、組成、粒径・粒度分布などの制御可能範囲が広く、合金粒子の生産性の観点から、優位性がある化学的方法の一つである液相還元法を利用するものである。該液相還元法では、合金の原料になる2種類以上の金属イオンを含んだ溶液に還元剤を混合することで、合金粒子を析出させる。このとき、反応系内に合金粒子の保護剤を共存させることで、合金粒子の溶媒への分散性を更に向上させることもできる。
工程(6)は、工程(2)で得られた酸化チタン粒子分散液と、工程(5)で得られた合金粒子分散液とを混合して、最終的に消臭・抗菌性を有する酸化チタン・合金粒子混合分散液の製造工程である。
以下、各工程についての詳細を述べる。
工程(1)では、原料チタン化合物、塩基性物質及び過酸化水素を水性分散媒中で反応させることにより、ペルオキソチタン酸溶液を製造する。
工程(2)では、上記工程(1)で得られたペルオキソチタン酸溶液を、圧力制御下、80~250℃、好ましくは100~250℃の温度において0.01~24時間水熱反応に供する。反応温度は、反応効率と反応の制御性の観点から80~250℃が適切であり、その結果、ペルオキソチタン酸は酸化チタン粒子に変換される。なお、ここで「圧力制御下」とは、反応温度が分散媒の沸点を超える場合には、反応温度が維持できるように、適宜加圧を行い、反応温度を維持することをいい、分散媒の沸点以下の温度とする場合に大気圧で制御する場合を含む。ここで、圧力は、通常0.12~4.5MPa程度、好ましくは0.15~4.5MPa程度、より好ましくは0.20~4.5MPaである。反応時間は、1分~24時間であることが好ましい。この工程(2)により、酸化チタン粒子分散液が得られる。
工程(3)では、原料抗菌性金属化合物を水性分散媒中に溶解させた溶液と、該原料抗菌性金属化合物を還元するための還元剤を水性分散媒中に溶解させた溶液とを製造する。
工程(4)では、工程(3)で調製した、原料抗菌性金属化合物を水性分散媒中に溶解させた溶液と、該原料抗菌性金属化合物を還元するための還元剤を水性分散媒中に溶解させた溶液とを混合し、合金粒子分散液を製造する。
工程(5)では、工程(4)で製造した合金粒子分散液を膜ろ過法により水性分散媒で洗浄する。
合金粒子分散液中の金属成分濃度は、合金粒子分散液を純水で適宜希釈し、誘導結合プラズマ発光分光分析装置(商品名“Agilent 5110 ICP-OES”、アジレント・テクノロジー(株))に導入して測定することができる。
ここで、合金粒子分散液の金属成分以外の不揮発性不純物濃度は、合金粒子分散液の一部をサンプリングし、105℃で3時間加熱して溶媒を揮発させた後の不揮発分(合金粒子+不揮発性不純物)の質量と、サンプリングした加熱前の合金粒子分散液の質量とから算出した不揮発分濃度から、上記ICP-OESで定量した金属成分濃度を引くことで算出することができる。
不揮発性不純物濃度(%)=〔不揮発分質量(g)/加熱前の合金粒子分散液質量(g)〕×100-合金粒子分散液中の金属成分濃度(%)
工程(6)では、工程(2)で得られた酸化チタン粒子分散液と、工程(5)で得られた合金粒子分散液とを混合し、消臭・抗菌性を有する酸化チタン・合金粒子混合分散液を得る。
また、平均粒子径を測定する装置も、上述の通りである。
酸化チタン・合金粒子混合分散液の濃度(質量%)=〔不揮発分質量(g)/加熱前の酸化チタン・合金粒子混合分散液質量(g)〕×100
上記の酸化チタン・合金粒子混合分散液は、内装材の表面に消臭・抗菌性薄膜(表面層)を形成させる目的で使用することができる。内装材は、それぞれの目的、用途に応じた様々な形状を有することができる。
非金属無機材料としては、例えば、ガラス、セラミック、石材、石膏等が挙げられる。これらは、タイル、硝子、ミラー、壁、意匠材等の様々な形に加工されていてもよい。
金属無機材料としては、例えば、鋳鉄、鋼材、鉄、鉄合金、ステンレス、アルミニウム、アルミニウム合金、ニッケル、ニッケル合金、亜鉛ダイキャスト等が挙げられる。これらは、上記金属無機材料のメッキが施されていてもよいし、上記有機材料が塗布されていてもよいし、上記有機材料又は非金属無機材料の表面に施すメッキであってもよい。
なお、「原料抗菌性金属化合物」は、単に、「原料金属化合物」ということがある。
本発明における各種の性能試験は次のようにして行った。
酸化チタン・合金薄膜を表面に有する本発明の内装材の消臭性能を評価するために、酸化チタン・合金粒子混合分散液とバインダーとから調製した評価用コーティング液を、100mm角に裁断した内装材に、1g塗布、乾燥することで試験片を作製した。該試験片について、(一般社団法人)繊維評価技術協議会のJEC301「SEKマーク繊維製品認証基準」内に記載されている消臭性試験に準拠した方法で試験し、次の基準で評価した(表5)。試験対象臭気成分は、該基準内に定められているアンモニア、酢酸、硫化水素、メチルメルカプタン、トリメチルアミン、アセトアルデヒド、ピリジン、イソ吉草酸、ノネナール、インドールの10種類とした。
・非常に良好(Aと表示)・・・臭気成分減少率30%以上のガスが7種類以上
・良好(Bと表示)・・・臭気成分減少率30%以上のガスが5種類以上
・やや不良(Cと表示)・・・臭気成分減少率30%以上のガスが3種類以上
・不良(Dと表示)・・・臭気成分減少率30%以上のガスが2種類以下
酸化チタン・合金薄膜を表面に有する本発明の内装材の抗菌性能を評価するために、酸化チタン・合金薄膜を50mm角の内装材表面に厚み100nmになるように塗布して試験片を作製した。該試験片について、日本工業規格JIS Z 2801:2012「抗菌加工製品-抗菌性試験方法・抗菌効果」に準拠した方法で試験し、次の基準で評価した(表6)。
・非常に良好(Aと表示)・・・全ての抗菌活性値が4.0以上の場合
・良好(Bと表示)・・・全ての抗菌活性値が2.0以上の場合
・不良(Cと表示)・・・抗菌活性値2.0未満がある場合
酸化チタン・合金薄膜の抗カビ性能を評価するために、酸化チタン・合金薄膜を50mm角の内装材表面に厚み100nmになるように塗布して試験片を作製した。該試験片について、日本工業規格JIS Z 2911:2010「カビ抵抗性試験方法」に準拠した方法で8週間後まで評価した。評価は附属書Aに規定のカビ発育状態の評価により行い次の基準で評価した(表6)。
・非常に良好(Aと表示)・・・カビ発育状態が0~1
・良好(Bと表示)・・・カビ発育状態が2~3
・不良(Cと表示)・・・カビ発育状態が4~5
酸化チタン粒子の結晶相は、得られた酸化チタン粒子の分散液を105℃、3時間乾燥させて回収した酸化チタン粒子粉末の粉末X線回折(商品名“卓上型X線回折装置 D2 PHASER”、ブルカー・エイエックスエス(株))を測定することで同定した(表1)。
合金粒子が合金であるかどうかの判定は、走査透過型電子顕微鏡観察(STEM、日本電子製ARM-200F)下でのエネルギー分散型X線分光分析によって行った。具体的には、得られた合金粒子分散液をTEM観察用カーボングリッドに滴下して水分を乾燥除去して拡大観察し、平均的な形状とみなせる粒子を複数含む視野を数箇所選んでSTEM-EDXマッピングを行い、合金を構成する各金属成分が一つの粒子内から検出されることが確認できた場合には合金粒子であるとして「○」、確認できなかった場合には合金粒子でないとして「×」と判定した。
酸化チタン粒子分散液、合金粒子分散液及び酸化チタン粒子と合金粒子との2種類の粒子混合物の平均粒子径D50は、ELSZ-2000ZS(大塚電子(株)製)を使用して、レーザー光を用いた動的光散乱法により測定される体積基準の50%累積分布径として算出した。
<酸化チタン粒子分散液の調製>
36質量%の塩化チタン(IV)水溶液を純水で10倍に希釈した後、10質量%のアンモニア水を徐々に添加して中和、加水分解することにより、水酸化チタンの沈殿物を得た。このときの溶液はpH9であった。得られた沈殿物を、純水の添加とデカンテーションとを繰り返して脱イオン処理した。この脱イオン処理後の、水酸化チタン沈殿物にH2O2/Ti(モル比)が5となるように35質量%過酸化水素水を添加し、その後室温で一昼夜撹拌して十分に反応させ、黄色透明のペルオキソチタン酸溶液(a)を得た。
エチレングリコールを溶媒とし、Agとしての濃度が2.50mmol/Lとなるように硝酸銀、Cuとしての濃度が2.50mmol/Lとなるように硝酸銅三水和物を溶解して原料金属化合物を含む溶液(I)を得た(表2)。
天井板として使用される化粧石膏ボードを各種試験のサイズにカットし、吐出圧力を0.2MPaに調整したエアスプレーガン(商品型番“LPH-50-S9-10”、アネスト岩田(株))で評価用コーティング液(E-1)を塗工し、20℃の室内で24時間乾燥させて、本発明の内装材を得た。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<酸化チタン粒子分散液の調製>
36質量%の塩化チタン(IV)水溶液に塩化スズ(IV)をTi/Sn(モル比)が20となるように添加・溶解したこと以外は実施例1と同様にして、黄色透明のペルオキソチタン酸溶液(b)を得た。
純水を溶媒とし、Agとしての濃度が4.50mmol/Lとなるように硝酸銀、Pdとしての濃度が0.50mmol/Lとなるように硝酸パラジウム二水和物を溶解した原料金属化合物を含む溶液(II)(表2)を使用したこと以外は実施例1と同様にして、合金粒子分散液(β)を得た(表3)。
室内の間仕切り板として使用されるメラミン化粧板を各種試験のサイズにカットし、実施例1と同様にエアスプレーガンで評価用コーティング液(E-2)を塗工し、50℃に設定したオーブンで3時間乾燥させて、本発明の内装材を得た。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<銀亜鉛合金粒子混合分散液の調製>
エチレングリコールを溶媒とし、Agとしての濃度が3.75mmol/Lとなるように硝酸銀、Znとしての濃度が1.25mmol/Lとなるように硝酸亜鉛六水和物を溶解した原料金属化合物を含む溶液(III)(表2)を使用したこと以外は実施例1と同様にして、合金粒子分散液(γ)を得た(表3)。
室内の床材として使用されるフロアタイル(塩ビ樹脂系)を各種試験のサイズにカットし、実施例1と同様にエアスプレーガンで評価用コーティング液(E-3)を塗工し、50℃に設定したオーブンで1時間乾燥させて、本発明の内装材を得た。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<銅亜鉛合金粒子混合分散液の調製>
エチレングリコールを溶媒とし、Cuとしての濃度が3.75mmol/Lとなるように硝酸銅三水和物、Znとしての濃度が1.25mmol/Lとなるように硝酸亜鉛六水和物を溶解した原料金属化合物を含む溶液(IV)(表2)を使用したこと以外は実施例1と同様にして、合金粒子分散液(δ)を得た(表3)。
コロナ表面処理を施したPETフィルム(商品型番“ルミラー T60”、東レ(株))を各種試験のサイズにカットし、コロナ表面処理を施したフィルム面に評価用コーティング液(E-4)をバーコーターで塗工し、80℃に設定したオーブンで30分間乾燥させて、本発明の内装材を得た。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<銀銅合金粒子混合分散液の調製>
分画分子量10,000の限外ろ過膜(マイクローザ、旭化成(株))による濃縮及び純水洗浄を行う際に、最終的に得られる合金粒子分散液量に対して使用する洗浄水量を1/2量(10倍量から5倍量)に減らしたこと以外は実施例1と同様にして、合金粒子分散液(ε)を得た(表3)。
室内の間仕切り板として使用されるメラミン化粧板を各種試験のサイズにカットし、実施例1と同様にエアスプレーガンで評価用コーティング液(E-5)を塗工し、50℃に設定したオーブンで3時間乾燥させて、本発明の内装材を得た。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<亜鉛マグネシウム合金粒子混合分散液の調製>
エチレングリコールを溶媒とし、Znとしての濃度が3.75mmol/Lとなるように硝酸亜鉛六水和物、Mgとしての濃度が1.25mmol/Lとなるように硝酸マグネシウム六水和物を溶解した原料金属化合物を含む溶液(V)(表2)を使用したこと以外は実施例1と同様にして、合金粒子分散液(ζ)を得た(表3)。
壁面材として使用される壁面タイル(陶磁器製)を各種試験のサイズにカットし、実施例1と同様にエアスプレーガンで評価用コーティング液(E-6)を塗工し、90℃に設定したオーブンで2時間乾燥させて、本発明の内装材を得た。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
酸化チタン粒子(A)の分散液のみから酸化チタン粒子分散液(c-1)を得た。
評価用コーティング液(C-1)を使用したこと以外は実施例1と同様にして、性能評価用サンプルを作製した。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
合金粒子分散液(α)の分散液のみから合金粒子分散液(c-2)を得た。
評価用コーティング液(C-2)を使用したこと以外は実施例2と同様にして、性能評価用サンプルを作製した。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<銀粒子分散液の調製>
エチレングリコールを溶媒とし、銀としての濃度が4.00mmol/Lとなるように硝酸銀を溶解して原料金属化合物を含む溶液(VI)を得た(表2)。
評価用コーティング液(C-3)を使用したこと以外は実施例3と同様にして、評価用サンプルを作製した。可視光下で目視により20cm離れた箇所で表面観察したが、外観異常はなく、透明性の高い表面層を有していた。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
<原料銀液の調製>
純水を溶媒とし、銀としての濃度が4.00mmol/Lとなるように硝酸銀を溶解して原料銀化合物を含む溶液(VII)を得た(表2)。
評価用コーティング液(C-4)を使用したこと以外は実施例2と同様にして、性能評価用サンプルを作製した。可視光下で目視により20cm離れた箇所で表面観察したところ、外観は白濁しており、透明性の高い表面層を有していなかった。消臭性試験の結果を表5に、抗菌性試験、抗カビ性試験の結果を表6にまとめた。
Claims (10)
- i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とを含有する表面層を有する内装材。
- ii)の抗菌性金属を含有する合金粒子に含有される抗菌性金属が、銀、銅及び亜鉛からなる群から選ばれる少なくとも1種類の金属である請求項1に記載の内装材。
- ii)の抗菌性金属を含有する合金粒子が、少なくとも銀を含有するものである請求項2に記載の内装材。
- ii)の抗菌性金属を含有する合金粒子に含有される抗菌性金属が、合金粒子の全質量に対して1~100質量%である請求項1~3のいずれか1項に記載の内装材。
- i)の酸化チタン粒子と、ii)の抗菌性金属を含有する合金粒子との粒子混合物の分散粒子径が、レーザー光を用いた動的散乱法により測定される体積基準の50%累積分布径D50で、5~100nmである請求項1~4のいずれか1項に記載の内装材。
- さらに、表面層がバインダーを含有するものである請求項1~5のいずれか1項に記載の内装材。
- 前記バインダーがケイ素化合物系バインダーである請求項6に記載の内装材。
- 室内の建築材、車内の内装材、家具及び電化製品からなる群から選ばれる部材である請求項1~7のいずれか1項に記載の内装材。
- 内装材の表面に、i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とを含む分散液を塗布する工程を有する、請求項1に記載の内装材の製造方法。
- i)酸化チタン粒子と、ii)抗菌性金属を含有する合金粒子とを含む分散液の塗布方法が、スプレーコート、フローコート、ディップコート、スピンコート、メイヤーバーコート、グラビアコート、ナイフコート、キスコート、ダイコート及び/又はフィルム転写である請求項9に記載の内装材の製造方法。
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JPWO2019198482A1 (ja) | 2021-02-25 |
KR20200143418A (ko) | 2020-12-23 |
US20210023252A1 (en) | 2021-01-28 |
KR102693681B1 (ko) | 2024-08-12 |
AU2019250301B2 (en) | 2024-07-18 |
JP7070670B2 (ja) | 2022-05-18 |
CN111971076B (zh) | 2022-11-08 |
AU2019250301A1 (en) | 2020-10-22 |
EP3753585A1 (en) | 2020-12-23 |
CN111971076A (zh) | 2020-11-20 |
TW202003715A (zh) | 2020-01-16 |
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EP3753585A4 (en) | 2021-11-03 |
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