WO2003033144A1 - Matiere composite photocatalytique, liquide d'application permettant de former une couche photocatalytique et structure portant un photocatalyseur - Google Patents

Matiere composite photocatalytique, liquide d'application permettant de former une couche photocatalytique et structure portant un photocatalyseur Download PDF

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Publication number
WO2003033144A1
WO2003033144A1 PCT/JP2002/010582 JP0210582W WO03033144A1 WO 2003033144 A1 WO2003033144 A1 WO 2003033144A1 JP 0210582 W JP0210582 W JP 0210582W WO 03033144 A1 WO03033144 A1 WO 03033144A1
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Prior art keywords
photocatalyst
layer
particles
forming
colloidal
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PCT/JP2002/010582
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English (en)
Japanese (ja)
Inventor
Shinji Abe
Shuntaro Kinoshita
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Nippon Soda Co.,Ltd.
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Priority to JP2003535930A priority Critical patent/JP4738736B2/ja
Publication of WO2003033144A1 publication Critical patent/WO2003033144A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • 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

Definitions

  • the present invention provides a structure supporting a photocatalyst used for water purification, deodorization, antifouling, sterilization, wastewater treatment, algae growth suppression, various chemical reactions, etc., and is particularly durable even in an outdoor environment having excellent transparency.
  • TECHNICAL FIELD The present invention relates to a photocatalyst composite having properties, a coating solution for forming a photocatalyst layer, and a photocatalyst supporting structure. Background technology:
  • a photocatalyst-supporting structure in which a photocatalyst is supported on a carrier with the intention of decomposing antibacterial, anti-humidity and harmful substances by the action of a photocatalyst has been known.
  • Such a photocatalyst-carrying structure is usually produced by applying and curing a coating solution for forming a photocatalyst layer containing a photocatalyst component on the surface of a carrier to form a photocatalyst layer.
  • the coating solution for forming the photocatalyst layer contains a binder component because it is difficult to fix the photocatalyst component consisting of metal oxides such as titanium dioxide to various carriers with sufficient strength.
  • Silica sol has often been used as a binder that can withstand the oxidizing action of photocatalysts.
  • a member hereinafter, referred to as a "photocatalyst-supporting structure" having a photocatalyst-containing coating or layer (hereinafter, referred to as a "photocatalyst layer”) formed on the surface of a carrier (substrate or substrate) is used outdoors. If used, they will be exposed to the elements for extended periods. At this time, if the photocatalyst film layer is poor in water resistance, the photocatalyst film layer is partially or entirely peeled off from the carrier, so that sufficient photocatalytic activity cannot be exhibited. Therefore, when the photocatalyst supporting structure is used outdoors for a longer period of time, it has been desired that the photocatalyst supporting structure has higher water resistance.
  • the present invention provides a photocatalyst-supporting structure that can be used for water purification, deodorization, antifouling, sterilization, wastewater treatment, algae growth suppression, and various chemical reactions, and can solve the above three problems. With the goal.
  • the present inventors have conducted intensive studies to solve the above-mentioned problems, and as a result, have found that the above-mentioned problems can be solved by using a silica sol having aluminum and zirconium as main components as binder components and having a special shape. It was completed.
  • a photocatalyst complex comprising at least one selected from the group consisting of a compound and an aluminum compound,
  • the ratio of the particle diameter measured by the dynamic light scattering method (D l nm) to the particle diameter measured by the nitrogen gas adsorption method (D 2 nm) is obtained by combining the spherical colloidal force particles into an elongated shape.
  • D 1 / D 2 is 5 or more, and this D 1 is 40 to 300 nm, and has a uniform thickness within the range of 5 to 20 nm observed by electron microscopy, and extends only in one plane.
  • the zirconium compound is selected from the group consisting of zirconium oxide, oxide hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide. It is characterized by being one or a mixture of two or more
  • the photocatalyst complex according to any one of (1) to (5),
  • the aluminum compound is selected from the group consisting of aluminum oxides, hydroxides, hydroxides, oxynitrates, oxycarbonates, alkoxides having 1 to 4 carbon atoms, and hydrolysates of the alkoxides.
  • the photocatalyst complex according to any one of (1) to (6), wherein the photocatalyst complex is a mixture of one or more kinds.
  • the colloidal silica particles are contained in an amount of 5 to 50% by weight and the photocatalyst is contained in an amount of 5 to 60% by weight in terms of oxide, based on the entire photocatalyst complex.
  • a coating liquid for forming a photocatalyst layer comprising: a silicide sol in which colloidal silicide particles in which spherical colloidal silica particles are bound in an elongated shape are dispersed; and a photocatalyst particle and / or a sol; and a zirconium compound.
  • a photocatalyst layer coating solution comprising at least one selected from the group consisting of aluminum compounds.
  • a solid sol in which, in terms of oxides, colloidal silicide particles in which spherical colloidal silicide particles are combined in an elongated shape is dispersed is 0.5.
  • the zirconium compound is selected from the group consisting of 0.5 to 5% by weight and the aluminum compound is 2 to 9% by weight in terms of oxide, as solids, based on the entire coating solution for forming a photocatalyst layer.
  • the spherical colloidal silica particles are elongated and colloidal silicide particles that are bound in a shape are the ratio of the particle diameter measured by the dynamic light scattering method (D l nm) to the particle diameter measured by the nitrogen gas adsorption method (D 2 nm).
  • D 1 / D 2 is 5 or more, and this D 1 is 40 to 300 nm, and has a uniform thickness within the range of 5 to 20 nm observed by electron microscopy, and extends only in one plane.
  • the zirconium compound is selected from the group consisting of zirconium oxide, hydroxide, hydroxide, oxynitrate, oxycarbonate, alkoxide having 1 to 4 carbon atoms, and hydrolyzate of the alkoxide.
  • the photocatalyst-forming coating liquid according to any one of (12) to (18), wherein the coating liquid is a sol of one or a mixture of two or more kinds thereof.
  • the aluminum compound is selected from the group consisting of aluminum oxides, hydroxides, hydroxides, oxynitrates, oxycarbonates, alkoxides having 1 to 4 carbon atoms, and hydrolysates of the alkoxides.
  • the photocatalyst-forming coating liquid according to any one of (12) to (19), wherein the coating liquid is a sol of one or a mixture of two or more kinds thereof.
  • a photocatalyst layer-supporting structure in which an adhesive layer is formed on a surface of a carrier and a photocatalyst layer is further formed on the surface of the adhesive layer, wherein the photocatalyst layer is any one of (1) to (11).
  • a photocatalyst layer-supporting structure comprising the photocatalyst composite according to
  • Adhesion by the cross-cut tape method specified in JI SK5400 after boiling for 1 hour in boiling ion-exchanged water is characterized by a score of 6 or more (23) or (24)
  • the photocatalyst composite of the present invention basically contains a photocatalytic component and colloidal silicide particles in which spherical colloidal silicide particles are bound in an elongated shape, and at least one member selected from the group consisting of zirconium compounds and aluminum compounds. It is characterized by containing.
  • any photocatalyst such as powder, sol, or solution
  • a sol having an average particle diameter of 50 nm or less, preferably 20 nm or less is used, transparency is required because the transparency of the photocatalyst layer is improved and the linear transmittance is increased. It is preferable when the composition is applied to a glass substrate or a plastic molded body.
  • the window glass of a toilet must have a high total light transmittance so that the inside of the toilet is bright, and must have a high haze rate because the inside cannot be clearly seen.
  • T i 0 2, Z n 0 in particular, S r T i 0 3, C d S, G a P, I n P, G a A s, B a T i 0 3 ⁇ KN b 0 3 ⁇ F e 2 0 3 ⁇ T a 2 0 5 ⁇ W0 3 ⁇ S n 0 2 ⁇ B i 2 0 3 , N i 0, Cu 2 0, S i C, S i 0 2 , Mo S 2, I n P b, can be exemplified R u 0 2, C e 0 2 or the like, P t for these photocatalysts, R h, R u 0 2 , n b, C u, S n, Metals or metal oxides such as Ni and Fe can be used.
  • titanium oxide titanium oxide (T i 0 2)
  • photocatalytic activity and anatase type acid titanium are preferred.
  • titanium oxide which exhibits catalytic activity with light containing a large amount of ultraviolet light such as sunlight but also titanium oxide which exhibits catalytic activity even in room light with little ultraviolet light by doping a noble metal can be used. .
  • the content of the photocatalyst in the photocatalyst composite is preferably from 5% by weight to 60% by weight in terms of oxide based on the entire photocatalyst composite. If it is less than 5% by weight, the photocatalytic activity is significantly reduced. On the other hand, when the content exceeds 60% by weight, the photocatalytic activity becomes high, but the adhesion to the adhesive layer becomes poor.
  • the colloidal sily particles used in the present invention are characterized in that spherical colloidal sily particles are combined in an elongated shape.
  • the spherical colloidal shiri particles are used in a pearl necklace.
  • Pearl net looks like pearl
  • a shape like a part of a cress can be exemplified. That is, examples in which three or more, preferably five or more, more preferably seven or more spherical silica particles are connected can be exemplified.
  • the shape of each spherical colloidal particle does not need to be clear, and it may be partially continuous and elongated in a cylindrical shape. Furthermore, it is not necessary that the spherical colloidal particles are bonded.
  • the particles have an elongated shape and a shape as a whole.
  • the length is preferably in the range of 50 to 400 nm
  • the thickness is preferably in the range of 10 to 50 nm
  • the thickness is preferably uniform throughout.
  • the elongated shape preferably extends in two-dimensional directions starting from certain spherical colloidal silica particles. Further, as long as the shape is elongated as a whole, it may have a somewhat branched structure.
  • the average particle size of the spherical colloidal silica particles is preferably in the range of 10 to 50 nm.
  • the colloidal silica particles having the above characteristics specifically, the ratio of the particle diameter measured by the dynamic light scattering method (D lnm) to the particle diameter measured by the nitrogen gas adsorption method (D 2 nm) D 1 ZD 2 Is greater than or equal to 5, and this D1 is 40 to 300 nm, and the elongation only in one plane with a uniform thickness within the range of 5 to 20 nm by electron microscopy.
  • the elongated colloidal silicide particles having an elongated shape can be exemplified.
  • the methods described in JP-A-1-31715 and JP-A-7-11808 are exemplified. be able to.
  • the zirconium compound used in the present invention is added for the purpose of improving the alkali resistance of the photocatalyst composite.
  • Such zirconium compounds include zirconium oxides, hydroxides, hydroxides, nitrates, oxynitrates, carbonates, oxycarbonates, oxalates, oxyoxalates, acetates, oxyacetates, and carbon atoms of 1 to A gel of one or a mixture of two or more selected from the group consisting of the alkoxide of 6 and the hydrolysis product of the alkoxide is preferred.
  • zirconium compound examples include zirconium oxide, zirconium oxynitrate, zirconium oxychloride, hydrated zirconium oxide, zirconium oxyhydroxide, hydrated zirconium nitrate, hydrated zirconium oxychloride, zirconium oxalate, zirconium acetate, zirconium acetate Examples include tetraisopropoxide, zirconium tetrabutoxide, zirconium dibutoxide acetylacetonate, zirconium dibutoxide lactate, a hydrolysis product of zirconium butoxide, and a hydrolysis product of zirconium isopropoxide.
  • the aluminum compound is added for the purpose of further improving the alkali resistance of the photocatalyst composite and reducing the haze ratio.
  • Aluminum compounds include aluminum oxides, Hydroxide hydroxide, hydroxide, nitrate, oxynitrate, carbonate, oxycarbonate, oxalate, oxyoxalate, acetate, oxyacetate, alkoxide having 1 to 6 carbon atoms, and hydrolysis of the alkoxide One or a mixture of two or more selected from the group consisting of products is preferred.
  • aluminum compounds include aluminum oxide, aluminum oxide hydroxide, aluminum hydroxide, aluminum oxide hydrate, boehmite, aluminum nitrate, aluminum oxynitrate, aluminum carbonate, aluminum oxycarbonate, Aluminum oxalate, aluminum oxalate, aluminum acetate, aluminum oxyacetate, aluminum triisopropoxide, aluminum tributoxide, aluminum dimethyl butoxide acetylacetonate, aluminum butoxy lactate, hydrolysis product of aluminum dimethyl butoxide, Hydrolysis products of aluminum isopropoxide can be exemplified.
  • the zirconium compound or aluminum compound used with the photocatalyst has an average particle diameter of 2 nm to 50 nm, preferably 2 ⁇ ! It is preferred to use ⁇ 20 nm sol.
  • the transparency of the photocatalyst layer is improved and the linear transmittance is increased. Preferred.
  • application of such a transparent photocatalyst layer does not impair the underlying color or pattern.
  • the particles having an average particle diameter of 50 nm or more are used, the linear transmittance decreases and the haze ratio increases.
  • a porous gel having a specific surface area after drying at 150 ° C. of 100 m 2 Z g or more is used. It is preferable to do so.
  • the porous gel has an adsorptive property and has an effect of enhancing photocatalytic activity.
  • the content of the zirconium compound in the photocatalyst composite is 5 to 4 in terms of oxide with respect to the entire photocatalyst composite. Preferably it is 0% by weight. If it is less than 5% by weight, the alkali resistance of the photocatalyst layer becomes poor. On the other hand, if it exceeds 40% by weight, the transparency becomes poor.
  • the content of the aluminum compound in the photocatalyst composite is preferably 20 to 90% by weight in terms of oxide based on the entire photocatalyst composite. If it is less than 20% by weight, the effect of suppressing the increase in the haze ratio of the photocatalyst layer and the effect of increasing the alkali resistance are poor. On the other hand, if the amount exceeds 90% by weight, the photocatalytic activity decreases.
  • the content of the zirconium compound and the aluminum compound in the photocatalyst composite is preferably from 40 to 95% by weight in terms of these acid compounds in total. If the amount is less than 40% by weight, the adhesion to the adhesive layer becomes insufficient. If the amount exceeds 95% by weight, the amount of the photocatalyst that can be added is reduced, so that the photocatalytic activity is remarkably reduced.
  • the film strength is improved by further containing a silicon compound in the photocatalyst composite. As a silicon compound,
  • R 1 is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, lipoxetyl, chloromethyl, chloroethyl, (May be substituted with an amino group, a carboxyl group or a chlorine atom).
  • R 2 is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, etc., or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxy
  • R 2 represents an alkyl group having 1 to 8 carbon atoms, which is substituted by an alkoxy group such as methyl, butoxymethyl, methoxethyl, ethoxymethyl, propoxyshetyl, methoxypropyl, and methoxybutyl.
  • the 1 ⁇ , n 2 and n 3 represents 0, 1 or 2
  • n 4 represents an integer of from 2 to 4
  • 1 ⁇ + 11 2 + 113Tasu 11 4 4.
  • Preferred specific examples of the silicon alkoxide represented by the above formula include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane and the like.
  • the content of the silicon compound in the photocatalyst composite is preferably 1 to 20% by weight in terms of oxide based on the entire photocatalyst composite.
  • tin, niobium, tantalum oxides or hydroxides thereof can be added to these multiple components for the purpose of improving the strength of the coating film.
  • the content of the aluminum oxide, hydroxide, or hydroxide in the photocatalyst layer is within the range of the content added for improving the alkali resistance, extremely excellent resistance to aluminum is obtained. It can show the strength
  • the coating solution for forming a photocatalyst layer of the present invention contains a silicic acid sol in which colloidal silicide particles having spherical colloidal silicide particles bonded in an elongated shape are dispersed, and a photocatalyst particle and / or a zolconium compound. It contains at least one member selected from the group consisting of aluminum compounds.
  • silica sol, the zirconium compound, the aluminum compound, and the photocatalyst which are contained in the photocatalyst layer forming coating solution and in which colloidal silica particles in which spherical colloidal silicide particles are combined in an elongated shape, are included in the photocatalyst composite.
  • colloidal silica particles, zirconium compounds, aluminum compounds and photocatalysts as those listed as preferable ones can be used.
  • the zirconium compound, aluminum compound and photocatalyst are preferably used in the form of a sol. preferable.
  • an acid or alkali deflocculant can be added to the photocatalyst coating solution for stabilization.
  • a surfactant or the like of 5% by weight or less based on the photocatalyst can be added to the sol suspension for the purpose of improving adhesion and operability.
  • the amount of each component contained in the coating solution for forming a photocatalyst layer is expressed in terms of oxide as a solid content with respect to the entire coating solution. It is preferable that the sol is 0.5 to 5% by weight, and the photocatalyst particles and Z or sol are 0.5 to 6% by weight as a solid content. It is preferable that the zirconium compound is 0.5 to 5% by weight and the aluminum compound is 2 to 9% by weight in terms of oxides.
  • the silicon compound is contained in the photocatalyst complex, it is preferable that the silicon compound is contained in an amount of 0.001 to 5% by weight in terms of oxide as a solid content with respect to the entire coating solution for forming the photocatalyst layer.
  • the silicon compound for example, a hydrolyzate of a silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a hydrolyzate product thereof is preferable. When the carbon number of the alkoxy group of the silicon alkoxide exceeds 6, the hydrolysis rate becomes very slow.
  • Polysiloxane obtained by hydrolyzing silicon alkoxide partially containing chlorine can be used.However, when polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as impurities. Or the adhesiveness may be reduced.
  • a silicon alkoxide for example, a compound represented by the following formula can be preferably used.
  • R 1 is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, lipoxetyl, chloromethyl, chloroethyl, (It may be substituted by an amino group, a carboxyl group or a chlorine atom.) Represents an alkyl group having 1 to 8 carbon atoms.
  • R2 is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, etc., or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxy
  • n 2 and n 3 represent 0, 1 or 2
  • n 4 represents an integer of 2 to 4
  • n i + n + ns + n Preferred specific examples of the silicon alkoxide represented by the above formula include S i (OCH 3 ) 4 , S i (OC 2 H 5 ) 4 , S i (OC 3 H 7 ) 4 , S i (OC 4 H 9 ) 4 , S i (0 C 5 H U ) 4 , S i (OC 6 H 13 ) 4 S i CH 3 (OCH 3 ) 3 ⁇ S i CH 3 (OC 2 H 5 ) 3 S i CH 3 ( OC 3 H 7 ) 3 ⁇ S i CH 3 (OC 3 H 7 ) 3 ⁇ S i CH 3 (0 C 4 H 9 ) 3 S i C 1 (OCH 3 ) 3 ⁇ S i C 1 (0 C 2 H 5 ) 3 , S i C 1 (OC 3 H 7 ) 3 , S i C 1 (OC
  • the method for preparing the coating solution for forming the photocatalyst layer includes: (a) a method of mixing zirconium or aluminum oxide, oxidized hydroxide or hydroxide sol solution, photocatalyst, colloidal sily sol, etc .; A method of mixing a photocatalyst and a colloidal sily sol in the state of a precursor solution of an oxide, oxide hydroxide or oxide 7 sol, (b) zirconium or aluminum oxide, hydroxide or hydroxide Any method can be employed as long as it is uniformly mixed in the photocatalyst layer, such as a method of mixing a sol solution of the product and a sol-solution for forming a photocatalyst with the colloidal silylation sol.
  • Photocatalyst particles or a sol, a colloidal sily sol, etc. are dispersed in a precursor solution of a zirconium or aluminum oxide, an oxide hydroxide or a hydroxide sol, and the coating solution is hydrolyzed or neutralized during coating. It can also be decomposed to form a sol.
  • solvent used examples include water, alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, and t-butanol, acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, and cyclohexane.
  • Ketones such as hexanone, ethers such as dimethyl ether, methylcellosolve, and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene, and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; sacaneethyl and acetic acid Esters such as propyl and butyl acetate; and saturated hydrocarbons such as pentane, hexane and cyclohexane can be mentioned. Also, two or more of these can be used in combination. Of these, water-alcohol solvents are particularly preferred.
  • the structure supporting the photocatalyst according to the present invention has a structure in which an adhesive layer is provided between the photocatalyst layer and the carrier.
  • the adhesive layer provided between the photocatalyst layer and the carrier has a function of protecting the underlying carrier from deterioration due to the photocatalytic action and a function of firmly adhering the photocatalyst layer to the carrier. Have a characteristic that they are not easily deteriorated by photocatalysis.
  • the carrier is not particularly limited as long as it can support a photocatalyst via an adhesive layer.
  • the ceramic, inorganic material, or carrier material is an organic polymer that cannot be heated or a metal that is easily oxidized and corroded by heat or water, it is possible to obtain a structure provided with the adhesive layer and the photocatalyst layer. it can.
  • the shape of the carrier any complicated shape such as a film, a sheet, a plate, a tube, a fiber, and a net can be used.
  • the thickness of the carrier is preferably 10 ⁇ m or more because it can be firmly supported.
  • the surface is easily treated by electric discharge treatment or Bramer treatment. A carrier that has been subjected to a deposition treatment can be used.
  • the material of the adhesive layer is not particularly limited as long as it can protect the carrier from being deteriorated by the photocatalytic action and can firmly fix the photocatalytic layer.
  • the silicon content is converted to oxide.
  • 2 to 10% by weight of silicon-modified resins such as (acrylic silicone resin, epoxy silicon resin, polyester silicone resin), and (2) a resin containing 3 to 90% by weight of polysiloxane as oxide.
  • a resin containing 5 to 90% by weight of colloidal silica in terms of oxide can be used. These resins adhere well to the photocatalyst and are suitable for protecting the carrier from the photocatalyst.
  • Silicon-modified resin such as acryl silicone resin whose silicon content is less than 2% by weight in terms of oxide, resin whose polysiloxane content is less than 3% by weight in terms of oxide, and colloidal silicide content If the resin is less than 5% by weight in terms of oxide, the adhesion to the photocatalyst layer will be poor. Further, the adhesive layer is deteriorated by the photocatalyst, and the photocatalyst layer is easily peeled.
  • Silicon-modified resin such as acryl-silicon resin whose silicon content exceeds 10% by weight as oxide, resin containing polysiloxane more than 90% by weight as oxide, colloidal silica If the amount of the resin exceeds 90% by weight in terms of oxide, the adhesion to the carrier will be reduced.
  • the resin for introducing silicon examples include an acrylic resin, an epoxy resin, a polyester resin, an alkyd resin, and a urethane resin.
  • acrylic resins, epoxy resins, and polyester resins are particularly preferable in view of film formability, toughness, and adhesion to a carrier.
  • These resins can be used in either a solution state or an emulsion type. Further, additives such as a crosslinking agent may be contained.
  • the polysiloxane contained in the resin of the adhesive layer is a hydrolyzate of a silicon alkoxide having an alkoxy group having 1 to 5 carbon atoms or a product of the hydrolyzate, adhesion and durability are further improved.
  • a supporting structure can be obtained. If the alkoxy group in the silicon alkoxide has more than 6 carbon atoms, the hydrolysis rate will be very slow, making it difficult to cure in the resin, resulting in poor adhesion and durability.
  • a polysiloxane obtained by hydrolyzing a silicon alkoxide partially containing chlorine can also be used.However, when a polysiloxane containing a large amount of chlorine is used, the carrier is corroded by chlorine ions as impurities. Or the adhesiveness may be reduced.
  • a silicon alkoxide for example, a compound represented by the following formula can be preferably used.
  • R 1 is methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, octyl, aminomethyl, aminoethyl, carboxymethyl, lipoxetyl, chloromethyl, chloroethyl,
  • Amino group, (It may be substituted with a carbonyl group or a chlorine atom.) It represents an alkyl group having 1 to 8 carbon atoms.
  • R 2 is an alkyl group having 1 to 8 carbon atoms such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl, t-butyl, hexyl, etc., or methoxymethyl, ethoxymethyl, propoxymethyl, isopropoxy
  • 1 ⁇ , n 2 and n 3 represent 0, 1 or 2
  • n 4 represents an integer of 2 to 4, and It is.
  • Preferred specific examples of the silicon alkoxide represented by the above formula include S i (OCH 3 ) 4 , S i (OC 2 H 5 ) 4 , S i (OC 3 H 7 ) 4 , S i (OC 4 H 9 ) 4 , S i (OC 5 H u ) 4 , S i (OC 6 H 13 ) 4 , S i CH 3 (OCH 3 ) 3 , S i CH 3 (OC 2 H 5 ) 3 , S i CH 3 ( 0 C 3 H 7 ) 3 , S i CH 3 (OC 3 H 7 ) 3 S i CH 3 (OC 4 H g ) 3 , S i C 1 (OCH 3 ) 3 , S i C 1 (0 C 2 H 5) 3, S i C 1 (OC 3 H 7) 3, S i C 1 (OC 4 H g) 3, S i C 1 (OC 6 H 13) 3, S i C 1 (OH) (OCH 3 ) 2 S i C 1 (
  • silicon of these silicon-modified resins there are various methods for introducing silicon of these silicon-modified resins, such as a transesterification reaction, a graft reaction using a silicon macromer or a reactive silicon monomer, a hydrosilylation reaction, and a block copolymerization method.
  • polysiloxane can be introduced into a resin by (1) a method in which silicon alkoxide is mixed with a resin solution in a monomer state and hydrolyzed with moisture in the air when an adhesive layer is formed;
  • methods such as mixing the partial hydrolyzate with a resin, and further hydrolyzing with the moisture in the air at the time of forming the adhesive layer, but any method can be used as long as it can be uniformly mixed with the resin.
  • a small amount of an acid or base catalyst may be added to adjust the hydrolysis rate of silicon alkoxide.
  • the amount of the polysiloxane to be added to the resin is preferably 3 to 90% by weight in terms of oxide in order to firmly adhere the photocatalyst layer to the carrier.
  • any resin such as an acrylic resin, an epoxy resin, a polyester resin, a urethane resin, and an alkyd resin can be used.
  • acrylic resin, epoxy resin, polyester resin, or a resin mixture thereof is preferable in terms of durability and resistance to stress when used as a silicone-modified resin.
  • the particle size of the colloidal silica is preferably 1 Onm or less.
  • the particle diameter is 1 Onm or more, not only the resin in the adhesive layer is easily degraded by the photocatalyst, but also the adhesion between the photocatalyst layer and the adhesive layer becomes poor.
  • a resin solution and a colloidal silica solution are used as a method of introducing colloidal sily force into a resin.
  • the simplest method is to mix the liquids, apply and dry to form a protective film.
  • a polymer obtained by polymerizing a resin in a state where the colloidal silicity is dispersed can be used.
  • colloidal silica treated with a silane coupling agent can be used to improve the adhesiveness and dispersibility between the colloidal silica and the resin.
  • the amount of colloidal silica added to the resin is preferably 5 to 90% by weight in terms of oxide in order to firmly adhere the photocatalyst layer to the carrier.
  • Any resin such as acrylic resin, epoxy resin, urethane resin, polyester resin, and alkyd resin can be used as the resin into which colloidal silica is introduced.
  • acrylic resin, epoxy resin and polyester resin are particularly preferable when they are made of silicone-modified resin, because they can obtain excellent durability and resistance to stress.
  • the colloidal silicity can be any type of silica sol obtained by cation exchange of an aqueous solution of sodium silicate or a silica sol obtained by hydrolyzing silicon alkoxide. it can.
  • a resin containing both polysiloxane and colloidal silicide can be used as the adhesive layer.
  • the total content of the polysiloxane and the colloidal sily in the adhesive layer is within the above range of the content showing the improvement in the alkali resistance when converted to oxides, the same excellent alkali resistance is obtained.
  • the colloidal silicity and the particle diameter of polysiloxane are preferably 10 nm or less. If the particle diameter of colloidal silica or polysiloxane exceeds 10 nm, the dispersibility becomes poor, and the transmissivity of the adhesive layer is reduced, so that the total wavelength of the total wavelength of the adhesive layer and the photocatalyst layer is 550 nm.
  • the light transmittance may be 70% or less.
  • a light stabilizer and a UV absorber or an ultraviolet absorber can be further added to the adhesive layer resin for the purpose of suppressing deterioration due to photocatalysis.
  • a light stabilizer that can be used a hindered amine type is preferable, but other substances can also be used.
  • As the ultraviolet absorber a triazole or the like can be used. These additives are added in an amount of 0.05 to 10% by weight, preferably 0.01 to 5% by weight, based on the resin. It is also preferable to treat the adhesive layer with a silane-based or titanium-based coupling agent to increase the adhesion to the photocatalyst layer.
  • Examples of a method for forming an adhesive layer on a carrier include a method of coating, drying and curing an adhesive resin solution by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, or the like. .
  • the drying temperature varies depending on the type of solvent and resin, but is generally preferably about 50 ° C. to 300 ° C.
  • the thickness of the adhesive layer is preferably about 0.1 jum to 20 jui in order to obtain good adhesion to the photocatalyst layer. When the thickness of the adhesive layer is 0.1 l ⁇ m or less, the function of firmly bonding the photocatalyst layer is weakened. On the other hand, when the thickness is 20 zm or more, there is no particular problem, but there is little merit in setting the thickness to 20 m or more in consideration of actual coating processing.
  • the photocatalyst layer can be formed by coating the coating solution for forming a photocatalyst layer on the surface of the adhesive layer by a printing method, a sheet forming method, a spray spraying method, a dip coating method, a spin coating method, etc., and then drying and curing. it can.
  • the preferred temperature for drying and curing varies depending on the carrier material and the resin material in the adhesive layer, but is usually about 50 ° C to 300 ° C.
  • the photocatalytic activity increases as the thickness of the photocatalyst layer increases, but when it exceeds 20 m, the photocatalytic activity is saturated, but in many cases it becomes difficult in actual coating processing, and the light transmittance of the photocatalytic layer increases. It is preferably 20 m or less because of lowering. On the other hand, when the thickness of the photocatalyst is less than 0.1 ⁇ m, although the translucency is improved, high activity cannot be expected because the ultraviolet light used by the photocatalyst is transmitted.
  • the photocatalyst layer and the adhesive layer can be formed.
  • the total light transmittance at a total wavelength of 550 nm is not less than 80% and the haze rate can be not more than 2%.
  • Such a photocatalyst-supporting structure is excellent in terms of decorativeness when a transparent carrier is used, because transmitted visible light can be used as illumination, and even when the carrier is opaque, the pattern on the carrier is not damaged. It will be.
  • the photocatalyst-carrying structure of the present invention thus obtained is characterized in that the turbidity of the coating film including the adhesive layer and the photocatalyst layer is 3% or less.
  • turbidity is used in the same meaning as the haze ratio described above.
  • the turbidity of the coating film including the adhesive layer and the photocatalyst layer after boiling for 1 hour in boiling ion-exchanged water is 3% or less, and the light intensity of black light having an ultraviolet intensity of 3 mWZ cm 2 is characterized. Is rated at 6 points or more by the cross-cut tape method specified in JISK540 after irradiating for 500 hours at a temperature of 40 ° C and a relative humidity of 90%.
  • the turbidity of the coated film is 3% or less.
  • Structures supporting the photocatalyst of the present invention include architectural paints, wallpapers, window glasses, blinds, curtains, carpets, lighting fixtures, lighting lights, road lights, tunnel lights, noise barriers on highways and bullet trains, and black lights.
  • Ship bottom fishing net antifouling paint, water treatment filler, agricultural film, It can be used for herbicidal sheets, packaging materials, etc. In particular, when used in a high-temperature and high-humidity environment or in an outdoor environment, it exhibits properties such as excellent durability and transparency.
  • A-1) Aluminum oxide hydroxide (boehmite) fine particles (Alumina sol 10 from Kawaken Fine Chemicals)
  • Z-1 A solution obtained by dissolving Wako Pure Chemical's special grade reagent zirconium nitrate hexahydrate in water to form a 10% aqueous solution, and then heating for 12 hours to distill half the volume of water at normal pressure. was used as a zirconium oxynitrate solution.
  • the above titanium oxide photocatalyst, sol solution and compound solution were prepared in an appropriate range of PHI. 5 to 9, mixed, and a predetermined amount of surfactant was added to obtain a coating solution for forming a photocatalyst layer.
  • Adhesive layer The following polysiloxane was used in the adhesive layer.
  • PS-2 Polymethoxysiloxane manufactured by Colcoat Methyl Silicate 51
  • PS-3 Polyethoxysiloxane manufactured by Corcot Tylsilicate 40
  • the following colloidal silica was used as the colloidal silica contained in the adhesive layer.
  • KS-1 Product name Cataroid SI-350, manufactured by Catalysis Kasei Co., Ltd., particle size 7-9 nm
  • KS-2 Product name, Snowtex ST-XS, manufactured by Nissan Chemical Co., Ltd. Particle size 4-6 nm
  • the following resin solutions were used to introduce siloxane or colloidal silica.
  • the silicon content was displayed in terms of S i 0 2 in the resin solids.
  • Polysiloxane or colloidal silica was mixed with the resin solution and the concentration was adjusted to obtain a solution for forming an adhesive layer.
  • the adhesive layer was formed by a dipping method when the thickness was 2 m or less or the carrier shape was other than a flat plate, and was formed by a baker applicator when the carrier was a flat plate and the thickness was 2 mm or more.
  • the drying of the adhesive layer was performed at 80 ° C when the material of the carrier was (TB), and at 120 ° C otherwise.
  • the photocatalyst layer is a dipping method when the thickness of the carrier is 2 m or less or when the shape of the carrier is other than a flat plate, and a bar coater when the carrier is a flat plate and the thickness is 2 m or more.
  • a coating was formed on the surface of the backseat phase.
  • the drying of the photocatalytic layer was performed at the same temperature as the drying of the adhesive layer.
  • a sample carrying a photocatalyst cut out to a size of 70 mm ⁇ 70 mm was placed in a Pyrex (registered trademark) glass container having a capacity of 4 liters.
  • a mixed gas of air and aldehyde was added to the container so that the aldehyde concentration became 2 OO pm.
  • UV intensity 2 mW / cm 2 of black light in carrying the sample FL 15BLB, Toshiba Lighting & Technology Corporation
  • an aldehyde gas concentration in the container was measured Ri by the gas chromatograph, by its decrease Photocatalytic activity was evaluated.
  • the evaluation criteria are as follows.
  • a boiling water test was performed in accordance with the boiling water test specified in JI SK5400. However, the immersion time was set to 1 hour.
  • Table 1 summarizes the embodiments and comparative examples in which the type and amount of each material were changed, and Table 2 summarizes the performance test results of the photocatalyst-carrying structure obtained.
  • Example 1 TA Jl 5 5 85 5 Example 2 TA Jl 5 5 80 10 Example 3 TA J2 5 20 65 10 Example 4 TA PS2 10 Jl 5 5 70 20 Example 5 TA PS3 30 Jl 20 20 40 20 Example 6 TA PS1 10 Jl 20 40 30 10 Example 7 TB PS1 30 Jl 40 5 50 5 Example 8 TB PS3 30 Jl 40 5 45 10 Example 9 TC PS1 10 Jl 40 10 10 40 Example 10 TA PS2 30 Jl 40 10 40 10 Example 11 TB PS2 30 Jl 40 10 30 20 Example 12 TA PS2 30 Jl 40 20 30 10 Example 13 TC PS2 30 Jl 40 10 10 Example 14 TA PS2 30 Jl 60 5 30 5 Example 15 TA PS2 30 J3 40 5 35 20 Example 16 TA PS2 30 J4 40 10 45 5 Example 17 TA PS2 30 J5 20 20 55 5 Example 18 TA PS1 50 J6 60 10 10 20 20
  • Example 1 C 8 8 8 0.7 0.8 0.7 Example 2 C 8 8 8 1.2 1.3 1.2 Example 3 C 10 10 10 1.9 2.2 2.0 Example 4 C 10 10 10 1.7 1.8 1.7 Example 5 B 10 10 10 2.5 2.8 2.6 Example 6 B 10 10 10 2.5 3.0 2.6 Example 7 A 8-8 0.9-0.9 Example 8 A 10 1 10 1.4-1.4 Example 9 A 10 10 10---Example 10 A 10 10 10 1.6 1.8 1.6 Example 11 A 10-10 2.1 2.1 Example 12 A 10 10 10 2.1 2.4 2.2 Example 13 A 10 10 10---Example 14 A 10 10 8 1.0 1.1 1.1 Example 15 A 10 10 10 1.9 2.0 1.9 Example 16 A 8 8 8 1.1 1.3 1.1 Example 17 B 10 10 10 1.5 1.8 1.6 Example 18 A 10 10 8 2.2 2.4 2.3 Example 19 C 10 10 10 2.2 2.3 2.2 Example 20 B 10 10 10 2.5
  • Comparative Examples 1 and 2 are cases in which Nissan Chemical Snowtex 20 was used as a silica sol having no necklace-like structure. Poor adhesion of photocatalyst layer after boiling water test.
  • the haze ratio was high, and the haze ratio was increased after the durability test.
  • Comparative Example 3 is a case where the photocatalyst layer contains too much zirconazole. Initial haze rate is high.
  • Examples 1 to 3 are examples in which an acrylic silicon resin was used for the adhesive layer and a photocatalytic layer using necklace-shaped colloidal silica was used. These samples were evaluated well by the boiling water test and had good durability.
  • Examples 4 to 14 are examples in which an acryl-silicon resin containing polysiloxane was used for the adhesive layer, and a photocatalytic layer using necklace-shaped colloidal silica was used.
  • Examples 7, 8, and 11 are examples in which they are supported on a transparent acrylic plate. These samples also had good durability.
  • epoxy-silicon resin (Example 16), polyester-silicone resin (Example 17), or ataryl polymer (Example 18) into which polysiloxane is introduced is used as the resin for the adhesive layer. It showed good performance.
  • Examples 19 to 26 a resin containing colloidal silica was used for the adhesive layer, and the catalyst activity, boiling water resistance, and durability were good.
  • Examples 27 to 31 show that a photocatalyst layer was formed directly on a sodium glyme glass plate without using an adhesive layer, and then dried at 200 ° C. Boiling water and durability were good.
  • Example 2 The samples obtained in 7 to 31 were subjected to a durability test using a black light under high temperature and high humidity, a boiling water test, and a sunshine force-bon arc weather meter (Suga test machine, WE L— SUN— The sample subjected to accelerated light resistance test (HCH type) for 2000 hours was again examined for photocatalytic activity by the amount of acetoaldehyde gas decomposed in the same manner as in the initial stage. It was found that both samples maintained the initial photocatalytic activity.
  • HSH type accelerated light resistance test
  • Example 27 The sample obtained in Examples 7 to 31 was subjected to accelerated light resistance test using a Sunshine Carbon Arc Weather Meter 1 (Suga Test Machine, WEL-SUN-HCH type) for 2000 hours. When the haze ratio was measured, all turbidity values were within 2%, It was found that transparency was maintained.
  • a film was formed in the same manner as in Example 12 except that a polymethoxysiloxane (reagent) was further added to the photocatalytic layer agent so as to be 10% by weight relative to the total solid content in terms of oxide.
  • the photocatalyst was rated B. However, when a felt abrasion test was performed using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd., the coating of Example 12 was peeled in 200 reciprocations. No peeling of the 32 coating film was observed even in 400 reciprocations.
  • a film was formed in the same manner as in Example 14 except that a polymethoxysiloxane (reagent) was further added to the photocatalytic layer agent in an amount of 20% by weight relative to the total solid content in terms of oxide.
  • the photocatalyst was rated C.
  • a felt abrasion test was performed using a rubbing tester manufactured by Ohira Rika Kogyo Co., Ltd.
  • the coating of Example 14 was peeled after 100 reciprocations. In Example 33, no peeling was observed even in 400 reciprocations.
  • the photocatalyst composite of the present invention has a very high photocatalytic activity and is excellent in transparency.
  • the photocatalyst layer-forming coating solution of the present invention has excellent storage stability and can easily form a photocatalyst layer.
  • the resulting photocatalyst layer can be a transparent one that transmits visible light, so that the catalyst can be supported without damaging the pattern of the carrier, and decorativeness can be applied to a wide range of carriers such as general-purpose resins and natural fibers.
  • a photocatalyst-carrying structure having excellent activity without any loss can be obtained.
  • the photocatalyst-supporting structure of the present invention has a photocatalyst firmly adhered to a carrier, has a very high photocatalytic activity, and does not cause deterioration of the carrier or desorption of the photocatalyst by the photocatalytic action.
  • the photocatalyst-supporting structure of the present invention can be used for a long time even under light irradiation.
  • the alkali resistance test has been evaluated well, and since it maintains high adhesion even after accelerated weathering test by the Sunshine Carbon Arc Meter, it can be used in hot and humid environments or in outdoor environments. Can be used.

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Abstract

L'invention concerne une matière composite photocatalytique contenant un photocatalyseur et des particules de silice colloïdale, caractérisée en ce que les particules de silice colloïdale comprennent des particules de silice colloïdale sphériques collées les unes aux autres de sorte à former une forme longue et étroite, et la matière composite photocatalytique comprend également au moins un composé sélectionné dans le groupe contenant un composé de zirconium et un composé d'aluminium. Cette matière composite photocatalytique peut être utilisée pour produire une structure portant un photocatalyseur, utile pour une clarification, une désodorisation, un traitement anti-coloration, une stérilisation d'eau, un traitement d'eaux usées, une suppression de croissance d'algues, et des réactions chimiques variées.
PCT/JP2002/010582 2001-10-12 2002-10-11 Matiere composite photocatalytique, liquide d'application permettant de former une couche photocatalytique et structure portant un photocatalyseur WO2003033144A1 (fr)

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EP1577008A2 (fr) * 2004-03-17 2005-09-21 Sumitomo Chemical Company, Limited Composition de revêtement photocatalytique
JP2007055207A (ja) * 2005-08-26 2007-03-08 Nippon Soda Co Ltd 光触媒担持構造体
JP2009039687A (ja) * 2007-08-10 2009-02-26 Nippon Soda Co Ltd 光触媒層形成用組成物
JP2009194120A (ja) * 2008-02-14 2009-08-27 Tokyo Ohka Kogyo Co Ltd 無機被膜形成用組成物
JP2010099647A (ja) * 2008-03-28 2010-05-06 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
JP2010270094A (ja) * 2008-06-09 2010-12-02 Sumitomo Chemical Co Ltd 蓚酸ジルコニウムゾル
US7919425B2 (en) 2008-03-26 2011-04-05 Toto Ltd. Photocatalyst-coated body and photocatalytic coating liquid for the same
US7977270B2 (en) 2007-03-26 2011-07-12 Toto Ltd. Photocatalyst-coated body and photocatalytic coating liquid therefor
JP2013139104A (ja) * 2011-12-29 2013-07-18 Toto Ltd 複合材およびコーティング組成物
WO2015133316A1 (fr) * 2014-03-03 2015-09-11 株式会社鯤コーポレーション Liquide de revêtement photocatalytique et film photocatalyseur l'utilisant
JP2018070781A (ja) * 2016-10-31 2018-05-10 国立大学法人徳島大学 植物成長調整用コーティング組成物
JPWO2017146015A1 (ja) * 2016-02-26 2018-12-06 日本曹達株式会社 光触媒構造体及びその製造方法

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JP4693949B2 (ja) * 1999-10-06 2011-06-01 日本曹達株式会社 光触媒層形成用塗布液、光触媒複合体および光触媒構造体
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JPH09313948A (ja) * 1996-05-28 1997-12-09 Nippon Parkerizing Co Ltd 光触媒表面を有する樹脂または樹脂被覆材料およびその製造方法
US6071606A (en) * 1996-08-26 2000-06-06 Nissan Motor Co., Ltd Hydrophilic film and method for forming same on substrate
JPH1110803A (ja) * 1997-06-26 1999-01-19 Toray Ind Inc 農業用資材
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Publication number Priority date Publication date Assignee Title
EP1577008A3 (fr) * 2004-03-17 2006-04-12 Sumitomo Chemical Company, Limited Composition de revêtement photocatalytique
US7521391B2 (en) 2004-03-17 2009-04-21 Sumitomo Chemical Company, Limited Coating composition of photocatalyst
EP1577008A2 (fr) * 2004-03-17 2005-09-21 Sumitomo Chemical Company, Limited Composition de revêtement photocatalytique
JP2007055207A (ja) * 2005-08-26 2007-03-08 Nippon Soda Co Ltd 光触媒担持構造体
US7977270B2 (en) 2007-03-26 2011-07-12 Toto Ltd. Photocatalyst-coated body and photocatalytic coating liquid therefor
US8372774B2 (en) 2007-03-26 2013-02-12 Toto Ltd. Photocatalyst-coated body and photocatalytic coating liquid therefor
US8216959B2 (en) 2007-03-26 2012-07-10 Toto Ltd. Photocatalyst-coated body, coating composition for the same, and process for producing photocatalyst-coated body
US8207079B2 (en) 2007-03-26 2012-06-26 Toto Ltd. Photocatalyst-coated body and photocatalytic coating liquid therefor
JP2009039687A (ja) * 2007-08-10 2009-02-26 Nippon Soda Co Ltd 光触媒層形成用組成物
JP2009194120A (ja) * 2008-02-14 2009-08-27 Tokyo Ohka Kogyo Co Ltd 無機被膜形成用組成物
US7919425B2 (en) 2008-03-26 2011-04-05 Toto Ltd. Photocatalyst-coated body and photocatalytic coating liquid for the same
JP2010099647A (ja) * 2008-03-28 2010-05-06 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
JP2010270094A (ja) * 2008-06-09 2010-12-02 Sumitomo Chemical Co Ltd 蓚酸ジルコニウムゾル
JP2013139104A (ja) * 2011-12-29 2013-07-18 Toto Ltd 複合材およびコーティング組成物
WO2015133316A1 (fr) * 2014-03-03 2015-09-11 株式会社鯤コーポレーション Liquide de revêtement photocatalytique et film photocatalyseur l'utilisant
CN106133078A (zh) * 2014-03-03 2016-11-16 株式会社鲲 光催化剂涂布液及使用其的光催化剂膜
JP2017042683A (ja) * 2014-03-03 2017-03-02 株式会社鯤コーポレーション 光触媒塗工液及びそれを用いた光触媒フィルム
JPWO2015133316A1 (ja) * 2014-03-03 2017-04-06 株式会社鯤コーポレーション 光触媒塗工液及びそれを用いた光触媒フィルム
JPWO2017146015A1 (ja) * 2016-02-26 2018-12-06 日本曹達株式会社 光触媒構造体及びその製造方法
JP2018070781A (ja) * 2016-10-31 2018-05-10 国立大学法人徳島大学 植物成長調整用コーティング組成物

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