WO2013089229A1 - Liquide de revêtement de photocatalyseur et matériau organique possédant une fonction photocatalytique - Google Patents

Liquide de revêtement de photocatalyseur et matériau organique possédant une fonction photocatalytique Download PDF

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Publication number
WO2013089229A1
WO2013089229A1 PCT/JP2012/082489 JP2012082489W WO2013089229A1 WO 2013089229 A1 WO2013089229 A1 WO 2013089229A1 JP 2012082489 W JP2012082489 W JP 2012082489W WO 2013089229 A1 WO2013089229 A1 WO 2013089229A1
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tio
copper
titanium oxide
coating liquid
photocatalytic
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PCT/JP2012/082489
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English (en)
Japanese (ja)
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達志 長江
義行 中西
創史 大山
賢治 井上
井筒　裕之
英和 上田
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Toto株式会社
多木化学株式会社
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Publication of WO2013089229A1 publication Critical patent/WO2013089229A1/fr

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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8926—Copper and noble metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • 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
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C09D1/02—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates
    • C09D1/04—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances alkali metal silicates with organic additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • 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
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2248—Oxides; Hydroxides of metals of copper
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/17—Amines; Quaternary ammonium compounds

Definitions

  • the present invention relates to a photocatalyst coating liquid and an inorganic material having a photocatalytic function.
  • Photocatalysts such as titanium oxide have been widely used in recent years. Utilizing light energy, the photocatalyst can exhibit functions such as antibacterial, antiviral, antifungal and antialgal.
  • Patent Document 1 JP-A-11-349423
  • Patent Document 2 JP-A-2002-69915
  • Patent Document 3 Publication No. 00/06300 Pamphlet
  • Patent Document 4 International Publication No. 00/06300 Pamphlet
  • Patent Document 1 JP-A-11-349423
  • one or two kinds of metal particles selected from metal silver and metal copper of nanometer order are dispersed and adhered to titanium oxide particles of submicron size.
  • An antibacterial / deodorizing material is disclosed. It is said that the antibacterial / deodorizing material is obtained by the following method. That is, first, anatase-type titanium oxide particles having an average particle diameter of 0.01 ⁇ m were prepared, 98 g of the titanium oxide particles were added to and stirred with 300 ml of pure water, and the ammonia complex solution of silver nitrate and copper nitrate was added. Further, the mixture was stirred and dispersed.
  • Patent Document 2 discloses a sol containing crystalline titanium oxide, a copper compound, and an alkanolamine as main components. And there is the following description about this sol. That is, “useful for materials and applications that require antibacterial properties in particular, ceramic products such as synthetic fibers, natural fibers, plastics, rubber, ceramics, tiles, plates, spheres, such as glass, mirrors, metals, and wood. It can be used by applying to various shapes such as granular materials, or by immersing them in a sol, and for heat-resistant materials, to further improve the adhesion to the materials after application. A higher baking temperature is desirable. In addition, for materials that are difficult to heat and fire, the material sol can be treated with a fluororesin or silica sol in advance, and then the sol of the present invention can be applied to improve the adhesion to the material. "
  • Patent Document 3 discloses a photocatalytic titanium oxide sol containing silver and copper and quaternary ammonium hydroxide, in which silver is Ag 2 O / against titanium oxide.
  • TiO 2 is 0.1 to 5% by mass, and the ratio of copper to silver is preferably 1 to 30 as CuO / Ag 2 O (mass ratio).
  • Patent Document 4 discloses a method for producing a functional material having a photocatalytic function, which comprises a photocatalytic metal oxide and / or a precursor thereof on a substrate surface. Coating the substrate, rapidly heating the surface of the base material, and fixing the photocatalytic metal oxide to the surface of the base material, wherein the rapid heating is performed at a heating value of 120 MJ / m per unit area.
  • the heating means is provided with a heating element having a length of 2 ⁇ h or more, the distance from the heating element to the surface of the substrate is in the range of 5 mm to 300 mm, and the rapid heating is performed for 2 to 60 seconds. A method is disclosed.
  • the following manufacturing methods are disclosed as an example. “After heating the surface temperature of the tile to 200 ° C. with a preheating device, a titanium oxide sol doped with copper and an alkali silicate were mixed, and TiO 2 was 0.08%, CuO was 0.004%, and SiO 2 was 0. .3%, Li 2 O is 0.025%, Na 2 O is 0.04%, B 2 O 3 is 0.005% concentration so as the adjusted aqueous solution the substrate surface 1 cm 2 per 2 ⁇ 3 [mu] g The water was immediately evaporated and the solid content was fixed on the tile surface, and then the furnace temperature was about 750 ° C. and the heat amount was 1200 MJ in the rapid heating device 9 continuously provided in the drying device 12. / M 2 ⁇ h, fired at a heating area of 0.6 m 2 ”
  • the present inventors have recently applied a photocatalyst coating solution containing an alkali silicate, copper, alkanolamine and / or quaternary ammonium to a substrate and then calcining it, so that it can be substantially free of silver.
  • a photocatalytic functional material having sufficient antibacterial activity can be obtained when used in an environment in contact with water.
  • the object of the present invention is to provide a photocatalyst coating liquid having an excellent antibacterial function when used in an environment where water comes into contact with the base material after firing.
  • the photocatalyst coating liquid according to one embodiment of the present invention is used after being applied to a substrate containing photocatalytic titanium oxide particles, alkali silicate, copper, alkanolamine and / or quaternary ammonium, and firing.
  • the content is Ag 2 O / TiO 2 ⁇ 0.001 in terms of Ag 2 O converted mass ratio.
  • the photocatalyst coating liquid according to another aspect of the present invention is a photocatalyst coating liquid containing photocatalytic titanium oxide particles, alkali silicate, copper, and alkanolamine, which is used after firing on a substrate,
  • the copper content is 0.03 ⁇ CuO / TiO 2 ⁇ 0.3 in terms of CuO with respect to the photocatalytic titanium oxide particles and contains silver as an optional component
  • the content thereof Is characterized by Ag 2 O / TiO 2 ⁇ 0.001 in terms of Ag 2 O equivalent mass ratio.
  • Photocatalyst coating liquid The photocatalyst coating liquid according to the present invention is used after being applied to a substrate and calcined.
  • the photocatalytic functional material thus obtained has an excellent antibacterial function when used in an environment in contact with water.
  • this antibacterial function depends on both the antibacterial performance of the copper component itself and the antibacterial performance due to the photocatalytic effect.
  • excellent antibacterial activity is expressed only with copper without containing silver, but the mechanism is not clear. However, it is considered as follows. Since quaternary ammonium combined with alkali silicate does not have a high ability to dissolve copper, it is considered that the copper component exists as ultrafine particles supported on titanium oxide in the photocatalytic coating solution. It is done.
  • the alkanolamine and the quaternary ammonium may be used alone or in combination.
  • an inorganic material having a photocatalytic function having various antibacterial properties and coating properties can be obtained.
  • the content of copper in the photocatalyst coating liquid according to the present invention is 0.03 ⁇ CuO / TiO 2 ⁇ 0.3 in terms of CuO mass ratio. If it exceeds 0.03, the antibacterial performance due to the copper component can be sufficiently obtained, and if it is less than 0.3, the active site of the photocatalytic titanium oxide particles is covered with excess copper due to the copper component, and the antibacterial effect due to the photocatalytic effect It can suppress suitably that property falls.
  • the photocatalyst coating liquid according to the present invention does not substantially contain silver, and if present, the amount thereof is extremely small.
  • silver as an arbitrary component is an amount of Ag 2 O / TiO 2 ⁇ 0.001 in terms of Ag 2 O-converted mass ratio.
  • alkali silicate used in the present invention examples include lithium silicate, sodium silicate, potassium silicate, and mixtures thereof.
  • lithium silicate is preferable, and a mixture of lithium silicate and potassium silicate is more preferable.
  • the photocatalytic coating liquid according to the present invention contains an alkali silicate in a mass ratio of 2 to 5 with respect to the photocatalytic titanium oxide particles, and the alkali silicate contains lithium as an alkali component.
  • the content of the lithium relative to the copper, in Li 2 O in terms of mass ratio is 0 ⁇ Li 2 O / CuO ⁇ 2.
  • the photocatalytic titanium oxide is buried, and the antibacterial property due to the photocatalytic function tends to be lowered.
  • the content of the alkali silicate is too small, sufficient coating film adhesion cannot be obtained.
  • the coating film adhesion and the antibacterial performance due to the photocatalytic function are preferably compatible.
  • antibacterial performance improves by including lithium as an alkali metal of an alkali silicate.
  • the antibacterial performance can be improved very effectively by adding a very small amount, the antibacterial performance tends to decrease when added in a large amount.
  • Higher antibacterial performance is obtained when the lithium content is 0 ⁇ Li 2 O / CuO ⁇ 2 by mass ratio with respect to the copper. The reason why lithium works as an auxiliary agent for improving antibacterial performance is not clear, but it is considered that the amount of copper eluted into water is appropriately controlled by lithium.
  • the alkali silicate further contains potassium as an alkali component in addition to lithium, and the content of potassium is 5 ⁇ K 2 O / Li 2 in terms of K 2 O-converted mass ratio with respect to lithium. O ⁇ 50.
  • potassium improves the antibacterial activity, and further has the advantage of improving the coating film adhesion.
  • the photocatalytic titanium oxide particles are not particularly limited as long as they are particles having photocatalytic activity, but preferred examples include anatase-type titanium oxide particles, rutile-type titanium oxide particles, and brookite-type titanium oxide particles. More preferred are anatase type titanium oxide particles.
  • the photocatalytic titanium oxide particles preferably have an average particle size of 10 nm or more and 100 nm or less, more preferably 10 nm or more and 60 nm or less in the photocatalytic coating solution. Within this range, a thin film with good adhesion can be obtained.
  • the alkanolamine used in the present invention is an alkanolamine having hydrogen or a lower alkyl group (preferably C 1-6 alkyl). Specific examples thereof include monoethanolamine, diethanolamine, triethanolamine, 2-diethylaminoethanol. , N-methyldiethanolamine, N, N-dimethylethanolamine, 2-amino-2-methylpropanol, 2-ethylaminoethanol, N-ethyldiethanolamine, monoisopropanolamine, diisopropanolamine, triisopropanolamine, and even those A mixture is mentioned.
  • monoisopropanolamine, diisopropanolamine, and triisopropanolamine are preferable because they have a good balance between the solubility of copper and the dispersibility of the titanium oxide sol, and can stabilize the photocatalytic coating solution over a long period of time.
  • quaternary ammonium hydroxide is preferable, and specific examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, and choline.
  • tetramethylammonium hydroxide is preferable because it can stabilize the titanium oxide sol in a small amount and is easily available.
  • the photocatalyst coating liquid according to the present invention may be prepared by appropriately mixing the above components, but according to a preferred embodiment of the present invention, it contains photocatalytic titanium oxide, copper, alkanolamine and / or quaternary ammonium.
  • a method of adding an alkali silicate to the sol to be prepared is preferable from the viewpoint of the stability of the photocatalyst coating solution.
  • the following (1) to (4) can be mentioned as examples of the preferred method for producing the photocatalyst coating liquid according to the present invention.
  • Copper hydroxide and alkanolamine and / or quaternary ammonium are added to a photocatalytic titanium oxide sol and dissolved, and then alkali silicate is added.
  • a commercially available product for example, trade name “Tynoch” (manufactured by Taki Chemical Co., Ltd.) can be used, and as described in JP-B-2-62499, titanium chloride is used.
  • an alkaline compound such as an alkali metal hydroxide or an ammonium compound
  • water-soluble titanium such as titanium sulfate
  • hydrothermally treating at 100 ° C. or higher It can also be easily produced by wet grinding the titanium oxide powder.
  • An alkanolamine and / or quaternary ammonium is added to the titanium gel, and after hydrosolation, the oxide or hydroxide of copper is added and dissolved, and further an alkali silicate is added. Added.
  • Copper oxide or hydroxide, alkanolamine and / or quaternary ammonium are added to the titanium gel, and the mixture is hydrothermally treated to form a sol, and then alkali silicate is added.
  • a copper oxide or hydroxide previously dissolved with alkanolamine is added to the photocatalytic titanium oxide sol, and then an alkali silicate is added.
  • the content of alkali silicate in the photocatalyst coating liquid is not particularly limited as long as the effect of the present invention is obtained, but is preferably 30% by mass or more and less than 95% by mass in terms of SiO 2 with respect to the dry weight of the photocatalyst coating liquid, More preferably, it is 50 mass% or more and less than 90 mass%, Most preferably, it is 60 mass% or more and less than 80 mass%.
  • the photocatalyst coating liquid in the photocatalyst coating liquid, it is preferable to set the molar ratio of alkanolamine / copper compound (CuO) in the range of 0.5 to 5.8.
  • the alkanolamine / copper compound (CuO) molar ratio is 0.5 or more, copper tends to exist as ions.
  • the molar ratio is 5.8 or less, the long-term storage property of the photocatalyst coating liquid is increased, and a denser photocatalyst coating film tends to be easily obtained.
  • the photocatalytic coating liquid preferably contains quaternary ammonium in a range of 0.01 to 0.1 mol with respect to 1 mol of photocatalytic titanium oxide.
  • Quaternary ammonium can stabilize the titanium oxide sol as long as it is at least the lower limit of the above range.
  • the addition exceeds the upper limit of the above range, the effect of improving the stability of the photocatalyst coating liquid cannot be obtained any more, so there is little need to add beyond the upper limit.
  • the photocatalyst coating liquid according to the present invention may contain other components in addition to the above components.
  • an additional function can be provided.
  • the components that can be added include a pigment component for coloring the photocatalyst coating composition, a silica component for imparting hydrophilic performance to the coating film, and maintaining the storage stability and workability of the photocatalyst coating composition.
  • a thickener, an antifoamer, a dispersing agent etc. are mentioned.
  • the photocatalytic coating liquid is alkaline. By making it alkaline, the photocatalyst coating liquid becomes more stable.
  • the pH is preferably 7.5 to 10 in order to maintain stability over a long period of time.
  • the concentration of the photocatalytic titanium oxide in the photocatalytic coating liquid is preferably 0.01 to 1% by mass as TiO 2 , more preferably 0.05 to 0.00%. 5% by mass.
  • the photocatalyst coating liquid according to the present invention may be a solvent of water, but according to another aspect, it may be a mixed solvent of water and an organic solvent (for example, ethanol).
  • an organic solvent for example, ethanol
  • the solid content concentration of the photocatalyst coating liquid according to the present invention is not particularly limited, but is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass in terms of ease of application.
  • the components in the photocatalyst coating solution are analyzed by separating the photocatalyst coating solution into particle components and filtrate by ultrafiltration, and analyzing them by infrared spectroscopic analysis, gel permeation chromatography, fluorescent X-ray spectroscopic analysis, etc. It can be evaluated by analyzing the spectrum.
  • the photocatalyst coating liquid according to the present invention is applied to a substrate and then baked to form a photocatalyst layer, which is used for producing an inorganic material having a photocatalytic function. Therefore, according to one aspect of the present invention, there is provided a method for producing an inorganic material having a photocatalytic function, which comprises applying the photocatalyst coating liquid according to the present invention to the surface of an inorganic material substrate, and then firing it. The According to yet another aspect of the present invention, there is provided the use of a photocatalytic coating liquid according to the present invention for the production of an inorganic material having a photocatalytic layer.
  • the substrate is preferably made of an inorganic material.
  • ceramics such as tiles, large ceramic panels, natural stones, glazing, ceramics, glass, and concrete can be suitably used.
  • the ceramic base material any of a ceramic base material, a stone base material, and a porcelain base material may be used.
  • shape and the like are not particularly limited, and can be suitably used for building materials, interiors, exteriors, windows, toilets, washbasins, sinks, system kitchens, tombstones, bridge girders, bridges, insulators, ceramic plugs, and the like.
  • the photocatalytic functional material obtained by the photocatalytic coating liquid according to the present invention is used in an environment where it comes into contact with water.
  • the “environment in contact with water” means a state in which water is constantly or sometimes in contact with water. Therefore, the obtained photocatalytic functional material is, for example, in an environment where it comes into contact with water, where it is constantly exposed to running water, where it is exposed to occasional rain, where it is often exposed to water, It is used as an article or structure that requires antibacterial properties and is used in a place where it is cleaned with an object containing selenium.
  • copper is eluted from the photocatalytic layer of the photocatalytic functional material, and antibacterial activity is exhibited.
  • the antibacterial performance by a photocatalytic effect is mainly exhibited.
  • a photocatalyst layer is formed on the inorganic material substrate by baking after applying the photocatalyst coating liquid.
  • the photocatalyst layer includes not only a complete film shape but also a partially filmed state, for example. Moreover, it may exist discretely in the shape of islands on the substrate surface.
  • the photocatalyst coating liquid according to the present invention adheres to the base material with the desired strength by firing.
  • the photocatalyst layer has wear resistance. Any method can be used for firing as long as heat is sufficiently transmitted to the interface between the photocatalyst layer and the inorganic material substrate. That is, even if the whole inorganic material provided with the photocatalyst layer is heated, the surface of the inorganic material substrate on which the photocatalyst layer is formed may be partially heated.
  • the film thickness of the formed photocatalyst layer is preferably 0.05 ⁇ m or more and 1 ⁇ m or less.
  • a method for applying the photocatalyst coating liquid to the substrate in the present invention generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, and screen printing can be used.
  • Calcination after applying the photocatalyst coating liquid to the substrate is preferably performed so that the temperature of the application surface is 300 ° C. or higher and lower than 800 ° C., preferably 300 ° C. or higher and 600 ° C. or lower.
  • the temperature of the application surface is 300 ° C. or higher and lower than 800 ° C., preferably 300 ° C. or higher and 600 ° C. or lower.
  • heating by an electric furnace or a gas furnace may be mentioned, and the temperature may be gradually raised to reach the above temperature.
  • the substrate surface is irradiated with high energy in a short time of about 1 second to 1 minute, and heated to the above temperature only near the surface, more preferably from the surface of the inorganic material to the interface between the inorganic material substrate and the photocatalyst layer. May be.
  • This technique can be preferably applied to an inorganic material substrate whose heat resistance of the substrate is relatively low, such as natural stone or concrete.
  • the substrate surface may be preheated before application of the photocatalytic coating liquid to the substrate.
  • the preheating is performed by heating the surface of the substrate to 20 ° C. to 200 ° C.
  • the photocatalytic coating applied to the heated substrate surface is advantageous because it provides a uniform coating and a uniform coating.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • colloidal silica and copper hydroxide were added to 200 g of this slurry so that SiO 2 was 0.05 by mass ratio with respect to titanium oxide (TiO 2 ) and copper was 0.075 by mass ratio with respect to titanium oxide (TiO 2 ) in terms of CuO. Added. Furthermore, after adding a 25% aqueous solution of tetramethylammonium hydroxide at 0.03 mol to 1 mol of titanium oxide (TiO 2 ) and stirring well, this was placed in an autoclave and hydrothermally treated at 130 ° C. for 10 hours.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • titanium oxide (TiO 2) 0.1 mol based on 1 mol of copper hydroxide so copper of 0.05 at a mass ratio relative to titanium oxide in terms of CuO (TiO 2)
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • copper is 0.05 by mass ratio with respect to titanium oxide (TiO 2 ) in terms of CuO.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • copper is 0.05 by mass ratio with respect to titanium oxide (TiO 2 ) in terms of CuO.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • copper is 0.05 by mass ratio with respect to titanium oxide (TiO 2 ) in terms of CuO.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • copper is 0.05 by mass ratio with respect to titanium oxide (TiO 2 ) in terms of CuO.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • the powder obtained by drying this sol at 100 ° C. was measured by a powder X-ray diffraction method, a peak of anatase-type titanium oxide was observed.
  • Example 1A Preparation of Photocatalyst Coating Solution Anatase-type titanium oxide sol in which 5.4% of Cu obtained in Preparation Example 1 is mixed with TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the content of lithium was 1.26 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 2A Preparation of photocatalytic coating solution
  • the mass ratio of each solid content was 1: 3
  • water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 0.91 in terms of Li 2 O / CuO in terms of mass ratio with respect to the copper.
  • Example 3A Preparation of Photocatalyst Coating Liquid Anatase-type titanium oxide sol in which 5.4% of the copper obtained in Preparation Example 5 is blended with respect to TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the content of lithium was 1.26 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 4A Preparation of Photocatalyst Coating Liquid Anatase-type titanium oxide sol in which the copper obtained in Preparation Example 8 is blended at 5.0% with respect to TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.36 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 5A Preparation of photocatalyst coating solution
  • the mass ratio of each solid content was 1: 3
  • water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.36 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Comparative Example 6A Preparation of Photocatalyst Coating Solution Silver obtained in Preparation Example 3 was blended with 0.8% of TiO 2 in terms of Ag 2 O and 5.1% of Cu with respect to TiO 2 in terms of CuO.
  • Anatase-type titanium oxide sol and alkali silicate (solid content concentration: 20 to 23%) were prepared so that the mass ratio of each solid content was 1: 3, and then water was added to obtain a solid content concentration of 0.4%.
  • the photocatalyst coating liquid was obtained.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.33 in terms of Li 2 O / CuO in terms of mass ratio with respect to the copper.
  • Example 7A Preparation of photocatalytic coating liquid Anatase-type titanium oxide sol in which 5.2% of Cu obtained in Preparation Example 4 is mixed with TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.31 in terms of Li 2 O / CuO in mass ratio with respect to the copper.
  • Example 8A Preparation of photocatalytic coating solution Anatase-type titanium oxide sol in which 5.4% of the copper obtained in Preparation Example 6 was mixed with TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the content of lithium was 1.26 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 9A Preparation of photocatalytic coating solution
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.31 in terms of Li 2 O / CuO in mass ratio with respect to the copper.
  • Example 10A Preparation of Photocatalyst Coating Liquid Anatase-type titanium oxide sol in which the copper obtained in Preparation Example 10 is blended at 5.0% with respect to TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.36 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 11A Preparation of Photocatalyst Coating Solution Anatase-type titanium oxide sol in which the copper obtained in Preparation Example 11 was blended with 6.2% of TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.36 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 12A Preparation of Photocatalyst Coating Solution Anatase-type titanium oxide sol in which the copper obtained in Preparation Example 12 is mixed with 5.0% of TiO 2 in terms of CuO, and an alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 1.36 in terms of mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 13A Preparation of Photocatalyst Coating Liquid Anatase-type titanium oxide sol in which the copper obtained in Preparation Example 13 was mixed with 7.3% of TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the lithium content was 0.93 in terms of a mass ratio with respect to the copper in terms of Li 2 O / CuO.
  • Example 14A Preparation of Photocatalyst Coating Liquid Anatase-type titanium oxide sol in which 9.6% of the copper obtained in Preparation Example 14 is mixed with TiO 2 in terms of CuO, and alkali silicate (solid content concentration: 20 to 23%) Were prepared so that the mass ratio of each solid content was 1: 3, and then water was blended to obtain a photocatalyst coating liquid having a solid content concentration of 0.4%.
  • the amount of the alkali component in the alkali silicate is 2.3 parts by mass of Li 2 O converted lithium and 33 parts by mass of K 2 O converted potassium when the amount of SiO 2 is 100 parts by mass.
  • the content of lithium was 0.71 in terms of Li 2 O / CuO in terms of mass ratio with respect to the copper.
  • Examples 1B to 5B, Comparative Example 6B Production of tile having photocatalytic function
  • the above photocatalyst coating solutions 1A, 2A, 3A, 4A, 5A, and 6A were spray-coated on glazed tiles preheated to 80 to 150 ° C in advance. Each was applied by the method.
  • the furnace atmosphere temperature is 800 to 1100 ° C.
  • the thermocouple is installed near the burner in a position where no direct flame hits.) Heating is performed using a heating element whose calorific value per unit area is 1000 MJ / m 2 ⁇ h.
  • the distance from the heating element to the surface to which the coating solution was applied was set in the range of 5 mm to 300 mm, and baked for 10 to 20 seconds.
  • glazed tiles 1B, 2B, 3B, 4B, 5B, and 6B in which a photocatalytic layer was formed on the tile surface were obtained.
  • the surface temperature of the glazed tile immediately after being carried out of the furnace was 300 to 400 ° C.

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  • Wood Science & Technology (AREA)
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Abstract

La présente invention concerne un liquide de revêtement de photocatalyseur apte à produire un matériau inorganique présentant une excellente fonction photocatalytique dans un environnement dans lequel il est en contact avec de l'eau. Ledit liquide de revêtement de photocatalyseur de la présente invention comprend des particules d'oxyde de titane photocatalytiques, du silicate alcalin, du cuivre, une alcanolamine et/ou un ammonium quaternaire. Ledit liquide de revêtement de photocatalyseur se caractérise en ce que la teneur en cuivre est 0,03<CuO/TiO2<0,3 en tant que rapport de masse convertie-CuO par rapport aux particules de titane photocatalytique ; si le liquide de revêtement de photocatalyseur contient de l'argent, la teneur en argent est Ag2O/TiO2<0,001 en tant que rapport de masse convertie-Ag2O. Le matériau organique possédant la fonction photocatalytique est obtenu par l'application dudit liquide de revêtement à un substrat et la cuisson dudit substrat avec le liquide de revêtement appliqué.
PCT/JP2012/082489 2011-12-15 2012-12-14 Liquide de revêtement de photocatalyseur et matériau organique possédant une fonction photocatalytique WO2013089229A1 (fr)

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CN113004727A (zh) * 2021-04-06 2021-06-22 上海淞叶新材料有限公司 一种透明无机涂料及其制备方法
CN113683910A (zh) * 2020-05-18 2021-11-23 金百利科技(深圳)有限公司 一种具有高效光催化功能的光催化涂料及制备方法

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JP5896034B2 (ja) * 2012-09-19 2016-03-30 信越化学工業株式会社 可視光応答型光触媒微粒子分散液、その製造方法、及び光触媒薄膜を表面に有する部材
WO2017132302A1 (fr) * 2016-01-29 2017-08-03 Corning Incorporated Matériau incolore à performance antimicrobienne améliorée
JP6283922B1 (ja) * 2016-12-16 2018-02-28 パナソニックＩｐマネジメント株式会社 光触媒材及び光触媒塗料組成物
JP2020182918A (ja) * 2019-05-09 2020-11-12 Dic株式会社 酸化チタン組成物の製造方法

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