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  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/04—Oxides; Hydroxides
  • C01G23/047—Titanium dioxide
  • C01G23/08—Drying; Calcining ; After treatment of titanium oxide
• • 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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  • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
• • 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
  • A61L2/00—Disinfection or sterilisation of materials or objects, in general; Accessories therefor
  • A61L2/16—Disinfection or sterilisation of materials or objects, in general; Accessories therefor using chemical substances
  • A61L2/23—Solid materials, e.g. granules, powders, blocks or tablets
  • A61L2/238—Metals or alloys, e.g. oligodynamic metals
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  • A61L9/00—Disinfection, sterilisation or deodorisation of air
• • 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
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  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
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  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/847—Vanadium, niobium or tantalum or polonium
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  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/847—Vanadium, niobium or tantalum or polonium
  • B01J23/8472—Vanadium
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  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
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  • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/887—Molybdenum containing in addition other metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/8875—Germanium, tin or lead
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  • 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
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/888—Tungsten
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
  • B01J35/39—Photocatalytic properties
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/04—Mixing
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/06—Washing
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/10—Heat treatment in the presence of water, e.g. steam
• • 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
  • B01J37/16—Reducing
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/04—Oxides; Hydroxides
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/04—Oxides; Hydroxides
  • C01G23/047—Titanium dioxide
  • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J2235/00—Indexing scheme associated with group B01J35/00, related to the analysis techniques used to determine the catalysts form or properties
  • B01J2235/15—X-ray diffraction
• • B—PERFORMING OPERATIONS; TRANSPORTING
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  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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• • C—CHEMISTRY; METALLURGY
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  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2002/00—Crystal-structural characteristics
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  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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  • C01P2004/51—Particles with a specific particle size distribution
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  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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  • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
  • C01P2004/00—Particle morphology
  • C01P2004/60—Particles characterised by their size
  • C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer

Definitions

• the present invention relates to a titanium oxide particle/metal particle composition and a method for producing the same, and more particularly, regardless of the presence or absence of light irradiation, it is possible to easily prepare a photocatalyst thin film exhibiting antibacterial properties and high transparency.
• the present invention relates to a titanium oxide particle/metal particle composition (a dispersion, a photocatalyst thin film formed using the dispersion, a member having a photocatalyst thin film on its surface) and a method for producing the same.
• Photocatalyst materials are widely effective in cleaning substrate surfaces, such as antibacterial, antifungal, antiviral, deodorant, and antifouling properties, through photocatalytic reactions that occur when exposed to light such as sunlight or artificial lighting. It is attracting attention because it is
• a photocatalytic reaction is a reaction caused by excited electrons and holes generated when a photocatalyst represented by titanium oxide absorbs light. Excited electrons and holes generated on the surface of titanium oxide by a photocatalytic reaction cause oxidation-reduction reactions with oxygen and water adsorbed on the surface of titanium oxide to generate active species. Since microorganisms, viruses, odors, and stains composed of organic matter are decomposed by these active species, it is believed that the effect of cleaning the substrate surface as described above can be obtained.
• photocatalysts can be said to be strong in that they can be effective against a wide variety of microorganisms, viruses, odors, and stains because they can be used with any organic matter, and that there is almost no deterioration over time.
• Visible-light-responsive photocatalyst titanium oxide obtained by mixing titanium oxide fine particles in which tin and a transition metal that enhances visible light activity in Patent Document 7 are prepared and titanium oxide fine particles in which an iron group element is dissolved, respectively.
• a photocatalyst film formed using a fine particle dispersion is used, high decomposition activity can be obtained under the condition of only light in the visible region.
• photocatalyst materials that complement the functions of photocatalysts by combining photocatalysts with antibacterial agents other than photocatalysts are being investigated. Since the photocatalyst decomposes organic matter, it is appropriate to use an inorganic antibacterial agent. For example, silver or copper is added as an antibacterial/antifungal component to acquire antibacterial and antifungal properties in the dark (JP 2000-051708: Patent Document 8, JP 2008-260684: Patent Document 9).
• photocatalysts are used by dispersing photocatalyst particles in a solvent, mixing film-forming components into a paint, and applying it to a substrate.
• metal components such as zinc often causes practical problems. That is, as a method for supporting a metal such as silver, copper, zinc, or a compound thereof, when the metal raw material is reacted with the photocatalyst particle powder to support it, a great deal of labor is required to disperse it in a solvent afterwards.
• the dispersion stability of the photocatalyst particles is inhibited and causes aggregation. It was often difficult to obtain the transparency required in practice when forming.
• the present invention provides a titanium oxide particle/metal particle composition that has higher photocatalytic activity than conventional ones, particularly visible light activity, and further exhibits high antibacterial properties regardless of the presence or absence of light irradiation, and a method for producing the same. With the goal.
• the present inventors have investigated the following: metal elements to be solid-dissolved in titanium oxide particles and their combinations; metal elements to modify titanium oxide particles and their combinations; combinations of titanium oxide particles and various materials and their amounts; As a result of detailed examination of the ratio, etc., two types of particles were selected: titanium oxide particles in which specific metals whose surfaces were modified with an iron component and a silicon component are solid-dissolved, and separately prepared metal particles containing an antibacterial metal.
• the contained titanium oxide particles and metal particle composition has dramatically improved photocatalytic activity, especially visible light activity, and exhibits high antibacterial properties regardless of the presence or absence of light irradiation, and is a highly transparent photocatalyst. The inventors have found that a thin film can be easily produced, and have completed the present invention.
• the present invention provides the following titanium oxide particle/metal particle composition and method for producing the same.
• a protective agent is adsorbed on the surface of the metal particles containing the antibacterial metal of ii).
• the titanium oxide particles according to [1] or [2], wherein the antibacterial metal contained in the metal particles containing an antibacterial metal of ii) is at least one metal selected from silver, copper and zinc. • Metal particle compositions.
• the mass ratio (TiO 2 /Fe 2 O 3 ) of i) the iron component (in terms of oxide) modified on the surface of the titanium oxide particles to titanium oxide is 10 to 100,000, and the silicon component (oxide
• the transition metal component that enhances visible light activity and is solid-dissolved in the titanium oxide particles is at least one selected from molybdenum, tungsten and vanadium.
• the amounts of molybdenum, tungsten and vanadium components dissolved in the titanium oxide particles in i) are 1 to 10,000 in molar ratio (TiO 2 /Mo, TiO 2 /W or TiO 2 /V) with titanium oxide.
• a step of producing a peroxotitanic acid solution containing a tin component and a transition metal component from a raw material titanium compound, a tin compound, a transition metal compound, a basic substance, hydrogen peroxide and an aqueous dispersion medium.
• the titanium oxide particle/metal particle composition of the present invention has higher photocatalytic activity than conventional ones, especially high photocatalytic activity even with only visible light (wavelength 400 to 800 nm), and further exhibits high antibacterial properties regardless of the presence or absence of light irradiation. , a highly transparent photocatalyst thin film can be easily produced. Therefore, the titanium oxide particle/metal particle composition of the present invention is suitable for use in indoor spaces illuminated by artificial lighting, such as fluorescent lamps and white LEDs, in which visible light is predominant, and where prompt cleaning of the substrate surface is required. It is useful for members used in
• the titanium oxide particle/metal particle composition of the present invention is i) titanium oxide particles in which a tin component and a transition metal that enhances visible light activity are solid-dissolved, and iron and silicon components are not solid-dissolved, and the surface of which is modified; ii) metal particles containing an antimicrobial metal; contains two types of particles.
• One aspect of the titanium oxide particle/metal particle composition of the present invention is that the composition is a dispersion of titanium oxide particles/metal particles.
• the composition is a thin film (photocatalytic thin film) of titanium oxide particles/metal particles.
• the titanium oxide particle/metal particle composition of the present invention is a dispersion of titanium oxide particles/metal particles, that is, a titanium oxide particle/metal particle dispersion
• the titanium oxide particle/metal particle dispersion of the present invention is in the aqueous dispersion medium, i) titanium oxide particles in which a tin component and a transition metal that enhances visible light activity are solid-dissolved, and iron and silicon components are not solid-dissolved, and the surface of which is modified; ii) metal particles containing an antimicrobial metal; obtained by mixing two types of particle dispersions, a titanium oxide particle dispersion and a metal particle dispersion, which are separately constituted, as described later. is.
• the content ratio of i) the titanium oxide particles and ii) the antibacterial metal component (M) contained in the metal particles in the titanium oxide particle/metal particle dispersion of the present invention is TiO 2 /M in mass ratio. It is 1 to 100,000, preferably 10 to 10,000, more preferably 100 to 1,000. When the mass ratio is less than 1, the photocatalytic performance is not sufficiently exhibited, and when it exceeds 100,000, the antibacterial performance is not sufficiently exhibited, which is not preferred.
• the dispersed particle diameter of the mixture of titanium oxide particles and metal particles in the titanium oxide particle/metal particle dispersion is the volume-based 50% cumulative distribution diameter ( D 50 ) is preferably 3 to 50 nm, more preferably 3 to 40 nm, still more preferably 3 to 30 nm. If D50 is less than 3 nm, the photocatalytic activity may be insufficient, and if it exceeds 50 nm, the dispersion and the photocatalytic thin film obtained from the dispersion may become opaque. Also, the volume-based 90% cumulative distribution diameter (D 90 ) is preferably 5 to 100 nm, more preferably 5 to 80 nm.
• D90 is less than 5 nm, the photocatalytic activity may be insufficient, and if it exceeds 100 nm, the dispersion and the photocatalytic thin film obtained from the dispersion may become opaque.
• Devices for measuring the dispersed particle size of a mixture of titanium oxide particles and metal particles include, for example, ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.), Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and LA-910. (manufactured by HORIBA, Ltd.) and the like can be used.
• a mixed solvent of water and a hydrophilic organic solvent that can be mixed with water at an arbitrary ratio may also be used.
• water for example, purified water such as filtered water, deionized water, distilled water, and pure water is preferable.
• hydrophilic organic solvents include alcohols such as methanol, ethanol, and isopropanol; glycols such as ethylene glycol; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol-n-propyl ether. kind is preferred.
• the proportion of the hydrophilic 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. is.
• the titanium oxide particle component i) contained in the metal particle dispersion contains titanium oxide particles in which a tin component and a transition metal that enhances visible light activity are solid-dissolved, an iron component, and a silicon component. Although the iron component and silicon component are modified on the surface of the titanium oxide particles, part of the iron component and silicon component may be left free in the dispersion.
• the titanium oxide particle component i) is preferably blended as a titanium oxide particle dispersion with the titanium oxide particle/metal particle dispersion of the present invention.
• the titanium oxide particles are those in which a tin component and a transition metal component that enhances visible light activity are dissolved in titanium oxide, which is used as a photocatalyst, and the surface is modified with an iron component and a silicon component.
• titanium oxide particles of the present invention are preferably mainly anatase or rutile.
• the term "mainly” as used herein means that the titanium oxide particles of the crystal phase are contained in an amount of 50% by mass or more, preferably 70% by mass or more, and more preferably 90% by mass, out of the total titanium oxide particles. or more, and may be 100% by mass.
• a solid solution is a phase in which an atom at a lattice point of one crystal phase is substituted with another atom or another atom enters the lattice gap, that is, a crystal phase It has a mixed phase in which the substance is dissolved, and the crystalline phase is a homogeneous phase.
• a substitutional solid solution is one in which solvent atoms at lattice points are replaced with solute atoms
• an interstitial solid solution is one in which solute atoms are placed in the interstitial spaces.
• the titanium oxide particles contained in the dispersion form a solid solution with tin atoms and transition metal atoms.
• Solid solutions may be either substitutional or interstitial.
• the substitutional solid solution of titanium oxide is formed by substituting the titanium sites of the titanium oxide crystal with various metal atoms, and the interstitial solid solution of titanium oxide is formed by inserting various metal atoms into the lattice gaps of the titanium oxide crystal. It is formed.
• various metal atoms are dissolved in titanium oxide, when the crystal phase is measured by X-ray diffraction etc., only the peak of the crystal phase of titanium oxide is observed, and the peak of the compound derived from the various metal atoms added is not observed. .
• the method of dissolving dissimilar metals in metal oxide crystals is not particularly limited, but gas phase methods (CVD method, PVD method, etc.), liquid phase methods (hydrothermal methods, sol-gel methods, etc.), solid A phase method (such as a high-temperature firing method) can be used.
• gas phase methods CVD method, PVD method, etc.
• liquid phase methods hydroothermal methods, sol-gel methods, etc.
• solid A phase method such as a high-temperature firing method
• the tin component solid - dissolved in the titanium oxide particles may be derived from a tin compound.
• oxides SnO , SnO2
• chlorides SnCl2, SnCl4
• sulfates SnSO4
• oxoacid salts Na2SnO3 , K2SnO3
• the amount of the tin component dissolved in the titanium oxide particles is preferably 1 to 1,000, more preferably 5 to 500, and still more preferably 5 to 100 in molar ratio (TiO 2 /Sn) to titanium oxide particles. . This is because when the molar ratio is less than 1, the content of titanium oxide decreases and the photocatalytic effect is not sufficiently exhibited, and when it exceeds 1,000, the visible light responsiveness may be insufficient. be.
• Transition metals that enhance visible light activity and are dissolved in titanium oxide particles include vanadium, chromium, manganese, niobium, molybdenum, rhodium, tungsten, and cerium among Groups 3 to 11 of the periodic table. Among them, molybdenum, tungsten and vanadium are preferred. Therefore, iron, which is a transition metal, is not included in transition metals that enhance visible light activity.
• silicon modifies the surface of titanium oxide particles, but does not form a solid solution with the titanium oxide particles. That is, i) the titanium oxide particles contained in the titanium oxide particle/metal particle composition of the present invention do not contain an iron component and a silicon component as a solid solution.
• the transition metal component solid-dissolved in the titanium oxide particles may be derived from the transition metal compound, and includes metals, oxides, hydroxides, chlorides, nitrates, sulfates, halogens other than chlorides ( Br, I) compounds, oxoacid salts, various complex compounds, and the like, and one or more of these may be used.
• the amount of the transition metal component solid-dissolved in the titanium oxide particles can be appropriately selected according to the type of the transition metal component, but the molar ratio (TiO 2 /transition metal) with titanium oxide is 1 to 10,000. is preferred.
• the transition metal to be solid-dissolved may be selected from the above.
• the molybdenum component should be derived from a molybdenum compound.
• molybdenum elemental metal (Mo) oxides ( MoO2 , MoO3 ), hydroxides, chlorides ( MoCl3 , MoCl5), nitrates, sulfates, halogens other than chlorides (Br, I) molybdic acid (oxoacid) and its salts (H 2 MoO 4 , Na 2 MoO 4 , K 2 MoO 4 ), complex compounds, and the like. good.
• oxides MoO2 , MoO3
• chlorides MoCl3 , MoCl5
• oxoacids and salts thereof H2MoO4 , Na2MoO4 , K2MoO4 .
• the amount of the molybdenum component dissolved in the titanium oxide particles is preferably 1 to 10,000, more preferably 5 to 5,000, and still more preferably 20 to 1 in molar ratio (TiO 2 /Mo) to titanium oxide particles. , 000. This is because if the molar ratio is less than 1, the titanium oxide content may decrease and the photocatalytic effect may not be sufficiently exhibited, and if it exceeds 10,000, the visible light responsiveness may be insufficient. be.
• the tungsten component may be derived from a tungsten compound. Hydroxides, chlorides (WCl 4 , WCl 6 ), nitrates, sulfates, halides other than chlorides (Br, I), tungstic acid and oxoacid salts (H 2 WO 4 , Na 2 WO 4 , K 2 WO 4 ), complex compounds, etc., and one or more of these may be used in combination. Among them, oxides ( WO3), chlorides ( WCl4 , WCl6 ) and oxoacid salts ( Na2WO4 , K2WO4 ) are preferably used.
• the amount of the tungsten component dissolved in the titanium oxide particles is preferably 1 to 10,000, more preferably 5 to 5,000, and still more preferably 20 to 2 in molar ratio (TiO 2 /W) to titanium oxide. , 000. This is because if the molar ratio is less than 1, the titanium oxide content may decrease and the photocatalytic effect may not be sufficiently exhibited, and if it exceeds 10,000, the visible light responsiveness may be insufficient. be.
• the vanadium component may be derived from a vanadium compound. O3 , VO2, V2O5 ), hydroxides, chlorides ( VCl5 ) , oxychlorides ( VOCl3 ), nitrates, sulfates, oxysulfates ( VOSO4 ), halogens other than chlorides ( Br, I) compounds, oxoacid salts (Na 3 VO 4 , K 3 VO 4 , KVO 3 ), complex compounds and the like, and one or more of these may be used in combination.
• oxides ( V2O3 , V2O5 ), chlorides ( VCl5 ), oxychlorides ( VOCl3 ), oxysulfates ( VOSO4 ), oxoacid salts ( Na3VO4 , K 3 VO 4 , KVO 3 ) are preferably used.
• the amount of the vanadium component dissolved in the titanium oxide particles is preferably 1 to 10,000, more preferably 10 to 10,000, and still more preferably 100 to 10 in terms of molar ratio (TiO 2 /V) to the titanium oxide particles. , 000. This is because if the molar ratio is less than 1, the titanium oxide content may decrease and the photocatalytic effect may not be sufficiently exhibited, and if it exceeds 10,000, the visible light responsiveness may be insufficient. be.
• a plurality of transition metal components can be selected from molybdenum, tungsten, and vanadium as the transition metal component to be solid-dissolved in the titanium oxide particles, and the amount of each component can be selected from the above range.
• the molar ratio [TiO 2 /(Mo+W+V)] of the total amount of each component to titanium oxide is 1 or more and less than 10,000.
• the titanium oxide particles may be used singly or in combination of two or more. When two or more kinds having different visible light responsiveness are combined, an effect of increasing visible light activity may be obtained.
• the iron and silicon components modified on the surface of the titanium oxide particles enhance the visible light responsiveness of the photocatalytic thin film.
• the iron component is for enhancing the visible light responsiveness of the photocatalyst thin film , but it may be derived from an iron compound. 3 O 4 ), hydroxides (Fe(OH) 2 , Fe(OH) 3 ), oxyhydroxides (FeO(OH)), chlorides (FeCl 2 , FeCl 3 ), nitrates (Fe(NO) 3 ), sulfates (FeSO 4 , Fe 2 (SO 4 ) 3 ), halogen (Br, I) compounds other than chlorides, complex compounds, etc., and these may be used alone or in combination of two or more. good too.
• the content of the iron component (as oxide) is preferably 10 to 100,000, more preferably 20 to 10,000, and still more preferably 50 to 100,000 in mass ratio (TiO 2 /Fe 2 O 3 ) to titanium oxide. 1,000. This is because when the mass ratio is less than 10, the quality of the photocatalyst thin film obtained by aggregating and precipitating the titanium oxide particles may deteriorate, and the photocatalytic effect may not be sufficiently exhibited. is insufficient.
• Silicon compounds include, for example, elemental silicon (Si), oxides (SiO, SiO 2 ), alkoxides (Si(OCH 3 ) 4 , Si(OC 2 H 5 ) 4 , Si(OCH (CH 3 ) 2 ) 4 ), silicates (sodium salts, potassium salts), and active silicic acid obtained by removing at least part of ions such as sodium and potassium from the silicates, and one of these Or you may use it in combination of 2 or more types. Among them, it is preferable to use silicate (sodium silicate) and activated silicic acid, particularly activated silicic acid.
• the content of the silicon component is preferably 1 to 10,000, more preferably 2 to 5,000, still more preferably 5 to 1,000 in mass ratio (TiO 2 /SiO 2 ) to titanium oxide. 000. This is because if the mass ratio is less than 1, the content of titanium oxide may decrease and the photocatalytic effect may not be sufficiently exhibited, and if it exceeds 10,000, the effect of suppressing aggregation and precipitation of titanium oxide will be insufficient. It is because there is something.
• the surface of the titanium oxide particles may be modified with a titanium component as a component that further enhances the photocatalytic activity.
• the titanium component is for further enhancing the photocatalytic activity of the photocatalytic thin film, but it may be derived from a titanium compound.
• oxyhydroxides TiO(OH) 2
• chlorides TiCl4 , TiCl3 , TiCl2
• nitrates Ti(NO) 4
• sulfates Ti( SO4 ) 2 , TiOSO4
• Halogen (Br, I) compounds other than chlorides, complex compounds, etc. may be mentioned, and these may be used singly or in combination of two or more.
• the content of the titanium component is preferably from 10 to 100,000, more preferably from 20 to 10,000 in mass ratio with titanium oxide (TiO 2 (titanium oxide particles)/TiO 2 (modifying component)). 000, more preferably 50 to 1,000. This is because when the mass ratio is less than 10, the quality of the photocatalyst thin film obtained by aggregation and precipitation of titanium oxide may deteriorate and the photocatalytic effect may not be sufficiently exhibited. This is because it may be insufficient.
• a mixed solvent of water and a hydrophilic organic solvent that can be mixed with water at an arbitrary ratio may also be used.
• water for example, purified water such as filtered water, deionized water, distilled water, and pure water is preferable.
• hydrophilic organic solvents include alcohols such as methanol, ethanol, and isopropanol; glycols such as ethylene glycol; and glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and propylene glycol-n-propyl ether. kind is preferred.
• the proportion of the hydrophilic 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. is.
• Titanium oxide particles in a titanium oxide particle dispersion liquid in which tin and a transition metal component that enhances visible light activity are solid-dissolved and the surface is modified with an iron component and a silicon component are measured by a dynamic light scattering method using a laser beam.
• the volume-based 50% cumulative distribution diameter (hereinafter sometimes referred to as D 50 ) is preferably 3 to 50 nm, more preferably 3 to 40 nm, still more preferably 3 to 30 nm. If D50 is less than 3 nm, the photocatalytic activity may be insufficient, and if it exceeds 50 nm, the dispersion and the photocatalytic thin film obtained from the dispersion may become opaque.
• the volume-based 90% cumulative distribution diameter (hereinafter sometimes referred to as D 90 ) is preferably 5 to 100 nm, more preferably 5 to 80 nm. If D90 is less than 5 nm, the photocatalytic activity may be insufficient, and if it exceeds 100 nm, the dispersion and the photocatalytic thin film obtained from the dispersion may become opaque.
• the titanium oxide particles have D 50 and D 90 within the above-described ranges, because they have high photocatalytic activity and a highly transparent dispersion and a photocatalytic thin film obtained from the dispersion can be obtained.
• Devices for measuring D 50 and D 90 of the titanium oxide particles in the titanium oxide particle dispersion include, for example, ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.) and Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.). (manufactured by HORIBA, Ltd.), LA-910 (manufactured by HORIBA, Ltd.) and the like can be used.
• the concentration of titanium oxide particles in the dispersion of titanium oxide particles is preferably 0.01 to 20% by mass, particularly 0.5 to 10% by mass, from the viewpoint of facilitating the preparation of a photocatalyst thin film having a required thickness. preferable.
• the metal particle component ii) contained in the dispersion of titanium oxide particles and metal particles of the present invention consists of a metal component containing at least one metal component that enhances antibacterial properties. It is.
• the metal component that enhances antibacterial properties refers to a metal component that is harmful to microorganisms such as fungi and molds but is relatively harmless to the human body. Silver, copper, zinc, platinum, palladium, nickel, aluminum, titanium, cobalt, zirconium, molybdenum and tungsten, which are confirmed to reduce the number of viable bacteria such as Staphylococcus aureus and Escherichia coli when performing standard tests on antibacterial processed products. etc. At least one metal selected from silver, copper and zinc is particularly preferred as the metal component that enhances the antibacterial properties.
• the metal particle component ii) is preferably added as a metal particle dispersion to the titanium oxide particle/metal particle dispersion of the present invention.
• These antibacterial-enhancing metal components can be used by themselves or by adding their solutions to titanium oxide particles. In that case, the effect of increasing the photocatalytic activity is reduced. In order to prevent this, it is preferable to add separately prepared metal particles to the titanium oxide particles, and more preferably to adsorb a protective agent on the surfaces of the metal particles.
• the metal particles are metal particles containing at least one of these metals, and may be alloy particles containing two or more metals.
• alloy particles include silver-copper, silver-palladium, silver-platinum, silver-tin, gold-copper, silver-nickel, silver-antimony, silver-copper-tin, gold-copper-tin, silver-nickel-tin, silver-antimony-tin, platinum-manganese, silver-titanium, copper-tin , cobalt-copper, zinc-magnesium, silver-zinc, copper-zinc, silver-copper-zinc and other combinations of metal components.
• the metal component other than the metal component that enhances antibacterial properties in the metal particles is not particularly limited, but examples include gold, antimony, tin, sodium, magnesium, silicon, potassium, calcium, scandium, vanadium, chromium, manganese, iron, and gallium.
• the content of the metal component that enhances the antibacterial property in the metal particles is 1 to 100% by mass, preferably 10 to 100% by mass, more preferably 50 to 100% by mass, based on the total mass of the metal particles. %. This is because if the metal component that enhances the antibacterial properties is less than 1% by mass, the antibacterial performance may not be sufficiently exhibited.
• a protective agent for metal particles it adsorbs to the surface of metal particles and stabilizes them, and it prevents the metal particles deposited by reduction from aggregating and enlarging.
• Any organic compound capable of functioning as a surfactant or a dispersant can be used without particular limitation as long as it can prevent the reduction in the effect of increasing the photocatalytic activity of the silicon component.
• those exhibiting reducing properties can also serve as a reducing agent, which will be described later.
• Protective agents for metal particles include, for example, surfactants such as anionic surfactants, cationic surfactants, and nonionic surfactants; polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol, polyethyleneimine, polyethylene oxide; , polysulfonic acid, polyacrylic acid, water-soluble polymer compounds such as methylcellulose; aliphatic amine compounds such as ethanolamine, diethanolamine, triethanolamine, propanolamine; butylamine, dibutylamine, hexylamine, cyclohexylamine, heptylamine, 3 - primary amine compounds such as butoxypropylamine, octylamine, nonylamine, decylamine, dodecylamine, hexadecylamine, oleylamine, octadecylamine; diamine compounds such as N,N-dimethylethylenediamine, NN-diethylethylenediamine; s
• the content of the protective agent is preferably from 0.01 to 100, more preferably from 0.05 to 20, in mass ratio with respect to the metal particles (metal particles/protective agent adsorbed on the surface of the metal particles). If the mass ratio is less than 0.01, the content of the metal particles may decrease and the antibacterial effect may not be sufficiently exhibited. This is because the conversion and photocatalytic activity may decrease.
• the content of the protective agent can be measured by the method described below.
• An aqueous solvent is usually used as the aqueous dispersion medium for the metal particle dispersion, and it is preferable to use water, a water-soluble organic solvent that is miscible with water, or a mixed solvent of water and a water-soluble organic solvent.
• Water is preferably deionized water, distilled water, pure water, or the like.
• water-soluble organic solvents 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, acetone, ketones such as methyl ethyl ketone, 2-pyrrolidone , water-soluble nitrogen-containing compounds such as N-methylpyrrolidone, and ethyl acetate, and these may be used alone or in combination of two or more.
• alcohols such as methanol, ethanol, n-propanol, 2-propanol, n
• the volume-based 50% cumulative distribution diameter (D 50 ) measured by a dynamic light scattering method using laser light is preferably 200 nm or less, It is more preferably 100 nm or less, still more preferably 70 nm or less.
• the lower limit of the average particle size is not particularly limited, and theoretically the smallest particle size that can have antibacterial properties can be used, but in practice it is preferably 1 nm or more.
• the average particle size exceeds 200 nm, the dispersion and the photocatalyst thin film obtained from the dispersion may become opaque, which is not preferable.
• the volume-based 90% cumulative distribution diameter (D 90 ) is preferably 1,000 nm, more preferably 500 nm or less, and even more preferably 200 nm or less.
• the lower limit of D90 is not particularly limited, it is preferably 1 nm or more in practice.
• the dispersion and the photocatalyst thin film obtained from the dispersion may become opaque, which is not preferable.
• Examples of devices for measuring the average particle size include ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.), Nanotrac UPA-EX150 (manufactured by Nikkiso Co., Ltd.), and LA-910 (manufactured by Horiba Ltd.). etc. can be used.
• the concentration of the metal particles in the metal particle dispersion is not particularly limited, but generally the lower the concentration, the better the dispersion stability. It is preferably 0.01 to 1% by mass. If it is less than 0.0001% by mass, the productivity will be significantly lowered, which is not preferable.
• a binder may be added to the titanium oxide particle/metal particle dispersion for the purpose of facilitating the application of the dispersion to the surfaces of various members described later and the adhesion of the particles.
• binders include metal compound binders containing silicon, aluminum, titanium, zirconium, etc., and organic resin binders containing fluorine resins, acrylic resins, urethane resins, and the like.
• the mass ratio of the binder to the titanium oxide particles/metal particles [(titanium oxide particles + metal particles)/binder] is 99 to 0.01, more preferably 9 to 0.1, and still more preferably 2.5 to 0.5. It is preferable to add and use it in the range of 4. This is because if the mass ratio exceeds 99, the adhesion of the titanium oxide particles to the surfaces of various members may be insufficient, and if it is less than 0.01, the photocatalytic activity may be insufficient.
• the mass ratio of the silicon compound binder is 99 to 0.01, more preferably 9 to 0.01. It is preferable to add it in the range of 0.1, more preferably 2.5 to 0.4.
• the silicon compound 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.
• silicate solution such as silicate; silane, siloxane hydrolyzate emulsion; silicone resin emulsion; silicone resin such as silicone-acrylic resin copolymer, silicone-urethane resin copolymer, etc. and an emulsion of a copolymer with a resin.
• a tin component and a transition metal component that enhances visible light activity are solid-dissolved in an aqueous dispersion medium, and an iron component and a silicon component are not solid-dissolved.
• a step of producing a peroxotitanic acid solution containing a tin component and a transition metal component from a raw material titanium compound, a tin compound, a transition metal compound, a basic substance, hydrogen peroxide and an aqueous dispersion medium.
• Step of producing a solution or dispersion of an iron component and a silicon component from an iron compound, a silicon compound and an aqueous dispersion medium (4) The titanium oxide particle dispersion produced in step (2) above and step (3) (5) A solution containing a starting antibacterial metal compound and the metal compound (6) The solution containing the starting antibacterial metal compound produced in step (5) above and the metal Step of producing a metal particle dispersion by mixing a solution containing a reducing agent for reducing the compound and a protective agent for coating and protecting the metal particles (7) The metal particle dispersion produced in the above step (6) (8) A step of mixing the titanium oxide particle dispersion obtained in steps (4) and (7) with the metal particle dispersion
• Steps (1) to (4) are for producing a titanium oxide particle dispersion in which a tin component and a transition metal component are solid-dissolved and the surface is modified with an iron component and a silicon component.
• Steps (5) to (7) are for producing a metal particle dispersion liquid, and among physical methods and chemical methods, it is particularly easy to adjust the synthesis conditions, and the composition, particle size, particle size distribution, etc. It uses the liquid-phase reduction method, which is one of the chemical methods that has a wide controllable range and is superior in terms of productivity. , are deposited as metal particles.
• the dispersibility of the metal particles in the solvent can be improved, the particle size can be controlled, and when mixed with the titanium oxide particles, the decrease in photocatalytic activity can be suppressed. become easier to do.
• the tin component and the transition metal component obtained in the step (4) are solid-dissolved, and the surface is modified with the iron component and the silicon component, and the titanium oxide particle dispersion obtained in the step (7).
• a titanium oxide particle/metal particle dispersion is produced by mixing with the metal particle dispersion containing the antibacterial metal. The details of each step are described below.
• a method for producing a dispersion of titanium oxide particles in which a tin component and a transition metal component are solid-dissolved and whose surface is modified with an iron component and a silicon component comprises titanium oxide particles in which a tin component and a transition metal component are solid-dissolved.
• a dispersion and a solution or dispersion of an iron component and a silicon component are produced respectively, and the titanium oxide particle dispersion in which a tin component and a transition metal component are solid-dissolved are mixed with the solution or dispersion of an iron component and a silicon component. It is prepared by
• the tin component- and transition metal component-containing peroxotitanic acid solution produced in the step is heated at 80 to 250°C under pressure control to obtain a titanium oxide particle dispersion.
• Step (3) Iron compound, silicon compound and aqueous dispersion medium
• the iron component and the silicon component are used in the same manner as in the above step (3) except that the titanium compound is further added. And a titanium oxide particle dispersion having a surface modified with a titanium component can be obtained.
• Steps (1) and (2) are steps of obtaining a titanium oxide particle dispersion in which a tin component and a transition metal component are solid-dissolved
• step (3) is a step of obtaining a solution or dispersion of an iron component and a silicon component
• step (4) is a step of obtaining a dispersion containing titanium oxide particles in which a tin component and a transition metal component are solid-dissolved and whose surfaces are modified with an iron component and a silicon component.
• a peroxotitanic acid solution containing a tin component and a transition metal component is produced by reacting a raw material titanium compound, a tin compound, a transition metal compound, a basic substance and hydrogen peroxide in an aqueous dispersion medium.
• any of the following methods i) to iii) may be used as the reaction method.
• a tin compound and a transition metal compound are added to and dissolved in the starting titanium compound and basic substance in the aqueous dispersion medium, and then the titanium hydroxide containing the tin component and the transition metal component is obtained, and the metal ions other than the contained metal ions are obtained.
• a basic substance is added to the starting titanium compound in the aqueous dispersion medium to form titanium hydroxide, impurity ions other than the contained metal ions are removed, a tin compound and a transition metal compound are added, and then hydrogen peroxide is added.
• a method of adding a tin component and a transition metal component-containing peroxotitanic acid iii) A basic substance is added to the raw material titanium compound in the aqueous dispersion medium to form titanium hydroxide, impurity ions other than the contained metal ions are removed, hydrogen peroxide is added to form peroxotitanic acid, and then the tin compound. and a method of adding a transition metal compound to obtain a peroxotitanic acid containing a tin component and a transition metal component
• the "raw material titanium compound and basic substance in the aqueous dispersion medium" are replaced by "the aqueous dispersion medium in which the raw material titanium compound is dispersed” and the “aqueous dispersion medium in which the basic substance is dispersed.” ”, and each compound of the tin compound and the transition metal compound is dissolved in either or both of the two liquids according to the solubility of each compound in the two liquids. After that, both may be mixed.
• step (2) After obtaining peroxotitanic acid containing a tin component and a transition metal component in this way, it is subjected to a hydrothermal reaction in step (2) described below to obtain titanium oxide particles in which the various metals are solid-dissolved in titanium oxide. be able to.
• the raw material titanium compound examples include inorganic acid salts such as titanium chlorides, nitrates, and sulfates; organic acid salts such as formic acid, citric acid, oxalic acid, lactic acid, and glycolic acid; titanium hydroxide or the like precipitated by hydrolyzing with a hydrolyzate, and these may be used singly or in combination of two or more.
• titanium chlorides TiCl 3 , TiCl 4
• TiCl 3 , TiCl 4 are preferably used.
• the concentration of the starting titanium compound aqueous solution formed from the starting titanium compound and the aqueous dispersion medium is preferably 60% by mass or less, particularly 30% by mass or less. Although the lower limit of the concentration is appropriately selected, it is usually preferably 1% by mass or more.
• the basic substance is used to smoothly convert the raw material titanium compound into titanium hydroxide, and examples thereof include hydroxides of alkali metals or alkaline earth metals such as sodium hydroxide and potassium hydroxide, ammonia, alkanolamines, alkyl Amine compounds such as amines may be mentioned, and among them, it is particularly preferable to use ammonia.
• the basic substance may be used together with the above aqueous dispersion medium in the form of an aqueous solution having an appropriate concentration.
• Hydrogen peroxide is for converting the 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 solution. be done.
• the amount of hydrogen peroxide to be added is preferably 1.5 to 20 times the molar amount of Ti or the total amount of Ti, transition metal and Sn.
• the reaction temperature is preferably 5 to 80° C.
• the reaction time is preferably 30 minutes to 24 hours. preferable.
• the peroxotitanic acid solution containing the tin component and the transition metal component thus obtained may contain an alkaline substance or an acidic substance for pH adjustment and the like.
• alkaline substances here include ammonia, sodium hydroxide, calcium hydroxide, and alkylamines
• acidic substances include sulfuric acid, nitric acid, hydrochloric acid, carbonic acid, phosphoric acid, hydrogen peroxide, and the like. and organic acids such as formic acid, citric acid, oxalic acid, lactic acid and glycolic acid.
• the obtained peroxotitanic acid solution preferably has a pH of 1 to 9, particularly 4 to 7, from the viewpoint of safety in handling.
• step (2) the tin component- and transition metal component-containing peroxotitanic acid solution obtained in step (1) above is heated to 0.01 at a temperature of 80 to 250°C, preferably 100 to 250°C, under pressure control.
• a suitable reaction temperature is 80 to 250° C. from the viewpoint of reaction efficiency and reaction controllability. converted into titanium particles.
• under pressure control means that when the reaction temperature exceeds the boiling point of the dispersion medium, the reaction temperature is maintained by appropriately pressurizing so as to maintain the reaction temperature. It includes the case of controlling at atmospheric pressure when the temperature is below the boiling point.
• the pressure used here is usually about 0.12 to 4.5 MPa, preferably about 0.15 to 4.5 MPa, more preferably about 0.20 to 4.5 MPa.
• the reaction time is preferably 1 minute to 24 hours.
• a titanium oxide particle dispersion in which the tin component and the transition metal component are solid-dissolved is obtained.
• the pH of the titanium oxide particle dispersion in which the tin component and the transition metal component are solid-dissolved in step (2) is preferably 7-14, more preferably 9-14.
• the titanium oxide particle dispersion in which the tin component and the transition metal component are solid-dissolved obtained in step (2) may contain an alkaline substance or an acidic substance for pH adjustment or the like so as to have the above-described pH. , the alkaline substance, the acidic substance and the pH adjustment method are the same as those for the peroxotitanic acid solution containing the tin component and the transition metal component obtained in step (1) above.
• the particle diameters (D 50 and D 90 ) of the titanium oxide particles obtained here are preferably within the ranges already described, and the particle diameter can be controlled by adjusting the reaction conditions.
• the particle size can be reduced by shortening the reaction time and the heating time.
• Step (3) separately from steps (1) and (2) above, a solution or dispersion of an iron component and a silicon component is prepared by dissolving or dispersing the starting iron compound and the starting silicon compound in an aqueous dispersion medium. manufacture.
• the raw material iron compound examples include the iron compounds described above, such as iron metal simple substance (Fe), oxides (Fe 2 O 3 , Fe 3 O 4 ), hydroxides (Fe(OH) 2 , Fe(OH) 3 ), oxyhydroxides (FeO(OH)), chlorides ( FeCl2 , FeCl3), nitrates (Fe(NO) 3 ), sulfates ( FeSO4 , Fe2 ( SO4 ) 3 ) , chlorides and halogen (Br, I) compounds, complex compounds, etc. of these may be used alone or in combination of two or more thereof.
• iron metal simple substance Fe
• oxides Fe 2 O 3 , Fe 3 O 4
• hydroxides Fe(OH) 2 , Fe(OH) 3
• oxyhydroxides FeO(OH)
• chlorides FeCl2 , FeCl3
• nitrates Fe(NO) 3
• sulfates FeSO4 , Fe2 ( SO4 ) 3
• oxides Fe2O3 , Fe3O4 ), oxyhydroxides (FeO(OH)), chlorides ( FeCl2 , FeCl3), nitrates (Fe(NO) 3 ) , sulfates ( FeSO 4 , Fe 2 (SO 4 ) 3 ) are preferably used.
• silicon compound starting material examples include the silicon compounds described above, for example, silicon elemental metal (Si), oxides (SiO, SiO 2 ), alkoxides (Si(OCH 3 ) 4 , Si(OC 2 H 5 ) 4 , Si( OCH(CH 3 ) 2 ) 4 ), silicates (sodium salts, potassium salts), active silicic acid obtained by removing ions such as sodium and potassium from these silicates, and the like, and one or two of these A combination of the above may be used. Among them, silicate (sodium silicate) and active silicic acid are preferably used.
• Active silicic acid is obtained, for example, by adding a cation exchange resin to an aqueous sodium silicate solution in which sodium silicate is dissolved in pure water to remove at least part of the sodium ions. It is preferable to add a cation exchange resin so that the pH becomes 2-10, preferably 2-7.
• the iron component- and silicon component-containing solution or dispersion thus obtained may also contain an alkaline substance or an acidic substance for pH adjustment or the like. can be handled.
• the pH of the iron component- and silicon component-containing solution or dispersion is preferably 1-7, more preferably 1-5.
• the raw material iron compound concentration in the solution or dispersion of the iron component and silicon component produced in step (3) is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and the raw material silicon compound concentration is 0.001 to 10% by mass is preferred, and 0.01 to 5% by mass is more preferred.
• iron component and silicon component solution or dispersion may further dissolve or disperse a titanium component.
• the raw material titanium compound includes the above-described titanium compounds, such as titanium simple substance (Ti), hydroxide (Ti(OH) 4 ), and oxyhydroxide (TiO(OH) 2 ). , chlorides (TiCl 4 , TiCl 3 , TiCl 2 ), nitrates (Ti(NO) 4 ), sulfates (Ti(SO 4 ) 2 , TiOSO 4 ), halogen (Br, I) compounds other than chlorides, complexes compounds, peroxotitanium compounds (titanium oxide compounds containing Ti--O--O--Ti bonds) and the like, and these may be used alone or in combination of two or more.
• titanium compounds such as titanium simple substance (Ti), hydroxide (Ti(OH) 4 ), and oxyhydroxide (TiO(OH) 2 ).
• chlorides TiCl 4 , TiCl 3 , TiCl 2
• nitrates Ti(NO) 4
• Step (4) the titanium oxide particle dispersion obtained in step (2) and the solution or dispersion of the iron component and silicon component obtained in step (3) are mixed.
• the mixing method is not particularly limited, and may be a method of stirring with a stirrer or a method of dispersing with an ultrasonic disperser.
• the temperature during mixing is 20 to 100° C., preferably 20 to 80° C., more preferably 20 to 40° C., and the time is preferably 1 minute to 3 hours.
• the mixing ratio if the mass ratio of TiO 2 and Fe and Si in terms of oxides (Fe 2 O 3 and SiO 2 ) in the titanium oxide particle dispersion becomes the mass ratio as described above, good.
• the titanium oxide particle dispersion liquid obtained in the above steps (1) to (4) may contain an alkaline substance or an acidic substance for pH adjustment or the like, and the above pH adjusters may be used. can be used. Further, ion exchange treatment or filtration washing treatment may be performed to adjust the ion component concentration, or solvent replacement treatment may be performed to change the solvent component.
• the pH of the titanium oxide particle dispersion is preferably 7-14, more preferably 8-12.
• the mass of the titanium oxide particles contained in the titanium oxide particle dispersion can be calculated from the mass and concentration of the titanium oxide particle dispersion.
• a method for producing a metal particle dispersion containing an antibacterial metal comprises mixing a solution containing an antibacterial metal compound with a solution containing a reducing agent and a protective agent to obtain a metal particle dispersion by membrane filtration to remove particles other than metal particles. It is prepared by removing and purifying the components of
• Specific examples of the method for producing a metal particle dispersion containing an antibacterial metal include a production method having the following steps (5) to (7).
• a step of producing a solution containing a raw material antibacterial metal compound and a solution containing a reducing agent for reducing the metal compound and a protective agent for coating and protecting the metal particles Above (5) A step of mixing the solution containing the raw material antibacterial metal compound produced in the step of (1) with a solution containing a reducing agent for reducing the metal compound and a protective agent for coating and protecting the metal particles to produce a metal particle dispersion (7) A step of washing the metal particle dispersion prepared in the above step (6) with an aqueous dispersion medium by a membrane filtration method.
• alloy particles composed of a plurality of metals are formed in the same manner as in the above step (5) except that the metal compound is further added to the solution containing the raw material antibacterial metal compound. A dispersion can be obtained.
• Step (5) a solution in which the starting antibacterial metal compound is dissolved in an aqueous dispersion medium and a solution in which a reducing agent for reducing the starting antibacterial metal compound is dissolved in the aqueous dispersion medium are produced.
• the method for producing these solutions may be a method in which the raw material antibacterial metal compound and the reducing agent for reducing the raw material antibacterial metal compound are separately added to the aqueous dispersion medium and stirred to dissolve.
• 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.
• antibacterial metal compounds can be used as raw material antibacterial metal compounds.
• examples include organic acid salts such as glycolic acid, complex salts such as ammine complexes, cyano complexes, halogeno complexes, and hydroxy complexes, and one or more of these may be used in combination.
• organic acid salts such as glycolic acid
• complex salts such as ammine complexes, cyano complexes, halogeno complexes, and hydroxy complexes
• inorganic acid salts such as chlorides, nitrates and sulfates.
• the reducing agent is not particularly limited, but any of various reducing agents capable of reducing the ions of the metals constituting the starting antibacterial metal compound can be used.
• hydrazines such as hydrazine, hydrazine monohydrate, phenylhydrazine, and hydrazinium sulfate
• amines such as dimethylaminoethanol, triethylamine, octylamine, dimethylaminoborane, and benzotriazole
• citric acid ascorbic acid, tartaric acid, malic acid.
• malonic acid organic acids such as formic acid; sodium borohydride, lithium borohydride, lithium triethylborohydride, lithium aluminum hydride, diisobutylaluminum hydride, tributyltin hydride, lithium tri(sec-butyl)borohydride , tri(sec-butyl)potassium borohydride, zinc borohydride, hydrides such as sodium acetoxyborohydride; pyrrolidones such as polyvinylpyrrolidone, 1-vinylpyrrolidone, N-vinylpyrrolidone, methylpyrrolidone; glucose, galactose , mannose, fructose, sucrose, maltose, raffinose, stachyose, and other reducing sugars; sugar alcohols, such as sorbitol; and these may be used alone or in combination of two or more.
• the aqueous dispersion medium for dissolving the reducing agent the a
• a protective agent may be added to a solution in which a reducing agent is dissolved in an aqueous dispersion medium.
• the protective agent it is preferable that the above-mentioned one is contained in the above-mentioned mass ratio with respect to the metal particles.
• aqueous dispersion medium aqueous solvent
• the above-mentioned ones are preferably used.
• a basic substance or an acidic substance may be added to the above solvent.
• 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- Examples thereof include alkali metal alkoxides such as butoxypotassium, sodium methoxide and sodium ethoxide, alkali metal salts of aliphatic hydrocarbons such as butyllithium, and amines such as triethylamine, diethylaminoethanol and diethylamine.
• acidic substances include inorganic acids such as aqua regia, hydrochloric acid, nitric acid and sulfuric acid, and 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.
• concentrations of these two solutions are not particularly limited, but in general, the lower the concentration, the smaller the primary particle size of the individual metal particles formed. It is preferable to set a suitable concentration range.
• the pH of these two solutions is not particularly limited, and it is preferable to adjust the pH to a suitable one depending on the molar ratio of the metal in the target metal particles and the primary particle size.
• Step (6) the solution prepared in step (5) in which the starting antibacterial metal compound is dissolved in the aqueous dispersion medium and the reducing agent for reducing the starting antibacterial metal compound are dissolved in the aqueous dispersion medium.
• the metal particle dispersion liquid is produced by mixing the obtained solution.
• the method for mixing these two solutions is not particularly limited as long as it is a method capable of uniformly mixing these two solutions.
• a method of dropping a reducing agent solution while stirring a metal compound solution placed in a reaction vessel and stirring and mixing a method of dropping a metal compound solution while stirring a reducing agent solution placed in a reaction vessel, and stirring and mixing;
• a method in which the compound solution and the reducing agent solution are continuously and quantitatively supplied and mixed in a reaction vessel, a flow reactor, or the like can be used.
• the temperature during mixing is not particularly limited, and it is preferable to adjust the temperature to a suitable temperature according to the target primary particle size, reaction time, etc.
• Step (7) the metal particle dispersion prepared in step (6) is washed with an aqueous dispersion medium by membrane filtration.
• aqueous dispersion medium it is preferable to use water, a water-soluble organic solvent that can be mixed with water, or a mixed solvent of water and a water-soluble organic solvent.
• Water is preferably deionized water, distilled water, pure water, or the like.
• water-soluble organic solvents include alcohols such as methanol, ethanol, isopropanol, n-propanol, 2-propanol, n-butanol, 2-butanol, tert-butanol, ethylene glycol and diethylene glycol, and ethylene glycol monomethyl ether.
• ethylene glycol monoethyl ether ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, glycol ethers such as propylene glycol-n-propyl ether, acetone, ketones such as methyl ethyl ketone, 2-pyrrolidone, Examples thereof include water-soluble nitrogen-containing compounds such as N-methylpyrrolidone and ethyl acetate, and the water-soluble organic solvent may be used alone or in combination of two or more thereof.
• the membrane filtration method removes unnecessary non-volatile components other than the metal particles from the metal particle dispersion, such as components other than metals in the raw material metal compound, reducing agents, and surplus protective agents that are not adsorbed on the surfaces of the metal particles. Wash and separate. Components other than the metal particles and the protective agent adsorbed on their surfaces are preferably separated from the metal particle dispersion in this step.
• the mass ratio of the metal particles having the protective agent adsorbed on their surfaces to the other non-volatile matter is 1 or more. is preferably 10 or more, and still more preferably 100 or more. This is because if the ratio is less than 1, the content ratio of the metal particles may decrease and the antibacterial effect may not be sufficiently exhibited.
• the metal component (metal particles) concentration C (% by mass) in the metal particle dispersion liquid was obtained by appropriately diluting the metal particle dispersion liquid with pure water, and using an inductively coupled plasma emission spectrometer (trade name “Agilent 5110 ICP-OES”, Agilent Technologies, Inc.) can be used for measurement.
• the non-volatile matter of mass M a (g) is dispersed in pure water and washed, and then the metal particles having the protective agent adsorbed on the surface are sedimented by centrifugal separation, and the metal particles having the protective agent adsorbed on the surface.
• the operation of removing the supernatant containing the non-volatile matter M 3 (g) other than the above was repeated 5 times, and the obtained sediment (protective agent adsorbed on the surface and metal particles) was further heated at 105 ° C. for 3 hours and cooled. After that, its mass M 2 (g) is measured.
• Mass M 2 (g) of metal particles with protective agent adsorbed on their surfaces mass M 1 (g) of sampled metal particle dispersion - solvent S (g) - non-volatile content M 3 (g) other than metal particles with protective agent adsorbed on the surface
• the membrane used in the membrane filtration method is not particularly limited as long as it can separate the metal particles to which the protective agent is adsorbed on the surface and the other non-volatile matter from the metal particle dispersion liquid.
• Examples include an outer filtration membrane and a nanofiltration membrane, and among these, a membrane having an appropriate pore size can be used.
• Any method such as centrifugal filtration, pressure filtration, or cross-flow filtration can be used as the filtration method.
• the shape of the filtration membrane an appropriate shape such as a hollow fiber type, spiral type, tubular type, or flat membrane type can be used.
• the material of the filtration membrane is not particularly limited as long as it is durable against the metal particle dispersion, and may be polyethylene, tetrafluoroethylene, polypropylene, cellulose acetate, polyacrylonitrile, polyimide, polysulfone, polyethersulfone, or the like. and inorganic films such as silica, alumina, zirconia and titania.
• filtration membranes include Microza (manufactured by Asahi Kasei Chemicals Co., Ltd.), Amicon Ultra (manufactured by Merck Millipore Co., Ltd.), Ultra Filter (Advantech Toyo Co., Ltd.), MEMBRALOX (Nippon Pole ( Ltd.), Sepilt (NGK Insulators, Ltd.), and the like.
• the titanium oxide particle dispersion obtained in the step (7) and the tin component and the transition metal component obtained in the step (4) are solid-dissolved and the surface is modified with the iron component and the silicon component.
• a dispersion of titanium oxide particles and metal particles is obtained by mixing with a dispersion of metal particles containing the antibacterial metal.
• the mixing method is not particularly limited as long as the two dispersions are uniformly mixed.
• they can be mixed by stirring using a generally available stirrer.
• the mixing ratio of the titanium oxide particle dispersion and the metal particle dispersion is 1 to 100,000, preferably 1 to 100,000 in mass ratio (titanium oxide particles/metal particles) in each dispersion of the titanium oxide particles and the metal particles. 10 to 10,000, more preferably 100 to 1,000. When it is less than 1, the photocatalytic performance is not sufficiently exhibited, and when it exceeds 100,000, the antibacterial performance is not sufficiently exhibited, which is not preferable.
• volume-based 50% cumulative distribution diameter ( D50 ) measured by a dynamic light scattering method using a laser beam relating to the dispersed particle size of a mixture of titanium oxide particles and metal particles in a titanium oxide particle/metal particle dispersion (sometimes referred to as "average particle size") is as described above.
• the apparatus for measuring the average particle size is also as described above.
• the total concentration of the titanium oxide particles, metal particles, and other non-volatile matter in the titanium oxide particle/metal particle dispersion prepared in this manner is determined in terms of the ease with which a photocatalyst thin film having the required thickness can be produced. 0.01 to 20 mass % is preferable, and 0.5 to 10 mass % is particularly preferable.
• concentration adjustment when the concentration is higher than the desired concentration, the concentration can be lowered by adding an aqueous solvent to dilute, and when the concentration is lower than the desired concentration, the aqueous solvent is volatilized or filtered. concentration can be increased.
• titanium oxide whose concentration is adjusted as described above so that the desired concentration is obtained after mixing the above-described binder solution (aqueous binder solution). It is preferable to add to the particle/metal particle dispersion.
• the silicon component contained in the titanium oxide particle dispersion suppresses the aggregation and precipitation of the titanium oxide particles and the iron component, and suppresses the decrease in photocatalytic activity. It is added.
• the binder enhances the film-forming property of the titanium oxide particle/metal particle dispersion liquid, and is added after preparation of the titanium oxide particle/metal particle dispersion liquid and before coating. It is.
• the titanium oxide particle/metal particle composition of the present invention is a thin film of titanium oxide particles/metal particles
• the titanium oxide particle/metal particle dispersion liquid which is one aspect of the present invention, can be used to form a photocatalyst thin film on the surface of various members.
• the various members are not particularly limited, but examples of materials for the members include organic materials and inorganic materials. These can have various shapes according to their respective purposes and uses.
• 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
• acrylonitrile-butadiene rubber NBR
• polyethylene terephthalate PET
• polyethylene naphthalate PEN
• polyvinyl butyral PVB
• ethylene-vinyl alcohol copolymer EVOH
• polyimide resin polyphenylene sulfide (PPS)
• PPS polyether Synthetic resin materials
• imide PEI
• PEEI polyetheretherimide
• PEEK polyetheretherketone
• melamine resin phenolic resin
• ABS acrylonitrile-butadiene-styrene
• ABS acrylonitrile-butadiene-styrene
• ABS acrylonitrile-butadiene-styrene
• Inorganic materials include, for example, non-metallic inorganic materials and metallic inorganic materials.
• nonmetallic inorganic materials include glass, ceramics, and stone materials. These may be commercialized in various forms such as tiles, glass, mirrors, walls, design materials, and the like.
• metal inorganic materials include cast iron, steel materials, iron, iron alloys, aluminum, aluminum alloys, nickel, nickel alloys, and zinc die-cast. These may be plated with the metal inorganic material, coated with the organic material, or plated on the surface of the organic material or the non-metallic inorganic material.
• the dispersion of titanium oxide particles and metal particles of the present invention is particularly useful for producing photocatalyst thin films by applying it to various members made of inorganic substances such as glass and metals, and organic substances such as resins. It is particularly useful for producing transparent photocatalyst thin films on various members.
• a titanium oxide particle/metal particle dispersion is applied to the surface of the member by a known coating method such as spray coating or dip coating, followed by far infrared drying, It may be dried by a known drying method such as IH drying or hot air drying, and the thickness of the photocatalyst thin film may be selected variously.
• a known coating method such as spray coating or dip coating, followed by far infrared drying
• IH drying or hot air drying a known drying method such as IH drying or hot air drying
• the thickness of the photocatalyst thin film may be selected variously.
• the thin film of titanium oxide particles and metal particles described above is formed.
• the dispersion liquid contains the binder in the amount described above, a thin film containing the titanium oxide particles, the metal particles and the binder is formed.
• the photocatalyst thin film formed in this way is transparent and not only provides good photocatalysis in the light of the ultraviolet region (wavelength 10 to 400 nm) as in conventional photocatalysts, but also provides sufficient photocatalysis with conventional photocatalysts.
• a superior photocatalytic action can be obtained even with light in the visible region (wavelength 400 to 800 nm), which was not possible before. Depending on the action, it is possible to exhibit effects such as cleaning, deodorizing, and antibacterial effects on the surface of the member.
• D50 and D90 50% and 90% cumulative distribution diameters ( D50 and D90 ) of titanium oxide particles and/or metal particles in dispersion liquid
• the D 50 and D 90 of the titanium oxide particles and metal particles in the dispersion were measured by a dynamic light scattering method using a laser beam using a particle size distribution analyzer (ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.)).
• ELSZ-2000ZS manufactured by Otsuka Electronics Co., Ltd.
• Acetaldehyde gas decomposition performance test of photocatalyst thin film The activity of the photocatalyst thin film prepared by coating and drying the dispersion liquid was evaluated by the decomposition reaction of acetaldehyde gas. The evaluation was performed by the batch-type gas decomposition performance evaluation method. Each titanium oxide particle dispersion liquid prepared in Examples or Comparative Examples was applied to one side of an A4 size (210 mm x 297 mm) PET film and coated with a #7 wire bar so that the dry weight of the titanium oxide particles and metal particles was about 20 mg. A sample for evaluation was prepared by spreading it with a coater and dried for 1 hour in an oven set at 80° C.
• the photocatalytic activity of titanium oxide particles and metal particles was evaluated by the decomposition reaction of acetaldehyde gas.
• the evaluation was performed by the batch-type gas decomposition performance evaluation method. Specifically, after placing the evaluation sample in a stainless steel cell with a volume of 5 L and equipped with a quartz glass window, the cell was filled with an initial concentration of acetaldehyde gas adjusted to a humidity of 50%, and the light source was placed on top of the cell. was irradiated with light. When the acetaldehyde gas is decomposed by the photocatalytic action of titanium oxide, the acetaldehyde gas concentration in the cell decreases.
• the intensity of photocatalytic activity can be confirmed by measuring the concentration change.
• the acetaldehyde gas concentration was measured using a photoacoustic multi-gas monitor (trade name “INNOVA1412”, manufactured by LumaSense) to measure the time from the start of light irradiation until the acetaldehyde gas concentration became 1 ppm or less to evaluate the photocatalytic activity. The shorter the time, the higher the photocatalytic activity, and the longer the time, the lower the photocatalytic activity.
• an LED product model number “TH-211 x 200SW”, CCS Co., Ltd., spectral distribution: 400 to 800 nm
• the illumination is visible under the condition of 10,000 lx. irradiated with light.
• the initial concentration of acetaldehyde in the cell was set to 5 ppm.
• test result was evaluated according to the following criteria. ⁇ Very good (marked with ⁇ ) ⁇ reduced within 5 hours ⁇ Good (marked with ⁇ ) ⁇ reduced within 10 hours ⁇ Slightly poor (marked with ⁇ ) ⁇ reduced within 20 hours ⁇ Poor (indicated as x): cannot be reduced within 20 hours
• Antibacterial test of photocatalyst thin film (dark place, under visible light irradiation) The antibacterial performance of the photocatalytic thin film was measured by applying the photocatalytic thin film to a 50 mm square glass substrate to a thickness of 100 nm, and under visible light irradiation, the Japanese Industrial Standard JIS R 1752: 2020 "Fine ceramics-visible light responsive type.
• Antibacterial property test method and antibacterial effect of photocatalyst antibacterial processed material Test method conforming to the test method for hybrid photocatalyst antibacterial processed flat products. A Type B sharp cut filter was used, and the illuminance was 3,000 lx.
• test result was evaluated according to the following criteria. ⁇ Very good (indicated by ⁇ ): When all antibacterial activity values are 4.0 or more ⁇ Good (indicated by ⁇ ) ... When all antibacterial activity values are 2.0 or more ⁇ Poor ( ⁇ and displayed) ... When there is an antibacterial activity value of less than 2.0
• the crystalline phase of titanium oxide particles is determined by powder X-ray diffraction (product It was identified by measurement under the name "desktop type X-ray diffractometer D2 PHASER” (Bruker AXS Co., Ltd.).
• the obtained precipitate was deionized by repeating addition of pure water and decantation.
• sodium molybdate (VI) is added to the tin-containing titanium hydroxide precipitate so that the obtained titanium oxide particle dispersion has a TiO 2 /Mo (molar ratio) of 400, and , H 2 O 2 /(Ti + Sn + Mo) (molar ratio) is 10, 35% by mass of hydrogen peroxide solution is added, and then stirred at 60 ° C. for 2 hours to sufficiently react, orange transparent tin and molybdenum A containing peroxotitanic acid solution (1a) was obtained.
• [Preparation Example 1-2] ⁇ Preparation of titanium oxide particle dispersion in which tin and tungsten are solid-dissolved> Tin (IV) chloride was added to and dissolved in a 36% by mass titanium (IV) chloride aqueous solution so that the resulting titanium oxide particle dispersion had a TiO 2 /Sn (molar ratio) of 10, and then dissolved in pure water to 10. After diluting to two times, 10 mass % aqueous ammonia was gradually added to neutralize and hydrolyze to obtain a precipitate of titanium hydroxide containing tin. The pH at this time was 8. The obtained precipitate was deionized by repeating addition of pure water and decantation.
• sodium tungstate (VI) is added to the tin-containing titanium hydroxide precipitate so that the obtained titanium oxide particle dispersion has a TiO 2 /W (molar ratio) of 100, Furthermore, 35% by mass of hydrogen peroxide solution is added so that H 2 O 2 /(Ti+Sn+W) (molar ratio) becomes 10, and then stirred at 60° C. for 2 hours to fully react, producing orange transparent tin and A tungsten-containing peroxotitanic acid solution (1b) was obtained.
• An autoclave with a volume of 500 mL is charged with 400 mL of tin and tungsten-containing peroxotitanic acid solution (1b), this is hydrothermally treated at 160 ° C. for 60 minutes, and then pure water is added to adjust the concentration.
• a dispersion liquid (1B) (1.2% by mass of titanium oxide concentration) of titanium oxide particles in which tin and tungsten are solid-dissolved was obtained.
• An autoclave with a volume of 500 mL is charged with 400 mL of tin and vanadium-containing peroxotitanic acid solution (1c), which is hydrothermally treated at 140 ° C. for 120 minutes, and then pure water is added to adjust the concentration.
• a dispersion liquid (1C) of titanium oxide particles in which tin and vanadium were dissolved was obtained.
• Powder X-ray diffraction measurement of the titanium oxide particles revealed that the peaks observed were those of anatase-type titanium oxide and rutile-type titanium oxide, indicating that tin and vanadium were dissolved in titanium oxide.
• sodium molybdate (VI) is added to the tin-containing titanium hydroxide precipitate so that the resulting titanium oxide particle dispersion has a TiO 2 /Mo (molar ratio) of 100, and , H 2 O 2 /(Ti + Sn + Mo) (molar ratio) is 12, 35 mass% hydrogen peroxide water is added, and then stirred at 60 ° C. for 2 hours to sufficiently react, orange transparent tin and molybdenum A containing peroxotitanic acid solution (1d) was obtained.
• Preparation Example 1-6 ⁇ Preparation of titanium oxide particle dispersion in which molybdenum is dissolved> A dispersion liquid (1F) of titanium oxide particles in which molybdenum was dissolved (concentration of titanium oxide: 1.2% by mass) was obtained in the same manner as in Preparation Example 1-1, except that tin (IV) chloride was not added. rice field. As a result of powder X-ray diffraction measurement of the titanium oxide particles, it was found that the observed peak was only that of the anatase-type titanium oxide, indicating that molybdenum was dissolved in the titanium oxide.
• Preparation Example 1-7 ⁇ Preparation of titanium oxide particle dispersion in which tungsten is dissolved> Dispersion (1G) of titanium oxide particles in which tungsten was solid-dissolved (titanium oxide concentration: 1.2% by mass) was obtained in the same manner as in Preparation Example 1-2, except that tin (IV) chloride was not added. rice field. As a result of powder X-ray diffraction measurement of the titanium oxide particles, it was found that the observed peak was only that of the anatase-type titanium oxide, indicating that tungsten was dissolved in the titanium oxide.
• Preparation Example 1-8 ⁇ Preparation of Titanium Oxide Particle Dispersion with Vanadium Solid-Soluted> Dispersion (1H) of vanadium-dissolved titanium oxide particles (titanium oxide concentration: 1.2% by mass) was obtained in the same manner as in Preparation Example 1-3, except that tin (IV) chloride was not added. rice field. As a result of powder X-ray diffraction measurement of the titanium oxide particles, it was found that the observed peak was only that of the anatase-type titanium oxide, and vanadium was dissolved in the titanium oxide.
• Preparation Example 1-9 ⁇ Preparation of titanium oxide particle dispersion> After diluting a 36% by mass titanium (IV) chloride aqueous solution 10-fold with pure water, 10% by mass aqueous ammonia was gradually added to neutralize and hydrolyze the solution to obtain a titanium hydroxide precipitate. rice field. The pH at this time was 8.5. The obtained precipitate was deionized by repeating addition of pure water and decantation. After this deionization treatment, 35% by mass hydrogen peroxide solution was added to the titanium hydroxide precipitate so that the H 2 O 2 /Ti (molar ratio) was 8, and then stirred at 60° C. for 2 hours. to obtain an orange transparent peroxotitanic acid solution (1i).
• Table 1 summarizes the molar ratio of titanium oxide particles prepared in each preparation example, hydrothermal treatment conditions, dispersed particle diameters (D 50 , D 90 ), and pH of titanium oxide particle dispersions after hydrothermal treatment.
• the dispersed particle size was measured by a dynamic light scattering method (ELSZ-2000ZS (manufactured by Otsuka Electronics Co., Ltd.)) using a laser beam.
• the aqueous solution of iron sulfate and active silicic acid prepared as described above was added to the titanium oxide particle dispersion (1A) so that TiO 2 /Fe 2 O 3 was 200 and TiO 2 /SiO 2 was 100 at 25° C. for 1 hour. After mixing with a stirrer, the solid content concentration was adjusted to 1% by mass with pure water to obtain a titanium oxide particle dispersion liquid (2A) whose surfaces were modified with an iron component and a silicon component.
• Preparation Example 2-2 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2B) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1B) was used.
• Preparation Example 2-3 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2C) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1C) was used.
• Preparation Example 2-4 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component, Titanium Component and Silicon Component>
• a strongly acidic cation exchange resin (Amberlite HPR1024H, manufactured by Organo Co., Ltd.) was added to an aqueous sodium silicate solution obtained by dissolving 1.71 g of JIS No. 3 sodium silicate (29.1% in terms of SiO 2 ) in 100 g of pure water. After stirring, the ion exchange resin was separated by filtration to obtain an aqueous active silicic acid solution.
• titanium oxide particle dispersion (1A) To the titanium oxide particle dispersion (1A), the aqueous solution of iron sulfate, titanium chloride and active silicic acid prepared as described above was added to 200 of TiO 2 /Fe 2 O 3 , 200 of TiO 2 /TiO 2 (modifying component), 200 of TiO After mixing with a stirrer at 25° C. for 1 hour so that 2 /SiO 2 becomes 20, the solid content concentration is adjusted to 1% by mass with pure water, and the iron component, titanium component and silicon component are modified on the surface. A titanium oxide particle dispersion (2D) was obtained.
• the aqueous solution of iron sulfate and active silicic acid prepared as described above was added to the titanium oxide particle dispersion (1D) so that TiO 2 /Fe 2 O 3 was 400 and TiO 2 /SiO 2 was 200 at 25° C. for 1 hour.
• the solid content concentration was adjusted to 1% by mass with pure water to obtain a titanium oxide particle dispersion liquid (2E) whose surfaces were modified with an iron component and a silicon component.
• Preparation Example 2-6 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2F) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1E) was used.
• Preparation Example 2-7 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2G) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1F) was used.
• Preparation Example 2-8 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2H) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1G) was used.
• Preparation Example 2-9 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2I) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1H) was used.
• Preparation Example 2-10 ⁇ Preparation of Titanium Oxide Particle Dispersion with Surface Modified Iron Component and Silicon Component> A titanium oxide particle dispersion (2J) whose surface was modified with an iron component and a silicon component was obtained in the same manner as in Preparation Example 2-1, except that the titanium oxide particle dispersion (1I) was used.
• the solid content concentration was adjusted with pure water.
• a titanium oxide particle dispersion liquid (2K) having a surface modified with a silicon component was obtained by adjusting the concentration to 1% by mass.
• the dispersion of titanium oxide particles (1A) was mixed with the aqueous solution of iron sulfate prepared as described above so that TiO 2 /Fe 2 O 3 was 200 at 25° C. for 1 hour. was adjusted to 1% by mass with pure water to obtain a titanium oxide particle dispersion liquid (2 L) whose surface was modified with an iron component. During the addition of the iron sulfate aqueous solution, the dispersion became cloudy, and some precipitation was confirmed.
• a solution obtained by mixing 0.2 L of a solution containing a reducing agent/protective agent at 25° C. with 2 L of a solution containing a raw material metal compound heated to 90° C. in a reactor was added to an ultrafine molecular weight cutoff of 10,000.
• a silver particle dispersion liquid (3A) was obtained by performing concentration and pure water washing with a filtration membrane (Microza, Asahi Kasei Co., Ltd.). The obtained metal particle dispersions are summarized in Table 3 below.
• a solution containing a reducing agent was obtained by mixing 10% by mass of polyvinylpyrrolidone as a reducing agent/protective agent.
• Preparation Example 3-3 ⁇ Preparation of silver-zinc particle dispersion> Contains a raw metal compound obtained by using ethylene glycol as a solvent and dissolving silver nitrate so that the Ag concentration is 3.75 mmol/L and zinc nitrate hexahydrate so that the Zn concentration is 1.25 mmol/L.
• a silver-zinc particle dispersion (3C) was obtained in the same manner as in Preparation Example 3-2, except that the solution was used.
• Preparation Example 3-4 ⁇ Preparation of silver particle dispersion> A silver particle dispersion (3D) was obtained in the same manner as in Preparation Example 3-1, except that the amount of washing with pure water by the ultrafiltration membrane was reduced.
• Preparation Example 3-5 ⁇ Preparation of silver particle dispersion> A silver particle dispersion (3E) was obtained in the same manner as in Preparation Example 3-1, except that the polyvinylpyrrolidone added as a reducing agent/protective agent was not added.
• Example 2 The surface-protected metal particle dispersion (3B) was added to the surface-modified titanium oxide particle dispersion (2B) so that the mass ratio of the particles contained in each dispersion (surface-modified titanium oxide particles/surface-protected metal particles) was 400. By mixing, a titanium oxide particle/metal particle dispersion (E-2) of the present invention was obtained.
• Example 3 The surface-protected metal particle dispersion (3C) was added to the surface-modified titanium oxide particle dispersion (2C) so that the mass ratio of the particles contained in each dispersion (surface-modified titanium oxide particles/surface-protected metal particles) was 200. By mixing, a titanium oxide particle/metal particle dispersion (E-3) of the present invention was obtained.
• Example 4 The surface-protected metal particle dispersion (3A) was added to the surface-modified titanium oxide particle dispersion (2D) so that the mass ratio of the particles contained in each dispersion (surface-modified titanium oxide particles/surface-protected metal particles) was 100. By mixing, a titanium oxide particle/metal particle dispersion (E-4) of the present invention was obtained.
• Example 5 The surface-protected metal particle dispersion (3A) was added to the surface-modified titanium oxide particle dispersion (2E) so that the mass ratio of the particles contained in each dispersion (surface-modified titanium oxide particles/surface-protected metal particles) was 100. By mixing, a titanium oxide particle/metal particle dispersion (E-5) of the present invention was obtained.
• Example 6 The surface-protected metal particle dispersion (3D) was added to the surface-modified titanium oxide particle dispersion (2A) so that the mass ratio of the particles contained in each dispersion (surface-modified titanium oxide particles/surface-protected metal particles) was 100. By mixing, a titanium oxide particle/metal particle dispersion (E-6) of the present invention was obtained.
• Example 7 The metal particle dispersion (3E) was mixed with the surface-modified titanium oxide particle dispersion (2A) so that the mass ratio of the particles contained in each dispersion (surface-modified titanium oxide particles/metal particles) was 1,000. Thus, a titanium oxide particle/metal particle dispersion (E-7) of the present invention was obtained.
• Example 8 A silicon compound-based (silica-based) binder (colloidal silica, trade name: Snowtex 20, manufactured by Nissan Chemical Industries, Ltd.) is added to titanium oxide particle/metal particle dispersion (E-1), and titanium oxide particles/metal particles/ A binder (mass ratio) was added so as to be 1.5 and mixed with a stirrer at 25° C. for 10 minutes to obtain a binder-containing titanium oxide particle dispersion (E-8).
• Table 5 summarizes dispersions of titanium oxide particles and metal particles to which a binder was added.
• a titanium oxide particle dispersion (C-1) for comparative evaluation was obtained from the surface-modified titanium oxide particle dispersion (2A).
• a metal particle dispersion (C-2) for comparative evaluation was obtained from the surface protective silver particle dispersion (3A).
• a binder-containing titanium oxide particle/metal particle dispersion (C-12) was obtained in the same manner as in Example 8 except that the titanium oxide particle/metal particle dispersion (C-3) was used.
• Example 1 and Comparative Examples 3 and 9 and Example 8 and Comparative Example 12 the photocatalytic activity under visible light irradiation is low unless the titanium oxide surface is modified with an iron component (Fe) and a silicon component (Si). I found out.
• Example 1 From Example 1 and Comparative Example 11, it was found that when the surface of the surface-modified titanium oxide was further modified with a silver component, the photocatalytic activity under visible light irradiation decreased and the components aggregated and precipitated.

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