[go: up one dir, main page]

WO2011118781A1 - Corps recouvert d'un photocatalyseur - Google Patents

Corps recouvert d'un photocatalyseur Download PDF

Info

Publication number
WO2011118781A1
WO2011118781A1 PCT/JP2011/057384 JP2011057384W WO2011118781A1 WO 2011118781 A1 WO2011118781 A1 WO 2011118781A1 JP 2011057384 W JP2011057384 W JP 2011057384W WO 2011118781 A1 WO2011118781 A1 WO 2011118781A1
Authority
WO
WIPO (PCT)
Prior art keywords
photocatalyst
beads
layer
intermediate layer
coated body
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2011/057384
Other languages
English (en)
Japanese (ja)
Inventor
信 早川
康次 大久保
浩 中野
理 浦
剛史 山元
泰志 新美
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toto Ltd
Original Assignee
Toto Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toto Ltd filed Critical Toto Ltd
Priority to JP2012507092A priority Critical patent/JP5707389B2/ja
Publication of WO2011118781A1 publication Critical patent/WO2011118781A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • B01J37/0219—Coating the coating containing organic compounds
    • 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
    • B01J37/024—Multiple impregnation or coating
    • B01J37/0244—Coatings comprising several layers
    • 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

Definitions

  • the present invention relates to a photocatalyst-coated body having a photocatalyst layer excellent in weather resistance, photocatalytic decomposability, light resistance and various film performances, which is particularly suitable for applications such as exterior materials and interior materials such as buildings.
  • photocatalysts such as titanium oxide have been used in many applications such as building exterior materials. Utilizing the activity excited by the photocatalyst's light energy, it is possible to decompose various harmful substances, or to make the substrate surface coated with the photocatalyst hydrophilic and easily wash away dirt adhering to the surface with water. It becomes.
  • an intermediate layer is provided between the base material serving as the base and the photocatalyst for the purpose of adhesion and / or suppression of deterioration of the base material surface due to the photocatalyst.
  • a technique for obtaining a photocatalyst-coated body coated with such a photocatalyst a technique is known in which an intermediate layer such as a silicone-modified resin is provided between a base substrate and a photocatalyst. (For example, refer to Patent Document 1 (International Publication No. 97/00134 pamphlet)).
  • Patent Document 2 Japanese Patent Laid-Open No. 2009-136811
  • the amount of the photocatalyst contained in the photocatalyst layer has been conventionally increased.
  • the base material may be deteriorated by the photocatalyst.
  • the present inventors can improve the photocatalytic activity by adding specific beads to the intermediate layer provided so as to be in contact with the lower side of the photocatalyst layer. As a result, the amount of photocatalyst in the photocatalyst layer is reduced. And the knowledge that deterioration of a base material can be prevented effectively was acquired. The present invention is based on such knowledge.
  • an object of the present invention is to provide a photocatalyst-coated body that is excellent in the photocatalytic decomposition function while reducing the amount of photocatalyst contained in the photocatalyst layer.
  • the photocatalyst-coated body according to the present invention includes a base material, a photocatalyst layer containing photocatalyst particles, and an intermediate layer provided between the base material and the photocatalyst layer so as to be in contact with the lower side of the photocatalyst layer.
  • a photocatalyst-coated body comprising at least The intermediate layer comprises at least one kind of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, and a silicone-modified resin, and the beads include the intermediate layer and the photocatalyst layer.
  • a convex portion due to the shape is formed on the interface.
  • the present invention also relates to a coating composition for forming the photocatalyst-coated body.
  • the coating composition comprises a substrate, a photocatalyst layer containing photocatalyst particles, and the substrate and the photocatalyst layer.
  • a coating composition for forming the intermediate layer of the photocatalyst-coated body comprising at least an intermediate layer provided so as to be in contact with the lower side of the photocatalyst layer, It comprises at least one kind of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, a silicone-modified resin, and a solvent, and the apparent density of the beads is smaller than that of the silicone-modified resin and the solvent. It is characterized by having been made.
  • the present invention also relates to a method for producing the above-mentioned photocatalyst-coated body, which comprises at least one kind of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads on the surface of the substrate, and a silicone-modified resin. And a step of applying a coating solution comprising at least a solvent and then drying to form an intermediate layer, and applying a photocatalyst coating solution comprising photocatalyst particles to the intermediate layer to form a photocatalyst layer. And a process.
  • the photocatalyst-coated body of the present invention it is possible to provide a photocatalyst-coated body that has an excellent photocatalytic decomposition function while reducing the amount of photocatalyst contained in the photocatalyst layer.
  • Photocatalyst-coated body is an intermediate provided between a base material, a photocatalyst layer containing photocatalyst particles, and the base material and the photocatalyst layer so as to be in contact with the lower side of the photocatalyst layer
  • a photocatalyst-coated body comprising at least a layer, wherein the intermediate layer includes at least one kind of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, and at least a silicone-modified resin.
  • the bead is formed by forming a convex portion due to its shape at the interface between the intermediate layer and the photocatalyst layer.
  • the photocatalyst-coated body according to the present invention can provide a photocatalyst-coated body that reduces the amount of photocatalyst contained in the photocatalyst layer and has an excellent photocatalytic decomposition function is not clear, but is considered as follows.
  • the convex part resulting from the shape of a bead is formed in the interface of the intermediate
  • this is only a hypothesis, and the present invention is not limited by this.
  • the bead forms a convex portion due to its shape at the interface between the intermediate layer and the photocatalyst layer.
  • the convex portion resulting from the shape of the beads refers to a portion formed due to a relatively protruding presence of at least a part of the beads at the interface between the intermediate layer and the photocatalytic layer.
  • the beads may or may not be exposed from the intermediate layer.
  • irregularities caused by other than the interface beads between the intermediate layer and the photocatalyst layer may exist.
  • the modified silicone when the beads are made of resin, the beads are not exposed at the interface, the modified silicone covers the beads, and the modified silicone is in contact with the photocatalyst layer from the viewpoint of weather resistance.
  • it may be a convex portion that substantially conforms to the shape of the bead, or a convex portion that slightly reflects the shape of the bead.
  • the photocatalyst-coated body according to the present invention is also advantageous in that the effect of enhancing the adhesion between the intermediate layer and the photocatalyst layer can be expected in some cases due to the unevenness at the interface between the intermediate layer and the photocatalyst layer.
  • the intermediate layer of the present invention comprises at least one kind of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, and at least a silicone-modified resin.
  • the beads are at least one kind of beads selected from the group consisting of resin beads, hollow glass beads, and hollow ceramic beads, and preferably resin beads.
  • the resin constituting the beads include acrylic resin, epoxy resin, polyamide resin, polyurethane resin, unsaturated polyester resin, vinyl ester resin, phenol resin, silicone resin, acrylic silicone resin, fluorine resin, ketone resin, polyethylene resin, Polypropylene resin, super short oil alkyd resin, short oil alkyd resin, medium oil alkyd resin, long oil alkyd resin, super long oil alkyd resin, melamine resin, amino alkyd cocondensation resin, urea resin, vinyl chloride resin, vinyl acetate resin, polyvinyl Examples include alcohol and polyvinyl butyral.
  • the particle size of the beads is larger than the film thickness of the photocatalyst layer of the photocatalyst-coated body.
  • the particle size of the beads is smaller than the film thickness of the intermediate layer of the photocatalyst-coated body.
  • the thickness of the intermediate layer is preferably 1 ⁇ m or more and 100 ⁇ m or less, a more preferred lower limit is 3 ⁇ m, a further preferred lower limit is 10 ⁇ m, and a preferred upper limit is 50 ⁇ m. Therefore, the particle size of the beads can be appropriately determined in consideration of the above, but more specifically, it is preferably in the range of 0.3 to 30 ⁇ m, more preferably 1 to 30 ⁇ m, and most preferably 3 to 30 ⁇ m.
  • the addition amount of beads is preferably 1 to 50%, more preferably 3 to 30%, and most preferably 5 to 20% with respect to the solid content weight of the intermediate layer.
  • a convex portion resulting from the shape can be efficiently formed at the interface between the intermediate layer and the photocatalyst layer. Conceivable.
  • the apparent density of the beads is higher than the components of the composition other than the beads, particularly at least the silicone-modified resin and the solvent. Is also considered to be small.
  • the beads float upward in the composition, and the beads can be collected near the interface with the photocatalyst layer of the intermediate layer, thereby efficiently forming the convex portion due to the shape thereof. be able to.
  • the convex portion due to the shape of the interface between the intermediate layer and the photocatalyst layer can be more efficiently used. It is thought that can be formed.
  • the intermediate layer of the photocatalyst-coated body according to the present invention is composed of at least the above beads and a silicone-modified resin.
  • the silicone-modified resin basically functions as a matrix for the intermediate layer. Specific examples thereof include silicone-modified acrylic resins, silicone-modified epoxy resins, silicone-modified urethane resins, and silicone-modified polyesters containing polysiloxane in the resin. Available.
  • the intermediate layer of the photocatalyst-coated body according to the present invention is formed by using, as a coating composition for forming the intermediate layer, an aqueous dispersion of a silicone-modified resin containing the above beads as a substrate. After application, preferably after application, it can be cured and formed.
  • an aqueous dispersion include a resin-based colloidal dispersion containing a siloxane of about 50 to 200 nm, a curable silicone-modified resin emulsion, and the like.
  • the resin-based colloidal dispersion is a water dispersion composed of a composite resin in which a polymer segment such as acrylic or urethane having a silyl group is combined with a branched polysiloxane segment having a hydroxyl group bonded to a silicon atom. Examples include the body.
  • the silicone-modified resin matrix of the intermediate layer may be formed by applying a curable silicone-modified resin emulsion to a substrate and then curing it.
  • a hydrolysis / condensation reaction, a photopolymerization reaction, or the like can be suitably used for the curing reaction.
  • the curing reaction is a hydrolysis / condensation reaction
  • a curable silicone emulsion having an alkoxide group as a functional group and generating a siloxane bond by the hydrolysis / condensation reaction can be suitably used.
  • the curable silicone emulsion in addition to the functional group causing the curing reaction, there is an organic cross-linked portion by emulsion polymerization.
  • a crosslinking part produced by radical polymerization such as an ethylene crosslinking part in which a vinyl group and a vinyl group are polymerized can be suitably used.
  • radical polymerization it is not particularly limited to a hydrocarbon group, and a combination of various modifying groups can be suitably used.
  • an organic group that binds to a silicon atom may be present in addition to the functional group that causes the curing reaction and the organic crosslinking portion.
  • the organic group include a hydrocarbon group such as an alkyl group, a phenyl group, and a cycloalkyl group, and an organic group in which a part of the hydrogen is substituted with a modifying group.
  • the modifying group include an amino group, a carboxyl group, a mercapto group, an acrylic group, and an epoxy group.
  • nonionic, cationic and anionic surfactants As the surfactant used as an emulsifier for the above-mentioned emulsion, conventionally known nonionic, cationic and anionic surfactants, and reactive emulsifiers containing functional groups capable of radical polymerization can be used.
  • specific examples of usable nonionic surfactants such as polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene carboxylic acid ester, sorbitan ester, polyoxyethylene sorbitan ester, and alkyltrimethylammonium chloride.
  • Cationic surfactants such as alkylbenzylammonium chloride, anionic surfactants such as alkyl or alkylallylsulfate, alkyl or alkylallylsulfonate, dialkylsulfosuccinate, amino acid type, betaine type, etc.
  • Ionic surfactants radicals containing hydrophilic groups such as sulfonates, polyoxyethylene chains, and quaternary ammonium salts in the molecules described in JP-A-8-27347 If possible (meth) acrylate, styrene, various reactive surfactants containing derivatives such as maleic acid ester compound.
  • surfactants may be used alone or in combination of two or more.
  • the surfactant is preferably used in an amount of 0.5 to 15% by weight, particularly 1 to 10% by weight, based on the resin solid content in the emulsion.
  • the siloxane (Si—O) content in the silicone-modified resin constituting the silicone-modified resin matrix is 0.4 mass% or more to the solid content of the silicone-modified resin. It is made to be less than mass%, more preferably 12 mass% or more and less than 33 mass%. Thereby, weather resistance to ultraviolet rays in the intermediate layer and erosion by the photocatalyst can be sufficiently suppressed, and generation of cracks can be efficiently suppressed.
  • the silicon atom content in the silicone-modified resin can be measured by chemical analysis using an X-ray photoelectron spectrometer (XPS).
  • the intermediate layer can further comprise an ultraviolet absorber.
  • the amount of the ultraviolet absorber added to the intermediate layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.
  • ultraviolet absorbers include benzophenone-based, benzotriazole-based, and triazine-based ultraviolet absorbers.
  • the triazine-based ultraviolet absorbers hydroxyphenyltriazine is excellent in absorption characteristics at a wavelength of 380 nm or less, and chemical. It is preferable because it is stable.
  • the hydroxyphenyl triazine compound is a derivative of hydroxyphenyl triazine and / or hydroxyphenyl triazine having a basic skeleton represented by the following general formula, and a commercially available hydroxyphenyl triazine-based ultraviolet absorber can be suitably used.
  • the intermediate layer further contains a light stabilizer such as a hindered amine and / or a hindered phenol. Due to the synergistic effect with the ultraviolet absorber, the weather resistance and light resistance of the photocatalyst-coated body according to the present invention can be expected to be improved.
  • a hindered amine is preferably selected as a light stabilizer.
  • the hydroxyphenyl triazine compound provides an advantage that the absorption performance of ultraviolet rays having a short wavelength of less than 380 nm is stabilized.
  • the content of the light stabilizer with respect to the intermediate layer is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass.
  • hindered amine light stabilizer examples include bis (2,2,6,6-tetramethyl-4-piperidyl) succinate, bis (2,2,6,6-tetramethylpiperidyl) sebacate, bis (1, 2,2,6,6-pentamethyl-4-piperidyl) 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-butylmalonate, 1- [2- [3- (3 5-Di-tert-butyl-4-hydroxyphenyl) propynyloxy] ethyl] -4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propynyloxy] -2,2,6 6-tetramethylpiperidine, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and methyl-1,2,2,6,6-pentamethyl-4-piperidyl-seba Mixture (product name: TINUVIN-292, manufactured by Ciba Japan Co
  • hindered amine ultraviolet absorbers examples thereof include polymerizable hindered amine ultraviolet absorbers and their (co) polymers.
  • Specific examples of hindered phenol light stabilizers include bis (3,5-tert-butyl) -4-hydroxytoluene, TINUVIN-144 (product name, manufactured by Ciba Japan Co., Ltd.), and the like. it can.
  • the intermediate layer of the photocatalyst-coated body according to the present invention can contain extender pigments, color pigments, anti-algae agents, viscosity modifiers and the like as optional components.
  • extender pigments examples include titanium oxide whisker, calcium carbonate whisker, aluminum borate whisker, potassium titanate whisker, mica, and talc.
  • the color pigment examples include titanium oxide white, zinc oxide white iron oxide, carbon black, spinel green, bengara, cobalt aluminate, ultramarine blue and the like, phthalocyanine series, benzimidazolone series, isoindolinone series, azo And organic color pigments such as those based on anthraquinone, quinophthalone, anthrapyridinine, quinacridone, toluidine, pyrathrone and perylene.
  • organic anti-fungal agents having good compatibility with the resin component of the intermediate layer can be suitably used.
  • viscosity modifier examples include organic bentonite, ultrafine silica, surface-treated calcium carbonate, amide wax, hydrogenated castor oil wax, benzylidene sorbitol, various metal soaps, polyethylene oxide, and polymerized vegetable oil. , Sulfate ester anionic surfactant, polyether ester type surfactant, polycarboxylic acid amine salt, magnesium aluminum silicate, xanthan gum, guar gum, polyacrylate soda, acrylic acid / acrylate copolymer (Alkali thickening system), polyvinyl alcohol system, polyethylene oxide system, urethane-modified polyether system and the like.
  • the intermediate layer can be produced by applying, preferably applying, the above-described composition composed of at least beads and a silicone-modified resin on a substrate.
  • a method for applying the intermediate layer generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, screen printing and the like can be used.
  • the intermediate layer is formed by drying at room temperature or, if necessary, drying by heating. By drying, it is possible to maintain the state in which the beads floating upward in the composition are collected near the surface of the intermediate layer serving as the interface with the photocatalyst layer, and it is possible to efficiently form convex portions due to the shape thereof It becomes possible.
  • the solvent of the coating composition for forming the intermediate layer any solvent can be used as long as it can disperse the above-mentioned constituents appropriately, and water and / or an organic solvent may be used.
  • the solid content concentration of the composition is not particularly limited, but is preferably about 10 to 60% by mass, more preferably about 15 to 50% by mass because of ease of application.
  • middle layer formation can be performed by infrared spectroscopy about a resin component.
  • the coating composition for forming the intermediate layer may contain paint additives such as pigment dispersants, antifoaming agents, antioxidants, and other components that are usually included in paints. Further, a matting agent such as silica fine particles may be included.
  • Photocatalyst layer of the present invention is a layer containing photocatalyst particles provided on an intermediate layer.
  • photocatalytic particles examples include metal oxide particles such as anatase type titanium oxide, rutile type titanium oxide, brookite type titanium oxide, tin oxide, zinc oxide, strontium titanate, tungsten oxide, and cerium oxide.
  • the photocatalyst particles preferably have an average particle size of 10 nm or more and less than 100 nm, more preferably 10 nm or more and 60 nm or less.
  • the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope.
  • a true sphere is the best, but it may be substantially circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2). Within this range, weather resistance, photocatalytic decomposability, and various desired coating properties (transparency, coating strength, etc.) are efficiently exhibited.
  • At least one selected from the group consisting of vanadium, iron, cobalt, nickel, palladium, zinc, ruthenium, rhodium, copper, silver, platinum and gold is used to develop higher photocatalytic ability.
  • / or a metal compound comprising the metal can be added to a photocatalyst coating solution applied on the intermediate layer to form a photocatalyst layer or a photocatalyst layer.
  • This addition can be performed by any method such as a method in which the metal or metal compound is mixed and dissolved or dispersed in a coating solution, or a method in which the metal or metal compound is supported on a photocatalyst layer or photocatalyst particles.
  • the content of the photocatalyst particles contained in the photocatalyst layer is more than 1% by mass and less than 20% by mass, more preferably more than 1% by mass and less than 5% by mass. To do.
  • the content of the photocatalyst particles is within this range, an effect that the decomposition function of the photocatalyst is effectively exhibited and the base material and the intermediate layer are hardly deteriorated can be efficiently obtained.
  • the photocatalyst layer has air permeability. Thereby, the contact opportunity of a photocatalyst particle and a to-be-decomposed thing increases, and the outstanding photocatalyst decomposition function is exhibited.
  • the photocatalyst layer of the photocatalyst-coated body according to the present invention preferably contains substantially no hydrolyzable silicone polycondensate in order to ensure air permeability, and more preferably does not contain at all.
  • the hydrolyzable silicone is a general term for an organosiloxane having an alkoxy group and / or a partially hydrolyzed condensate thereof.
  • the content of the hydrolyzable silicone polycondensate is 0 to 10 parts by mass with respect to 100 parts by mass of the total amount of photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone polycondensate in terms of silica. Is preferably 5 parts by mass or less, and most preferably 0 part by mass.
  • hydrolyzable silicone a silicone compound having a bi- to tetrafunctional silane as a monomer unit is often used.
  • ethyl silicate, methyl silicate, alkyl group-containing silicone, phenyl group-containing silicone and the like can be suitably used.
  • the photocatalyst layer of the photocatalyst-coated body according to the present invention preferably contains substantially no polycondensate of a hydrolyzate of an organometallic compound, and more preferably does not contain at all, in order to ensure air permeability.
  • the organometallic compound is a metal alkoxide containing a metal element such as titanium, zirconium, or aluminum, a metal organic complex, or the like.
  • the content of the polycondensation product of the hydrolyzate of the organic metal is 0 parts by mass or more and 10 parts by mass with respect to 100 parts by mass of the total amount of photocatalyst particles, inorganic oxide particles, and hydrolyzable silicone in terms of metal oxide. Is preferably 5 parts by mass or less, and most preferably 0 part by mass.
  • the photocatalyst layer of the present invention comprises at least one selected from the group consisting of a hydrolyzable silicone condensation polymer and an organometallic compound hydrolyzate as an optional component.
  • the content of the optional component is preferably 0 parts by mass or more and less than 10 parts by mass with respect to 100 parts by mass of the total amount of the photocatalyst particles, the inorganic oxide particles, and the oxide conversion amount of these optional components, Preferably it is 5 mass parts or less, Most preferably, it is 0 mass part.
  • the photocatalyst layer can contain inorganic oxide particles in addition to the photocatalyst particles.
  • This inorganic oxide particle functions as a binder component, gives sufficient air permeability to the photocatalyst layer, increases the chance of contact between the photocatalyst particle and the substance to be decomposed, and provides an advantage that an excellent photocatalytic decomposition function is exhibited. .
  • the inorganic oxide particles are not particularly limited as long as they are inorganic oxide particles capable of forming a layer together with photocatalyst particles.
  • examples of such inorganic oxide particles include silica, alumina, zirconia, ceria, yttria, Examples include single oxide particles such as tin oxide, iron oxide, manganese oxide, nickel oxide, cobalt oxide, and hafnia; and composite oxide particles such as barium titanate, calcium silicate, aluminum borate, and potassium titanate. More preferably, it is a silica particle.
  • These inorganic oxide particles are preferably in the form of an aqueous colloid using water as a dispersion medium; or an organosol dispersed in a hydrophilic solvent such as ethyl alcohol, isopropyl alcohol, or ethylene glycol, and particularly preferably. Colloidal silica.
  • the inorganic oxide particles have an average particle diameter of more than 5 nm and not more than 20 nm, preferably not less than 10 nm and not more than 20 nm.
  • the average particle diameter is calculated as a number average value obtained by measuring the length of any 100 particles that enter a 200,000-fold field of view with a scanning electron microscope.
  • a true sphere is the best, but it may be approximately circular or elliptical, and the length of the particle in this case is approximately calculated as ((major axis + minor axis) / 2).
  • the photocatalyst layer comprises more than 1 part by weight and less than 20 parts by weight of photocatalyst particles, more than 70 parts by weight and less than 99 parts by weight of inorganic oxide particles, and as optional components, At least one selected from the group consisting of a polycondensation product of degradable silicone and a polycondensation product of a hydrolyzate of an organometallic compound is used in an amount of 0 part by mass or more and less than 10 parts by mass, the photocatalyst particles, the inorganic oxide particles, and The total amount of the optional component in terms of oxide is included to be 100 parts by mass.
  • the photocatalyst layer has a photocatalyst particle of more than 1 part by mass and less than 5 parts by mass, an inorganic oxide particle of more than 85 parts by mass and less than 99 parts by mass, and condensation polymerization of hydrolyzable silicone as an optional component. And at least one selected from the group consisting of polycondensates of hydrolysates of organometallic compounds, wherein the photocatalyst particles, the inorganic oxide particles, and the oxides of the optional components The total amount of the conversion amount is configured to be 100 parts by mass.
  • the opportunity of contact between the photocatalyst particles and the substance to be decomposed is increased, and an excellent photocatalyst decomposition function is effectively exhibited. It is possible to improve to such an extent that it can withstand use. Furthermore, the deterioration of the base material and the intermediate layer due to the photocatalyst can be suppressed.
  • the photocatalyst layer of the photocatalyst-coated body according to the present invention is substantially transparent.
  • the film thickness of the photocatalyst layer is preferably from 0.1 ⁇ m to 5.0 ⁇ m, more preferably from 0.5 ⁇ m to 3.0 ⁇ m, and most preferably from 1.0 ⁇ m to 2. 0 ⁇ m or less.
  • the photocatalyst particles having a lower content ratio than the inorganic oxide particles can be increased in the film thickness direction, and the photocatalytic decomposability can be improved. Furthermore, excellent characteristics can be obtained in terms of transparency.
  • the photocatalyst-coated body according to the present invention can be easily produced by applying, preferably applying, a photocatalyst coating liquid containing photocatalyst particles and a solvent on a substrate having an intermediate layer formed by the above-described method.
  • a photocatalyst coating liquid containing photocatalyst particles and a solvent
  • a method for applying the photocatalyst layer generally used methods such as brush coating, roller, spray, roll coater, flow coater, dip coating, flow coating, and screen printing can be used.
  • After applying the coating liquid to the substrate it may be dried at room temperature, or may be heat-dried if necessary.
  • the photocatalyst added to the photocatalyst coating liquid may be added in the form of a sol.
  • a solvent that can appropriately disperse the above constituent components can be used, and water and / or an organic solvent. And water is particularly preferred.
  • the solvent of the photocatalyst coating liquid a solvent capable of appropriately dispersing the constituent components can be used, and water and / or an organic solvent may be used.
  • the solid content concentration of the photocatalyst coating liquid is not particularly limited, but it is preferably 1 to 10% by mass because it is easy to apply.
  • the components in the photocatalyst coating composition are analyzed by separating the coating solution into particle components and filtrate by ultrafiltration, and analyzing each 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 may contain a surfactant as an optional component.
  • the surfactant may be contained in an amount of 0 to 10 parts by mass with respect to the photocatalyst coating liquid, preferably 0 to 8 parts by mass, more preferably 0 to 6 parts by mass. is there.
  • One of the effects of adding a surfactant is leveling to the substrate, and the lower limit for obtaining the effect is about 0.1 parts by mass.
  • the surfactant is an effective component for improving the wettability of the photocatalyst coating liquid, but in the photocatalyst layer formed after coating, the inevitable impurities that no longer contribute to the effect of the photocatalyst-coated body of the present invention. It corresponds to.
  • the surfactant may be used within the above content range depending on the wettability required for the photocatalyst coating solution, but if the wettability is not a problem, the surfactant is substantially or not included. It is not necessary.
  • the type of the surfactant can be appropriately selected in consideration of the dispersion stability of the photocatalyst and the inorganic oxide particles and the wettability when coated on the intermediate layer, but a nonionic surfactant is preferred, more Preferably, ether type nonionic surfactants, ester type nonionic surfactants, polyalkylene glycol nonionic surfactants, fluorine-based nonionic surfactants, silicon-based nonionic surfactants, and the like It is done.
  • the base material of the photocatalyst-coated body of the present invention may be any material, regardless of inorganic material or organic material, as long as the intermediate layer can be formed thereon, and the shape thereof is not limited.
  • Preferred examples of the base material from the viewpoint of materials include metal, ceramic, glass, plastic, rubber, stone, cement, concrete, fiber, fabric, wood, paper, combinations thereof, laminates thereof, Examples thereof include those having at least one layer of coating on the surface.
  • base materials from the viewpoint of applications include building materials, building exteriors and interiors, window frames, window glass, structural members, exteriors and coatings of vehicles, exteriors of machinery and articles, dust covers and coatings, traffic signs, Various display devices, advertising towers, sound insulation walls for roads, sound insulation walls for railways, bridges, guard rail exteriors and paintings, tunnel interiors and paintings, insulators, solar battery covers, solar water heater heat collection covers, plastic houses, vehicle lighting Covers, outdoor lighting fixtures, tables, bathroom materials, kitchen panels, sinks, ranges, ventilation fans, air conditioning, filters, toilets, bathtubs, and films, sheets, seals and the like for attachment to the surface of the article.
  • Example 1 As the substrate, a white enamel coated substrate was prepared.
  • the intermediate layer was formed as follows. That is, 100 parts by weight of a silicone-modified acrylic resin emulsion (solid content concentration: 40%) having a siloxane content of 30% by mass with respect to the solid content of the silicone-modified resin, a color pigment slurry (rutile titanium oxide, solid content concentration: 65%) is mixed with 43 parts by weight, acrylic resin beads (average particle size: 18 ⁇ m) is 16 parts by weight, ion-exchanged water is 55 parts by weight, viscosity modifier is mixed with 4 parts by weight, and water is used as a solvent to coat the intermediate layer. A liquid was obtained. This coating solution was roller-coated on the substrate, dried at room temperature (23 ° C.) for 24 hours, and then an intermediate layer having a thickness of 40 ⁇ m was formed.
  • a silicone-modified acrylic resin emulsion solid content concentration: 40%
  • a color pigment slurry rutile titanium oxide, solid content concentration:
  • a photocatalyst layer was formed as follows. That is, an anatase-type titanium oxide aqueous dispersion (average particle size: about 50 nm, dispersant: diethylamine) and water-dispersed colloidal silica (average particle size: about 11 nm, basic) are mixed to obtain a photocatalyst coating liquid. It was. The total solid concentration of the photocatalyst and the inorganic oxide in the photocatalyst coating solution was 5.5% by mass. The obtained photocatalyst coating liquid was spray-applied on the above-mentioned intermediate coating material heated in advance and dried at room temperature (23 ° C.) for 24 hours. The obtained photocatalyst layer contained 10 parts by mass of titanium oxide and 90 parts by mass of silica. The film thickness of the photocatalyst layer was 0.5 ⁇ m.
  • the acrylic resin beads shall have the average particle diameter described in the table described later, and the thickness of the intermediate layer was changed to the film thickness described in the table below by adjusting the amount of the intermediate layer coating solution.
  • a photocatalyst-coated body was obtained in the same manner as in Example 1.
  • 8 parts by weight of hollow inorganic glass beads (average particle size: 30 or 16 ⁇ m) were added instead of the acrylic resin beads.
  • acrylic resin beads were not added.
  • the resulting photocatalyst-coated body was evaluated for methylene blue resolution according to the test method of JIS R 1703-2 “Testing method for self-cleaning performance of photocatalytic material—Part 2: wet decomposition performance”.
  • the obtained degradation activity index was as shown in the following table.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne un corps recouvert d'un photocatalyseur qui présente une dégradabilité photocatalytique tout en réduisant la quantité de photocatalyseur incluse dans une couche de photocatalyseur. Le corps recouvert de photocatalyseur comporte au moins une matière de base, une couche de photocatalyseur comprenant des particules de photocatalyseur et une couche intermédiaire disposée entre ladite matière de base et ladite couche de photocatalyseur de manière à venir en contact avec la partie inférieure de la couche de photocatalyseur. La couche intermédiaire comprend au moins une résine modifiée au silicium et au moins un type de grain sélectionné dans un groupe formé par les grain de résine, les grains de verre creux et les grains de céramique creux. Les grains forment une partie saillante au niveau de l'interface entre la couche intermédiaire et la couche de photocatalyseur, ladite partie saillante étant provoquée par la forme de l'interface.
PCT/JP2011/057384 2010-03-25 2011-03-25 Corps recouvert d'un photocatalyseur Ceased WO2011118781A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2012507092A JP5707389B2 (ja) 2010-03-25 2011-03-25 光触媒塗装体

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2010-070198 2010-03-25
JP2010070198 2010-03-25

Publications (1)

Publication Number Publication Date
WO2011118781A1 true WO2011118781A1 (fr) 2011-09-29

Family

ID=44673320

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2011/057384 Ceased WO2011118781A1 (fr) 2010-03-25 2011-03-25 Corps recouvert d'un photocatalyseur

Country Status (3)

Country Link
JP (1) JP5707389B2 (fr)
TW (1) TW201200355A (fr)
WO (1) WO2011118781A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018025370A1 (fr) * 2016-08-04 2018-02-08 株式会社オー・ティー・エー Filtre photocatalyseur
JPWO2019065504A1 (ja) * 2017-09-28 2020-11-05 株式会社フルヤ金属 分解材及びそれを用いた分解方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1071312A (ja) * 1996-08-30 1998-03-17 Hoya Corp フィルター素材及びその製造方法並びに該フィルター素材を用いたフィルター装置
JP2000107527A (ja) * 1998-09-30 2000-04-18 Hoya Corp フィルター素材、フィルター、光触媒フィルター及びそれらの製造方法並びに該フィルター素材、フィルター、光触媒フィルターを用いたフィルター装置
JP2008272718A (ja) * 2007-03-30 2008-11-13 Toto Ltd 光触媒塗装体およびそのための光触媒コーティング液
JP2008307528A (ja) * 2007-03-30 2008-12-25 Toto Ltd 光触媒塗装体およびそのための光触媒コーティング液
JP2009136811A (ja) * 2007-12-07 2009-06-25 Kubota Matsushitadenko Exterior Works Ltd 塗装体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1071312A (ja) * 1996-08-30 1998-03-17 Hoya Corp フィルター素材及びその製造方法並びに該フィルター素材を用いたフィルター装置
JP2000107527A (ja) * 1998-09-30 2000-04-18 Hoya Corp フィルター素材、フィルター、光触媒フィルター及びそれらの製造方法並びに該フィルター素材、フィルター、光触媒フィルターを用いたフィルター装置
JP2008272718A (ja) * 2007-03-30 2008-11-13 Toto Ltd 光触媒塗装体およびそのための光触媒コーティング液
JP2008307528A (ja) * 2007-03-30 2008-12-25 Toto Ltd 光触媒塗装体およびそのための光触媒コーティング液
JP2009136811A (ja) * 2007-12-07 2009-06-25 Kubota Matsushitadenko Exterior Works Ltd 塗装体

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018025370A1 (fr) * 2016-08-04 2018-02-08 株式会社オー・ティー・エー Filtre photocatalyseur
JPWO2019065504A1 (ja) * 2017-09-28 2020-11-05 株式会社フルヤ金属 分解材及びそれを用いた分解方法

Also Published As

Publication number Publication date
JPWO2011118781A1 (ja) 2013-07-04
JP5707389B2 (ja) 2015-04-30
TW201200355A (en) 2012-01-01

Similar Documents

Publication Publication Date Title
JP5614709B2 (ja) 光触媒塗装体
WO2009145209A1 (fr) Objet muni d’un revêtement contenant un photo-catalyseur
CN1263547A (zh) 亲水性无机涂膜的形成方法及无机涂料组合物
JP2012250134A (ja) 光触媒塗装体およびそのための光触媒コーティング液
JP2012096188A (ja) 光触媒塗装体および光触媒コーティング液
JP5361513B2 (ja) 光触媒塗装体
TWI480099B (zh) Photocatalyst coating body
JP5707389B2 (ja) 光触媒塗装体
JP5305231B2 (ja) 光触媒塗装体
JP5491922B2 (ja) 光触媒塗装体
JPH111661A (ja) 機能性無機塗料、それを用いた塗装品およびそれらの用途
JP5614945B2 (ja) 光触媒塗装体
WO2012060398A1 (fr) Objet revêtu d'un photocatalyseur et liquide de revêtement photocatalyseur pour l'objet
JP5391902B2 (ja) 光触媒塗装体、および光触媒コーティング液
JP4088995B2 (ja) 機能性無機塗膜の形成方法および機能性塗装品
JPH1161042A (ja) 高親水性無機塗料、それを用いた塗装品およびそれらの用途
JP5428620B2 (ja) 光触媒塗装体、および光触媒コーティング液
JP5327713B2 (ja) 光触媒塗装体、および光触媒コーティング液
JP5418972B2 (ja) 光触媒塗装体、および光触媒コーティング液
JP5327714B2 (ja) 光触媒塗装体、および光触媒コーティング液
JP2010270582A (ja) 建材
JP2010029806A (ja) 光触媒塗装体およびそのための光触媒コーティング液
JP2011016057A (ja) 光触媒塗装体、および光触媒コーティング液
JP2011051246A (ja) 光触媒塗装体、および光触媒コーティング液
JP2011056475A (ja) 光触媒塗装体、および光触媒コーティング液

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11759585

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 2012507092

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11759585

Country of ref document: EP

Kind code of ref document: A1