WO2004069946A1 - Materiau de revetement destine a former un film composite a base d'oxyde de titane/photocatalyseur - Google Patents

Materiau de revetement destine a former un film composite a base d'oxyde de titane/photocatalyseur Download PDF

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Publication number
WO2004069946A1
WO2004069946A1 PCT/JP2004/001366 JP2004001366W WO2004069946A1 WO 2004069946 A1 WO2004069946 A1 WO 2004069946A1 JP 2004001366 W JP2004001366 W JP 2004001366W WO 2004069946 A1 WO2004069946 A1 WO 2004069946A1
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Prior art keywords
titanium
oxide
fine particles
parts
aqueous solution
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PCT/JP2004/001366
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English (en)
Japanese (ja)
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Hideo Kogure
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Kansai Paint Co., Ltd.
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Publication of WO2004069946A1 publication Critical patent/WO2004069946A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G79/00—Macromolecular compounds obtained by reactions forming a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon with or without the latter elements in the main chain of the macromolecule
    • 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
    • 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
    • C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
    • C01P2004/86—Thin layer coatings, i.e. the coating thickness being less than 0.1 time the particle radius

Definitions

  • the present invention relates to a coating material for forming a photocatalytic titanium monoxide composite film. Background technology
  • the semiconductor When a semiconductor such as titanium oxide is irradiated with ultraviolet light, Z or visible light, the semiconductor absorbs light to generate excited electrons having a reducing effect and holes having an oxidizing effect, thereby oxidizing molecular species in contact with the semiconductor. Decomposes by reduction reaction.
  • Such an action is called a photocatalytic action, and in recent years, this photocatalytic action has been applied in various fields. For example, decomposition of NOX in the atmosphere; prevention of contamination in living and working spaces; decomposition and removal of odorous substances and mold; decomposition and removal of environmental pollutants such as organic solvents, pesticides, and surfactants in water. It is an application.
  • Photocatalysis is exerted at the contact surface between a substance that undergoes a redox reaction and a semiconductor that has photocatalytic activity. Therefore, when a coating material is coated on a substrate and dried to form a film containing a photocatalyst, in order to maximize the photocatalytic action, a high concentration of the coating material is contained in the binder. It is necessary to contain semiconductor fine particles. However, in the case of a coating agent using an ordinary organic binder, the binder is decomposed due to the photocatalytic action of the semiconductor fine particles in the formed film and the film becomes brittle, that is, the light resistance is insufficient. The problem was that long-term durability could not be obtained. Disclosure of the invention
  • An object of the present invention is to provide a coating agent for film formation.
  • the present inventor has made intensive studies to achieve the above object.
  • an aqueous solution of peroxotitanic acid was used as an inorganic binder for semiconductor fine particles having photocatalytic activity.
  • a coating agent containing them can form a titanium oxide film tightly integrated with the fine particles, and the formed photocatalyst It has been found that the titanium monoxide composite film exhibits an excellent photocatalytic action, and that the resulting composite film has excellent light resistance and long-term durability.
  • the present invention has been completed based on such new findings.
  • the present invention provides a coating material for forming a photocatalytic titanium monoxide composite film described below, a method for forming a photocatalytic film using the same, and an article obtained by the method.
  • At least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, a titanium hydroxide and a low condensate of titanium hydroxide is mixed with hydrogen peroxide water.
  • a coating agent for forming a photocatalytic titanium monoxide composite film comprising: the fine particles, the surface of which is coated with a titanium oxide film having a hydroxytitanium group.
  • the hydrolyzable titanium compound has the general formula
  • R represents the same or different and represents an alkyl group having 1 to 5 carbon atoms.
  • the coating agent according to the above item 2 which is a tetraalkoxytitanium represented by the formula:
  • the low-condensation product of the hydrolyzable titanium compound has the general formula
  • R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.
  • the above item which is a compound having a condensation degree of 2 to 30 obtained by subjecting a tetraalkoxytitanium represented by 2.
  • the aqueous solution of peroxotitanic acid (A) is composed of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. At least one titanium compound selected from the group and hydrogen peroxide solution were obtained by mixing 100 parts by weight of the former with 1 to 1,000 parts by weight of the latter in terms of hydrogen peroxide. 2.
  • Semiconductor fine particles having photocatalytic activity are composed of titanium oxide, tungsten oxide, zinc oxide, hafnium oxide, zirconium oxide, strontium titanate, titanium oxide, zirconium monoxide composite oxide and silicon oxide titanium oxide composite oxide.
  • the titanium oxide fine particles are at least one metal selected from the group consisting of Cr, Ru, V, Nb, Fe, Ni, Cu, Mg, Ag, Mn, Pd and Pt; Item 8.
  • the coating composition according to the above item 1 comprising 10 to 500 parts by weight of the semiconductor fine particles (B) based on 100 parts by weight of the solid content of the aqueous solution of peroxotitanic acid (A).
  • a method for forming a photocatalytic film which comprises applying the coating agent according to item 1 above on a substrate and drying to form a photocatalytic monoxide composite film.
  • the coating agent for forming a photocatalytic titanium monoxide composite film of the present invention contains a peroxotitanic acid aqueous solution (A) and semiconductor fine particles having photocatalytic activity whose surface is coated with a titanium oxide film having a hydroxytitanium group (B). Things.
  • the aqueous solution of peroxotitanic acid (A) in the coating composition of the present invention functions as an inorganic binder for the semiconductor fine particles.
  • the aqueous solution of peroxotitanic acid (A) contains at least one titanium compound selected from the group consisting of a hydrolyzable titanium compound, a low condensate of a hydrolyzable titanium compound, titanium hydroxide and a low condensate of titanium hydroxide. It is obtained by mixing with a hydrogen oxide solution.
  • the hydrolyzable titanium compound is preferably a compound represented by the general formula (1)
  • R is the same or different and represents an alkyl group having 1 to 5 carbon atoms.
  • alkyl group having 1 to 5 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, a sec-butyl group, a tert- Butyl group and the like.
  • the low-condensation product of the hydrolyzable titanium compound it is preferable to use a compound having a degree of condensation of 2 to 30 obtained by subjecting the compound of the general formula (1) to a self-condensation reaction. More preferably, 0 is used.
  • titanium hydroxide for example, orthotitanic acid (titanium hydroxide gel) obtained by reacting an aqueous solution such as titanium chloride or titanium sulfate with an aqueous alkali solution such as ammonia or caustic soda can be used.
  • an aqueous solution such as titanium chloride or titanium sulfate
  • an aqueous alkali solution such as ammonia or caustic soda
  • degree of condensation in the low-condensation product of titanium hydroxide compounds having a degree of condensation of 2 to 30 can be used, and those having a degree of condensation of 2 to 10 are particularly preferably used.
  • the raw material titanium compound and the hydrogen peroxide solution are used in an amount of 1 to 1,000 parts by weight in terms of hydrogen peroxide with respect to 100 parts by weight of the former. Preferably, it is appropriate to mix them in a proportion of 10 to 200 parts by weight. If the amount of the latter is less than 1 part by weight in terms of hydrogen peroxide, the formation of peroxotitanic acid becomes insufficient and cloudy precipitation occurs, which is not preferable. On the other hand, if it exceeds 1,000 parts by weight, unreacted hydrogen peroxide is apt to remain, and dangerous active oxygen is released during storage.
  • the hydrogen peroxide concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is preferably in the range of 3 to 40% by weight from the viewpoint of easy handling.
  • the mixing of the titanium compound as the raw material and the aqueous hydrogen peroxide is usually preferably performed at about 1 to 70 ° C. with stirring for about 10 minutes to 20 hours.
  • alcohol solvents such as methanol, ethanol, n-propanol and iso-isopropanol
  • water-soluble solvents such as alcohol ether solvents such as ethylene glycol monobutyl ether and propylene glycol monomethyl ether. Soluble organic solvents can also be used.
  • the aqueous solution of peroxotitanic acid (A) is prepared by mixing a titanium compound as a raw material with an aqueous solution of hydrogen peroxide, whereby the former is hydrolyzed with water to produce a hydroxyl-containing titanium compound, and then the hydrogen-containing titanium compound is added to the hydrogen-containing titanium compound. Is presumed to be obtained by immediate coordination to form peroxotitanic acid.
  • the solid content concentration of this aqueous solution of peroxotitanic acid (A) is usually about 0.1 to 10% by weight.
  • This aqueous solution of peroxotitanic acid (A) is highly stable at room temperature and withstands long-term storage.
  • At least one compound selected from acetoanilide, phenacetin and oxyquinoline may be added to the aqueous solution of peroxotitanic acid (A) in order to improve storage stability.
  • the amount of the compound to be added is in the range of 0.01 to 20 parts by weight, particularly 0.2 to 2.0 parts by weight, based on 100 parts by weight of the solid content of (A). Is preferred.
  • peroxotitanic acid aqueous solution (A) is mixed with 100 parts by weight of semiconductor fine particles having photocatalytic activity at a specific ratio of 0.5 to 10 parts by weight in terms of a converted solid content. It is essential to use the fine particles (B) which are dried by heating and coated with a titanium oxide film having a hydroxytitanium group on the surface.
  • the converted solid content of the aqueous solution of peroxotitanic acid (A) means a value obtained by multiplying the weight of the aqueous solution by the solid content concentration.
  • the coating composition of the present invention contains the semiconductor fine particles (B) subjected to the surface treatment as described above, whereby a titanium oxide film tightly integrated with the semiconductor fine particles can be formed.
  • the heating and drying conditions it is usually desirable to perform the heating at about 40 to 250 ° C. for about 1 to 24 hours.
  • the semiconductor fine particles to be used as the raw material may be any as long as they can absorb ultraviolet light, Z or visible light and exhibit a photocatalytic action, and known semiconductor fine particles can be used without any particular limitation.
  • the semiconductor fine particles include titanium oxide, tungsten oxide, zinc oxide, Fine particles such as metal oxides such as hafnium oxide, zirconium oxide, strontium titanate, titanium oxide-zirconium oxide composite oxide, and silicon oxide-titanium monoxide composite oxide are exemplified.
  • V vanadium
  • Cr chromium
  • Mn manganese
  • Fe iron
  • Co cobalt
  • Ni nickel
  • Cu copper
  • Zn zinc
  • Ru Ruthenium
  • Rhodium Rh
  • rhenium Re
  • osmium Os
  • palladium Pd
  • platinum Pt
  • iridium Ir
  • niobium Nb
  • Mo molybdenum
  • Metals, oxides, halides or complexes thereof that carry or contain the metal itself are also included.
  • These semiconductor fine particles can be used alone or in combination of two or more.
  • titanium oxide fine particles which are inexpensive and have excellent photocatalytic activity are preferable.
  • any of anatase type titanium oxide fine particles, rutile type titanium oxide fine particles, and wurtzite type titanium oxide fine particles can be used.
  • the metal itself such as Cr, Ru, V, Nb, Fe, Ni, Cu, Mg, Ag, Mn, Pd, and Pt, or an oxide, halide, or complex thereof is supported on the surface of the titanium oxide fine particles. What contained it can be used preferably.
  • titanium oxide fine particles having stable oxygen vacancies whose g value is 2.004 to 2.007 in the electron spin resonance spectrum (ESR) measured under light irradiation in the wavelength region of 420 nm or more. Titanium oxide fine particles in which a signal and two sub-signals having g values of 1.985 to 1.986 and 2.024 can be also used.
  • ESR electron spin resonance spectrum
  • the primary average particle diameter of the semiconductor fine particles is suitably in the range of 1 nm to: about 1,000 nm, preferably in the range of about 5 nm to 100 nm. It is difficult to manufacture semiconductor fine particles having a primary average particle size of less than 1 nm, while if the semiconductor fine particle has a primary average particle size of more than 1, OO Onm, the surface area is reduced and photocatalytic activity is exhibited. It is not preferable because it becomes difficult to be performed.
  • the primary average particle diameter of the semiconductor fine particles can be measured, for example, using a transmission electron microscope (TEM).
  • TEM transmission electron microscope
  • Pel is an essential component in the coating material for forming a photocatalytic titanium monoxide composite film of the present invention.
  • the content ratio of the aqueous solution of peroxotitanic acid (A) and the semiconductor particles (B) surface-treated as described above is usually 100 parts by weight of the solid content of the aqueous solution of peroxotitanic acid (A), ) Is about 10 to 500 parts by weight. If the amount of the component (B) is less than the above range, the thickness of the multi-layered layer on the surface of the semiconductor fine particles is undesirably increased because the photocatalytic reaction is inhibited. On the other hand, if the content of the component (B) is larger than the above range, the semiconductor fine particles (B) tend to deviate, which is not preferable.
  • the content is about 50 to 300 parts by weight of the semiconductor fine particles (B) with respect to 100 parts by weight of the converted solid content of the aqueous solution of peroxotitanic acid (A).
  • the mixing of the aqueous peroxotitanic acid solution (A) and the semiconductor fine particles (B) is performed so that the dispersed particle diameter of the fine particles (B) is 10 nm to 10 m, preferably about 10 nm to 1 zm. Dispersion treatment is desirable from the viewpoint of increasing the surface area of photocatalytic activity.
  • the term “dispersed particle size” refers to the particle size of the agglomerated state where the primary particles are present as a single particle when the semiconductor fine particles are dispersed.
  • the dispersed particle size can be measured in the state of the dispersion by, for example, a submicron particle analyzer.
  • a submicron particle analyzer for example, "C0ULTER MODEL N4SDJ (trade name, manufactured by COULTER ELECTRONICS, IN)" can be used.
  • the coating agent for forming a photocatalytic titanium monoxide composite film of the present invention may contain various additives, if necessary, in addition to the components (A) and (B).
  • Such additives include, for example, organic acids and Z or salts thereof from the viewpoint of improving the storage stability of the coating composition.
  • organic acid examples include organic carboxylic acids such as acetic acid, oxalic acid, glycolic acid, lactic acid, malic acid, citric acid, tartaric acid, and dalconic acid; methanesulfonic acid, ethanesulfonic acid, p-benzenesulfonic acid, and the like.
  • Organic sulfonates organic sulfinic acids such as 2-aminomonoethanesulfinic acid and p-toluenesulfinic acid; organic nitro compounds such as nitromethane, nitroethane, nitropropionic acid, nitrocatechol, 2-nitroresorcinol and nitrobenzoic acid; phenol , Strength alcohol, resorcinol, hydroquinone, pyrogallol, salicylic acid, gallic acid, cheap Phenols such as benzoic acid, thiophenol, 2-aminothiophenol, 4-ethylthiophenol, etc .; 1-hydroxymethane-1,1-diphosphonic acid, 1-hydroxixetane-1,1,1-diphosphonic acid, 1 -Hydroxypropane-1,1-diphosphonic acid, 2,3-amino (triamino) trimethylene phosphonic acid, 2,3-amino (triamino) triethylene phosphonic
  • a salt of an organic acid formed by adding an alkali compound to the above organic acid can be used.
  • the alkali compound include an organic or inorganic alkaline compound containing lithium, sodium, potassium, ammonium and the like.
  • organic acid or organic acid salt those which are soluble in water are preferably used.
  • hydroxycarboxylic acids such as glycolic acid, lactic acid, malic acid, citric acid, tartaric acid, and dalconic acid
  • Hydroxy group-containing organic phosphorous acid such as hydroxymethane-1,1-diphosphonic acid, 1-hydroxyxetane-1,1-diphosphonic acid, 1-hydroxypropane-1,1-diphosphonic acid
  • 2-hydroxyphosphonoacetic acid The use of at least one compound selected from the group consisting of organic phosphites containing lipoxyl groups, such as 2-phosphonobutane-1,2,4-tricarboxylic acid, and salts thereof, can improve the storage stability of coating agents.
  • the amount of the organic acid and / or organic acid salt to be added to the coating composition of the present invention is usually about 1 to 400 parts by weight based on 100 parts by weight of the solid content of the component (A). And particularly preferably in the range of about 10 to 200 parts by weight.
  • the coating composition of the present invention may further contain, if necessary, additives such as a basic neutralizer, a thickener, an organic solvent, a surfactant, a bactericide, a bactericide, a lubricant, a defoamer, and a chelating agent. , A reppelling agent, a coloring pigment, an extender pigment, a sunscreen pigment and the like.
  • the basic neutralizing agent include ammonia, organic basic compounds, alkali metal hydroxides, alkaline earth metal hydroxides, and the like.
  • the organic basic compound include dimethylethanolamine, 2-amino-12-methyl-11-propanol, triethylamine, and morpholine.
  • examples of the alkali metal hydroxide include lithium hydroxide, sodium hydroxide, and hydration power.
  • chelating agent for example, acetyl acetone and the like can be used.
  • coloring pigment examples include bengara, colored glass frit powder, and the like.
  • extender examples include Myriki, talc, silica, finely divided silica, barita, and clay.
  • the solid content concentration of the coating composition for forming a photocatalytic titanium monoxide composite film of the present invention is usually about 0.1 to 60% by weight, and has excellent storage stability.
  • the method for forming a photocatalyst film of the present invention is a method of applying the coating agent for forming a photocatalytic titanium monoxide composite film of the present invention on a base material and drying it to form a photocatalytic film as the composite film.
  • the substrate to which the method of the present invention can be applied is not limited as long as it is a substrate that is to exert a photocatalytic action.
  • the material of the base material there is no limitation on the material of the base material.
  • base materials of any material such as metal, ceramics, plastics, fiber, glass, and concrete can be used.
  • base materials such as plastics and fibers that are decomposable against photocatalysis, for example, a coating solution containing silicate such as silicate, peroxotitanic acid, etc. is applied or impregnated on the base material surface in advance.
  • a treatment can be applied to form a coating for insulating from photocatalysis.
  • the shape of the substrate may be any shape such as a plate shape, a spherical shape, a rectangular parallelepiped shape, and a cylindrical shape.
  • porous body, powder, or the like as a base material to perform internal treatment and surface treatment of the porous body and surface treatment of the powder.
  • the porous body include a foam, a honeycomb structure, a corrugated structure, and the like.
  • the powder include my strength, talc, silica, barium sulfate, clay, and the like. Color pigments such as pigment, red iron oxide, cobalt blue, and colored glass frit can be used.
  • Specific base materials include exteriors, interiors, windows and windows of architectural structures; road barriers; tunnel inner walls; vehicle interiors and windows; mirrors.
  • the surface of these substrates requiring photocatalysis can be coated with the coating composition of the present invention. Further, the members constituting these base materials may be painted in advance.
  • the coating agent of the present invention is coated on a substrate and dried to form a titanium oxide film with peroxotitanic acid in the component (A) and a photocatalyst treated with a specific surface treatment with a part of peroxotitanic acid. At least a part of the surface of the semiconductor fine particles having activity reacts to form a photocatalytic titanium monoxide composite film in which the fine particles and the titanium oxide film are integrated.
  • the coating method on the substrate may be a known coating method.
  • various coating methods such as print coating, knife coater coating, doctor blade coating, dip coating, shower coating, spray coating, roll coating, and electrodeposition coating can be employed.
  • the substrate surface may be impregnated and painted.
  • a photocatalyst-titanium oxide composite film having a thickness of 1 or more, which is generally hard to peel off and has excellent adhesion, can be formed by applying 10 times. Of course, if necessary, it may be applied several times.
  • Drying can be performed at room temperature. However, in order to sufficiently integrate the semiconductor fine particles and the titanium oxide film, it is preferable to heat and dry.
  • the heating temperature is usually about 40 ° C. to 250 ° C., and preferably about 80 to 200 ° C.
  • the heating time varies depending on the temperature, but it is usually appropriate to set the heating time at about 10 minutes to 3 hours.
  • the heating means for example, an electric furnace, a gas heating furnace, microwave heating, microwave induction heating, or the like is desirable.
  • the dry film thickness of the photocatalytic titanium monoxide composite film is not particularly limited. Usually, the film thickness is preferably about 0.001 to 20 m, more preferably about 0 :! to about 15 m.
  • an article in which a uniform photocatalytic titanium monoxide composite film is formed on a substrate can be prepared by the method for forming a photocatalytic film.
  • aqueous peroxotitanic acid solution A mixture of 1 part of tetra-iso-propoxytitanium and 10 parts of iso-propanol is mixed with 10 parts of 30% hydrogen peroxide solution and 100 parts of deionized water. The mixture was added dropwise at 20 ° C. over 1 hour with ultrasonic stirring. Thereafter, the mixture was aged at 25 ° C. for 2 hours to obtain a slightly viscous aqueous solution of peroxotitanic acid which was yellow and transparent. This was diluted with water to obtain a peroxotitanic acid aqueous solution (i) having a solid concentration of 3%.
  • a mixture of 10 parts of tetra_n-butoxytitanium and 10 parts of iso-propanol was added to a mixture of 20 parts of 30% hydrogen peroxide solution and 100 parts of deionized water at 20 ° C for 1 hour.
  • the mixture was added dropwise with ultrasonic stirring. Thereafter, aging was performed at 25 ° C for 2 hours to obtain a yellow transparent, slightly viscous aqueous solution of peroxotitanic acid. This was diluted with water to obtain a peroxotitanic acid aqueous solution (ii) having a solid concentration of 1%.
  • a mixture of 10 parts of tetraethoxytitanium and 15 parts of methoxyethanol is ultrasonically stirred at 20 ° C for 1 hour in a mixture of 20 parts of 30% hydrogen peroxide and 100 parts of deionized water. While dripping. Thereafter, the mixture was aged at 25 ° C for 2 hours to obtain a yellow transparent, slightly viscous aqueous solution of peroxotitanic acid. This was diluted with water to obtain a peroxotitanic acid aqueous solution (iiii) having a solid concentration of 2%.
  • alumina beads were added thereto, and 80 parts of a peroxotitanic acid aqueous solution (i) having a solid concentration of 3% was added, and the mixture was shaken and dispersed for 15 minutes.
  • An application agent (I) for forming a titanium monoxide composite film was obtained.
  • the above coating agent (I) is applied to an aluminum substrate (49.5 mm x 10 Omm x 3. Omm) by the air spray method so that the dry film thickness becomes 2 m, and heated and dried at 170 ° C for 30 minutes Thus, a photocatalytic titanium monoxide composite film was formed.
  • the pencil hardness of this composite film was 5H.
  • the decomposition rate of NOx gas was measured using the aluminum substrate on which the composite film was formed. That is, using a nitrogen oxide measuring instrument (trade name: Nitrogen oxide analyzer for environmental air CLAD-1000, manufactured by Shimadzu Corporation), NOx gas (NO (Gas concentration l ppm) was flowed at 2 L / min, and the irradiation rate of an AM 1.5 halogen 100 W artificial sun lamp was applied to evaluate the NOx gas decomposition rate of the aluminum substrate on which the composite film was formed. As a result, a NOx decomposition rate of 81% was obtained.
  • a photocatalytic titanium monoxide composite film was prepared in the same manner as above except that the above-mentioned coating agent (I) was used for dip coating on a foamed aluminum base material (a porous plate having a size of 49.5 mm ⁇ 10 Omm ⁇ 3.0 mm). Was formed. The cross section of this composite film is scanned with a scanning electron microscope.
  • a 25% aqueous solution of peroxotitanic acid having a solid content of 1% (ii) obtained in Production Example 2 was mixed with 25% brookite-type photocatalytic titanium oxide (trade name "NTB-200", manufactured by Showa Denko KK, 2.5% aqueous dispersion). 100 parts of a sol and an average particle diameter before solification were added (100 nm), dispersed by shaking, and then heated and dried at 80 ° C. for 4 hours to perform a surface treatment of the titanium oxide particles.
  • This coating agent (II) is applied to an ITO transparent conductive glass substrate (5 OmmX 10 OmmX 2 mm) by an air spray method so that the dry film thickness becomes 0.1 m, and is applied at 150 ° C for 30 minutes. After heating and drying for minutes, a photocatalytic titanium monoxide composite film was formed. The pencil hardness of this composite film was 2H.
  • the glass substrate on which the composite film was formed was immersed in a 1% aqueous solution of methylene blue for 10 minutes to adsorb methylene blue on the film surface.
  • the aqueous solution on the film surface was sucked off by a filter paper and removed to obtain a substrate for evaluation in which the film surface was stained blue.
  • the photodegradability of methylene blue was evaluated under irradiation of a 27W fluorescent lamp stand (distance 3 Ocm). As a result, methylene blue decomposed in 30 hours.
  • alumina beads were added thereto, and 80 parts of a peroxotitanic acid aqueous solution (iii) having a solid concentration of 2%, 10 parts of a 10% hydrogen peroxide solution, and 0.2 parts of butyl ether mouth solvent were added, and 15 minutes. After shaking and dispersion, the beads were separated and removed from the dispersion to obtain a coating agent (III) for forming a photocatalytic titanium monoxide composite film.
  • alumina beads were added thereto, and 80 parts of a peroxotitanic acid aqueous solution (i) having a solid concentration of 3% was added, and the mixture was shaken and dispersed for 15 minutes.
  • An application agent (IV) for forming a titanium monoxide composite film was obtained.
  • the above coating agent (IV) is applied to an aluminum substrate (49.5 mm x 10 Omm x 3. Omm) by the air spray method so that the dry film thickness becomes 2 m, and heated and dried at 170 ° C for 30 minutes Thus, a photocatalyst-titanium oxide composite film was formed.
  • the pencil hardness of this composite film was 5H.
  • the abrasion test was repeated 20 times with a load of 200 g using a gakushin abrasion tester, and it was confirmed that there was no abnormality in the composite membrane.
  • the decomposition rate of NOx gas was measured using the aluminum substrate on which the composite film was formed.
  • NOx gas calibrated with a standard gas with a NO concentration of 2 ppm using a nitrogen oxide measurement device (trade name: Nitrogen oxide analyzer for environmental air measurement C LAD-1000, manufactured by Shimadzu Corporation) (Gas concentration: 1 ppm) at a flow rate of 2 L / min and ultraviolet ⁇ intensity: While irradiating ultraviolet rays with black light of 0.8 mW / cm 2 , the decomposition rate of NOx gas on the aluminum substrate on which the composite film was formed was determined. evaluated. As a result, a NO decomposition rate of 87% was obtained.
  • Visible light responsive photocatalyst titanium oxide (trade name: MPT-621, manufactured by Ishihara Sangyo Co., Ltd., average particle size: 7 nm) 7 parts and alumina beads 40 in 20 parts of an anatase type titanium oxide sol aqueous solution with a solid content of 3% After shaking and dispersing for 2 hours, 80 parts of an anatase-type titanium oxide sol aqueous solution with 3% form concentration was added and shaken for 15 minutes.After dispersion, the beads were separated and removed from the dispersion, and a photocatalyst titanium monoxide composite film for comparison was applied. Agent (V) was obtained.
  • MPT-621 manufactured by Ishihara Sangyo Co., Ltd., average particle size: 7 nm
  • the above coating agent (V) is applied to an aluminum base material (49.5 mmX10 OmmX3.0 Omm) by an air spray method so that the dry film thickness becomes 2 m, and 170 ° After heating and drying with C for 30 minutes, when the formed film was brittle, vibrated, or the substrate was tilted, the film peeled off and could not be used for evaluation.
  • the above coating agent (VI) was applied to an aluminum substrate (49.5 mm ⁇ 10 Omm ⁇ 3.0 Omm) by an air spray method so that the dry film thickness became 2 m.
  • the resultant was dried by heating at 30 ° C. for 30 minutes to form a photocatalytic titanium monoxide composite film.
  • the pencil hardness of this composite film was 2B.
  • the abrasion test was repeated 20 times with a load of 200 g using a gakushin abrasion tester, the film was peeled off and the aluminum surface was exposed.
  • the invention's effect was applied to an aluminum substrate (49.5 mm ⁇ 10 Omm ⁇ 3.0 Omm) by an air spray method so that the dry film thickness became 2 m.
  • the resultant was dried by heating at 30 ° C. for 30 minutes to form a photocatalytic titanium monoxide composite film.
  • the pencil hardness of this composite film was 2B.
  • the abrasion test was repeated 20 times with a load of 200 g using
  • the peroxotitanic acid in the component (A) forms a titanium oxide film, and a part of peroxotitanic acid and a specific surface treatment are performed. At least a portion of the surface of the semiconductor fine particles (B) having the photocatalytic activity reacts to form a photocatalytic film that is a strong photocatalytic titanium monoxide composite film in which the fine particles and the titanium oxide film are integrated.
  • titanium oxide is formed by a self-condensation reaction of the peroxotitanic acid in the component (A), and that the hydroxytitanium group formed on the surface of the semiconductor fine particles (B) by the specific surface treatment is condensed with the peroxotitanic acid.
  • reaction (A) It is presumed that this is due to the chemical bond between the component and the component (B).
  • the photocatalytic titanium monoxide composite film obtained by the coating agent of the present invention exhibits an excellent photocatalytic action.
  • it is a robust inorganic film, and is not affected by deterioration such as photolysis due to radicals generated by a photocatalytic reaction, and has excellent light resistance, so that long-term durability can be obtained.
  • decomposition of NOX in the air prevention of contamination in living and working spaces; decomposition and removal of odorous substances and mold; decomposition and removal of environmental pollutants such as organic solvents, pesticides, and surfactants in water; It can be preferably applied to applications such as electrodes.
  • the coating agent of the present invention has dramatically improved storage stability. The reason is presumed to be that the hydroxytitanium group on the surface of the semiconductor fine particles (B) is protected by a hydrophilic and sterically hindered functional group called peroxo group of peroxotitanic acid in the component (A). You.
  • the coating agent of the present invention can form a photocatalytic titanium monoxide composite film capable of forming a titanium oxide film which is firmly integrated with fine particles of semiconductor particles having photocatalytic activity even at a high concentration.
  • a porous composite film can be formed by including semiconductor particles at a high concentration.

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Abstract

L'invention concerne un matériau de revêtement destiné à former un film composite d'oxyde de titane/photocatalyseur, caractérisé en ce qu'il comprend (A) une solution d'acide de peroxotitane aqueux obtenue par mélange d'au moins un composé de titane choisi dans le groupe constitué d'un composé de titane hydrolysable, d'un faible condensat d'un composé de titane hydrolysable, d'un hydroxyde de titane, et d'un faible condensat d'hydroxyde de titane à solution de peroxyde d'hydrogène aqueux et (B) des particules fines obtenues par mélange de 100 parties en poids de particules à semiconducteurs fines à activité photocatalytique avec 0,5 à 10 parties en poids, sur une base solide, de la solution d'acide de peroxotitane aqueuse (A) et par séchage du mélange par chauffage afin de revêtir la surface de particules à semiconducteurs d'un film d'oxyde de titane à groupes d'hydroxytitane.
PCT/JP2004/001366 2003-02-10 2004-02-10 Materiau de revetement destine a former un film composite a base d'oxyde de titane/photocatalyseur WO2004069946A1 (fr)

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TW200837156A (en) * 2007-02-22 2008-09-16 Kansai Paint Co Ltd Coating agent for forming titanium/zirconium film, method for forming titanium/zirconium film and metal substrate coated with titanium/zirconium film
JP5255359B2 (ja) * 2008-07-28 2013-08-07 住友化学株式会社 膜形成用前駆体溶液
JP5308117B2 (ja) * 2007-10-29 2013-10-09 住友化学株式会社 透明導電性基板の製造方法
JP2010234355A (ja) * 2009-01-20 2010-10-21 Shin-Etsu Chemical Co Ltd 可視光応答性に優れる光触媒塗工液
CN102614931B (zh) * 2012-03-02 2014-05-14 湖州师范学院 溶液浇筑法制备PHBV装载改性纳米TiO2薄膜
JP2013209558A (ja) * 2012-03-30 2013-10-10 Central Japan Railway Co 薄膜形成方法
CN102974336A (zh) * 2012-12-11 2013-03-20 常州大学 一种负载光催化薄膜制备方法
JP6265410B2 (ja) * 2013-10-02 2018-01-24 国立研究開発法人物質・材料研究機構 コア−シェル型光触媒の製造方法
CN104907086A (zh) * 2015-05-21 2015-09-16 河南师范大学 具有微观分级结构的花状磷酸铋光催化剂的仿生合成方法

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