WO2016181622A1 - Liquide de revêtement contenant un photocatalyseur et structure support de photocatalyseur - Google Patents

Liquide de revêtement contenant un photocatalyseur et structure support de photocatalyseur Download PDF

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WO2016181622A1
WO2016181622A1 PCT/JP2016/002168 JP2016002168W WO2016181622A1 WO 2016181622 A1 WO2016181622 A1 WO 2016181622A1 JP 2016002168 W JP2016002168 W JP 2016002168W WO 2016181622 A1 WO2016181622 A1 WO 2016181622A1
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photocatalyst
coupling agent
silane coupling
containing coating
mass
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PCT/JP2016/002168
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Japanese (ja)
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大哉 小林
一徳 齋藤
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日本曹達株式会社
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Priority to JP2017517604A priority Critical patent/JP6467502B2/ja
Publication of WO2016181622A1 publication Critical patent/WO2016181622A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical 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
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B9/00—Layered products comprising a layer of a particular substance not covered by groups B32B11/00 - B32B29/00
    • 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
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D185/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing atoms other than silicon, sulfur, nitrogen, oxygen, and carbon; Coating compositions based on derivatives of such polymers
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

Definitions

  • the present invention relates to a photocatalyst-supporting structure and a photocatalyst-containing coating liquid for forming the same, and more specifically, a photocatalyst-supporting structure in which a photocatalyst layer is directly provided on a substrate and a photocatalyst coating liquid for forming the photocatalyst layer About.
  • a photocatalyst is supported on the surface of a plastic for applications such as building materials, interior materials, appliances, and packaging materials.
  • a titanium oxide (titania) sol known as a representative substance having a photocatalytic effect is also used as a coating agent component for forming a transparent hard coat layer as a use different from the effect.
  • Patent Document 1 a coating solution containing a titania sol dispersed in an organic solvent, an acrylic silicone resin or an epoxy silicone resin, and a partial hydrolysis product of tetraalkoxysilane is directly applied to a substrate such as glass. A photocatalyst carrying structure is described.
  • Patent Document 2 describe an example in which an epoxysilane coupling agent is contained in the photocatalyst layer in order to improve the adhesion between the photocatalyst layer and the intermediate layer.
  • Patent Document 3 describes a cured product obtained by photocuring a photocurable composition containing a photocatalyst, a photoacid generator, and ⁇ -glycidoxypropyltrimethoxysilane.
  • Patent Document 4 describes a coating composition for forming a photocatalytic coating film containing a silane coupling agent having an ultraviolet polymerizable functional group and a photopolymerization initiator.
  • Patent Document 5 discloses titanium oxide nanoparticles, condensates of silane compounds including 3-methacryloxypropyltrimethoxysilane and 3-glycidoxypropyltrimethoxysilane, and other functional substances (such as photocatalytic titanium oxide). Organic-inorganic composites containing are described.
  • Patent Document 6 a photocatalyst containing titanium oxide, a tetrafunctional silane compound, and a coating film forming agent containing an epoxy or acrylic silane coupling agent as the case may be applied and cured with ultraviolet rays.
  • a coating film is described, and it is described that when the coating film forming agent further contains a metal alkoxide, the cloudiness of the coating film due to condensation of water-repellent fine particles can be suppressed.
  • the coating obtained by directly applying to the substrate by the methods of Patent Documents 3 to 6 has a certain level of strength, but it remains a problem that the organic substrate is choked by UV irradiation. In particular, it has been a problem to achieve both photocatalytic activity and prevention of choking. It is an object of the present invention to provide a photocatalyst-supporting structure that exhibits sufficient photocatalytic activity and does not cause deterioration of the substrate.
  • the present inventors include, as a photocatalyst-containing coating solution, a silane coupling agent that is an epoxy silane coupling agent or an acrylic silane coupling agent, and a metal coupling agent that does not have silicon as a central metal, and the silane cup
  • a photocatalyst-containing coating solution a silane coupling agent that is an epoxy silane coupling agent or an acrylic silane coupling agent
  • a metal coupling agent that does not have silicon as a central metal
  • the present invention (1) Photocatalyst material fine particles, epoxy silane coupling agent and acrylic silane coupling agent selected from at least one silane coupling agent and / or hydrolysis condensate of the silane coupling agent, silicon as a metal element A total amount of the silane coupling agent and hydrolysis condensate of the silane coupling agent in a ratio of 300 parts by mass or more with respect to 100 parts by mass of the photocatalyst material fine particles.
  • Photocatalyst-containing coating solution (2) The photocatalyst-containing coating solution according to (1), which does not contain a silane compound other than the silane coupling agent, (3) The photocatalyst-containing coating solution according to (1) or (2), further containing fine-particle silica, (4)
  • the metal coupling agent having no silicon as a metal element is at least one selected from a titanate coupling agent, an aluminate coupling agent and a zirconate coupling agent, (1) or (2)
  • the hydrolytic condensate relates to a photocatalys
  • the present invention also provides: (8) A photocatalyst-supporting structure in which a photocatalyst layer is directly provided on a base material, wherein the photocatalyst-containing coating liquid according to any one of (1) to (7) is applied on a base material and dried. (9) The photocatalyst carrying structure according to (8), wherein the substrate is an organic material, and (10) the photocatalyst carrying structure according to (9), wherein the organic material is a synthetic resin. Furthermore, the present invention provides (11) The present invention relates to a method for forming a photocatalyst-supporting structure by directly applying the photocatalyst-containing coating liquid according to any one of (1) to (7) onto a substrate and drying it.
  • the photocatalyst-supporting structure of the present invention exhibits excellent photocatalytic activity, has excellent adhesion to the base material, and does not cause deterioration such as choking on the base material.
  • 3 is a graph showing the antiviral properties of the photocatalyst-supporting structure of the present invention when KBM-403 (epoxysilane coupling agent) is used.
  • 3 is a graph showing the antiviral properties of the photocatalyst-supporting structure of the present invention when KBM-5103 (acrylic silane coupling agent) is used.
  • the photocatalyst-containing coating liquid of the present invention is a silane coupling agent that is at least one selected from photocatalyst material fine particles, a solvent, an epoxy silane coupling agent, and an acrylic silane coupling agent, and / or hydrolytic condensation of the silane coupling agent. And a liquid composition containing a metal coupling agent having no silicon as a central metal element, and a solvent.
  • the photocatalyst material fine particles used in the photocatalyst-containing coating solution of the present invention are fine particles made of an inorganic material containing a metal oxide having photocatalytic activity.
  • the main components of the photocatalytic material are titanium oxide, zinc oxide, tin oxide, zirconium oxide, tungsten oxide, chromium oxide, molybdenum oxide, iron oxide, nickel oxide, ruthenium oxide, vanadium oxide, niobium oxide, tantalum oxide, rhodium oxide, Examples include rhenium oxide.
  • titanium oxide, tungsten oxide and the like, particularly anatase type or rutile type titanium oxide are preferable.
  • the photocatalyst material fine particles is not particularly limited, but in particular, when a metal oxide such as silica is used in combination as a filler, it has an average particle diameter larger than the average particle diameter of the filler from the viewpoint of exerting sufficient photocatalytic activity.
  • the average particle diameter is more preferably 40 to 500 nm.
  • R 1 Si (X) 3 As a silane coupling agent used for the photocatalyst containing coating liquid of the present invention, a general formula: R 1 Si (X) 3 , R 1 (R 2 ) Si (X) 2 , or R 1 (R 2 ) 2 SiX (however, In each formula, R 1 represents an organic group having a carbon atom directly connected to a silicon atom represented by Si, and at least one functional group selected from an epoxy group and a (meth) acryloxy group, and R 2 represents a non-hydrolyzed group.
  • X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, an alkoxy group, a phenoxy group or an acyloxy group, a group represented by R 2 or a group represented by X
  • R 2 or X may be the same or different from each other.
  • the silane coupling agent in which R 1 has an epoxy group is referred to as an epoxy silane coupling agent
  • the silane coupling agent in which R 1 has a (meth) acryloxy group is referred to as an acrylic silane coupling agent.
  • R 1 is a group having an epoxy group or a (meth) acryloxy group in an organic group such as an alkyl group which may have a substituent and / or —O— group, and specifically, ⁇ -glycol. Sid propyl group, beta-(3,4-epoxycyclohexyl) ethyl group, .gamma.-acryloxypropyl group, .gamma.-methacryloxypropyltrimethoxysilane, etc. b propyl group.
  • R 2 C1, such as a methyl group, an ethyl group And an organic group exemplified as the R 1
  • the X is a chlorine atom, a C1-C5 alkoxy group such as a methoxy group, an ethoxy group, and a ⁇ -methoxyethoxy group
  • examples thereof include C1-C6 acyloxy groups such as formyloxy group, acetyloxy group and propionyloxy group.
  • the silane coupling agent used in the photocatalyst-containing coating solution of the present invention has a general formula: R 1 Si (OR 3 ) 3 (wherein R 1 represents the same as described above, and R 3 represents a C1-3 alkyl group.
  • the photocatalyst-containing coating liquid of the present invention includes at least one of at least one epoxysilane coupling agent or a hydrolysis condensate thereof, and at least one acrylic silane coupling agent or a hydrolysis condensate thereof. It is preferable to contain.
  • the photocatalyst-containing coating solution of the present invention preferably contains no silane compound other than the silane coupling agent.
  • silane compounds other than the silane coupling agent include general formulas: Si (X) 4 , R 4 Si (X) 3 , (R 4 ) 2 Si (X) 2 , (R 4 ) 3 SiX, and their condensations.
  • R 4 ) 4 Si (wherein R 4 represents a non-hydrolyzable organic group having no epoxy group, acryloxy group or methacryloxy group, and represented by R 4)
  • R 4 may be the same or different from each other
  • X represents the same as above, and more specifically, an organic substance.
  • dialkoxydialkylsilane dialkoxydiphenylsilane, trialkoxyalkylsilane, trialkoxyphenylsilane, tetraalkoxysilane, tetraphenoxysilane, etc. It is shown.
  • the strength of the coating film can be increased by hydrolytic condensation of the silane coupling agent contained in the photocatalyst-containing coating solution of the present invention.
  • an epoxy silane coupling agent is used as the silane coupling agent, it is preferable to hydrolyze and condense the silane coupling agent before mixing with other components.
  • an aluminate coupling agent as a metal coupling agent described later.
  • a titanate coupling agent or a zirconate coupling agent if water is present, these undergo hydrolysis and the coating strengthening effect by the metal coupling agent may be impaired.
  • the photopolymerization initiator may be a compound that can start a polymerization reaction between (meth) acryloxy groups when irradiated with ultraviolet rays. Thereby, superposition
  • Specific examples of the photopolymerization initiator include benzoin derivatives that generate radicals by irradiation with ultraviolet rays, and the radicals cause polymerization.
  • the metal coupling agent having no silicon as a metal element used in the photocatalyst coating solution of the present invention is a metal compound having a hydrolyzable group and thereby undergoing a crosslinking reaction. More specifically, any of a metal complex in which a ligand is coordinated to a metal element and a metal alcoholate in which an alkoxy group is bonded to the metal element (including compounds classified into both) is also included. . Of these, titanate coupling agents, aluminate coupling agents and zirconate coupling agents are preferred.
  • titanate coupling agents include titanium alkoxides such as tetraisopropyl titanate, tetra-n-butyl titanate, tetrakis (2-ethylhexyloxy) titanium, titanium-i-propoxyoctylene glycolate; titanium acetylacetonate, titanium Tetraacetylacetonate, di-i-propoxy bis (acetylacetonato) titanium, di-n-propoxy bis (acetylacetonato) titanium, di-n-butoxy bis (acetylacetonato) titanium, diethoxy bis
  • titanium complexes such as (acetylacetonato) titanium and propanedioxytitanium bis (ethylacetoacetate).
  • aluminate coupling agent examples include aluminum alcoholates such as aluminum isopropylate, mono-sec-butoxyaluminum diisopropylate, and aluminum ethylate; ethyl acetoacetate aluminum diisopropylate, aluminum bisethylacetoacetate monoacetyl Acetonate, aluminum tris (ethyl acetoacetate), aluminum tris (acetylacetonate), diethoxymono (acetylacetonato) aluminum, di-i-propoxymono (acetylacetonato) aluminum, di-n-propoxymono (acetylacetonate) ) Aluminum, di-n-butoxymono (acetylacetonato) aluminum, ethoxybis (acetylacetonato) aluminum Um, i- Puropokishibisu (acetylacetonate) aluminum, n- Puropokishibisu (acetylacetonate) aluminum, n- butoxy
  • Zirconate coupling agents include zirconium tetrakis (acetylacetonate), di-n-butoxybis (acetylacetonato) zirconium, zirconium tetrakis (ethylacetoacetate), diethoxybisacetylacetonatozirconium, di-i-propoxybis (Acetylacetonato) zirconium, di-n-propoxybis (acetylacetonato) zirconium, tri-n-butoxymonoethylacetoacetate zirconium, tri-n-butoxymonoacetylacetonatozirconium and the like.
  • acetylacetonate coupling agent examples include those that are acetylacetonate coupling agents among the titanate coupling agents, aluminate coupling agents, and zirconate coupling agents.
  • the photocatalyst-containing coating solution of the present invention contains a solvent.
  • the solvent is not particularly limited. For example, water; alcohols such as methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, and t-butanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetyl acetone, and cyclohexanone; diethyl ether, Ethers such as methyl cellosolve and tetrahydrofuran; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as dichloromethane and chloroform; esters such as ethyl acetate, propyl acetate and butyl acetate; pentane, hexane and cyclohexane And saturated hydrocarbons. Moreover, these 2 types or more can also be mixed and used.
  • the photocatalyst-containing coating solution of the present invention includes a film forming aid, a thickener, an antifoaming agent, a pigment, a filler, a dispersant, a dye, a preservative, and the like, and the effects of the present invention are impaired It can mix
  • a metal oxide composed of fine particles as a filler, effects such as enhancement of light resistance can be obtained.
  • Metal oxides used as fillers include magnesium, aluminum, silicon, titanium, vanadium, iron, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, indium, tin, antimony, tantalum, tungsten, cerium, etc. Examples thereof include oxides containing elements (excluding photocatalytic materials).
  • the photocatalyst-containing coating solution of the present invention preferably contains fine particle silica.
  • the fine particle silica preferably has an average particle diameter of 100 nm or less.
  • the shape of the fine particle silica is preferably spherical silica particles or particles formed by bonding spherical silica particles in an elongated shape (the average particle diameter of the whole is preferably 100 nm or less).
  • the average particle diameter of the spherical silica particles referred to here is preferably 40 nm or less, and more preferably 5 to 20 nm. When the average particle diameter is larger than 100 nm, the abrasion resistance due to steel wool or nails is inferior.
  • the photocatalyst-containing coating solution of the present invention contains 300 parts by mass or more of the total of the silane coupling agent and the hydrolysis condensate of the silane coupling agent with respect to 100 parts by mass of the photocatalyst material fine particles.
  • the total of the silane coupling agent and the hydrolysis condensate of the silane coupling agent is more preferably contained in a ratio of 300 to 1000 parts by mass.
  • Metal coupling agent 20 parts by mass or more, more preferably 50 to 300 parts by mass.
  • Filler made of metal oxide, preferably fine particle silica 0 to 400 parts by mass, more preferably 50 to 400 parts by mass.
  • the photocatalyst-containing coating solution of the present invention has a photocatalyst of 0.5 to 20% by mass and a silane coupling agent and / or a hydrolysis condensate of the silane coupling agent in a total of 5 to 5% by mass in the solid component. 80% by mass, more preferably 20-80% by mass, metal coupling agent 2-60% by mass, more preferably 2-30% by mass, metal oxide filler, preferably fine particle silica, 0-40% by mass. %, More preferably 1 to 20% by mass.
  • the photocatalyst carrying structure of the present invention is a photocatalyst carrying structure in which the photocatalyst layer is in direct contact with the base material, which is obtained by applying the photocatalyst-containing coating liquid of the present invention onto the base material and drying it.
  • the base material is not particularly limited, but inorganic materials include metal, glass, ceramics, cement, etc., and organic materials include wood; paper; natural fibers; rubber; leather; polyethylene, polypropylene, acrylic resin, polyethylene terephthalate, poly Examples thereof include synthetic resins such as vinyl chloride, polyvinylidene chloride, polycarbonate, polystyrene, ABS resin, phenol resin, urea resin, polyurethane, epoxy resin, and melamine resin.
  • organic materials particularly synthetic resins, which have conventionally been difficult to directly provide a photocatalytic layer are preferred. It is preferable to subject the surface of the synthetic resin photocatalyst layer to contact with the surface before applying the photocatalyst-containing coating solution.
  • the easy adhesion treatment include a method of performing corona discharge treatment or UV-ozone treatment on the surface.
  • the method for applying the photocatalyst-containing coating solution of the present invention to the substrate is not particularly limited, and is a known method such as a spray coating method, a flow coating method, a spin coating method, a Meyer bar method, a dip coating method, or a roll coating method. What is necessary is just to dry after apply
  • the thickness of the photocatalyst layer in the photocatalyst-supporting structure of the present invention is not particularly limited, but the thickness after drying is usually 0.01 to 10 ⁇ m, and more preferably 0.5 to 5.0 ⁇ m.
  • the photocatalyst-containing coating solution of the present invention contains an acrylic silane coupling agent and a photopolymerization initiator
  • an apparatus such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a metal lamp, an excimer lamp, a carbon arc lamp, or a xenon arc lamp can be used.
  • the ultraviolet irradiation amount is preferably from 0.1 to 100 J / cm 2 .
  • This slurry was filtered, and the obtained solid content was washed with pure water, dried at 80 ° C., and pulverized with a mixer.
  • This pulverized product was heat-treated at 450 ° C. for 3 hours in the air to obtain Sample 1.
  • the sample 1 was heated and dissolved in a hydrofluoric acid solution, and the extract was quantified by ICP emission spectroscopic analysis.
  • the copper ion was 3.0 parts by mass with respect to 100 parts by mass of titanium oxide. It was. That is, the total amount of charged copper ions (derived from CuCl 2 ⁇ 2H 2 O) was supported on the titanium oxide surface as CuO.
  • the average particle size of Sample 1 was about 150 nm.
  • a certain amount of Sample 1 was added to isopropyl alcohol and suspended therein to prepare a photocatalyst suspension having a solid content of 0.25 to 5.0% by mass.
  • Example 1 Effect of metal coupling agent [Examples 1, 2, 3, 4 and Comparative Example 1]
  • the solid content obtained in Production Example 1 was 0.25% by mass (Example 1), 0.5% by mass (Example 2), 1.0% by mass (Example 3), 2.5% by mass. (Example 4) or 2.27 g of KBM-5103 ( ⁇ -acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone) was added to 21.67 g of the photocatalyst suspension of 5.0% by mass (Comparative Example 1).
  • a photocatalyst having a solid content of 0.25% by mass (Comparative Example 2), 0.5% by mass (Comparative Example 3), 1.0% by mass (Comparative Example 4), or 2.5% by mass (Comparative Example 5)
  • KBM-5103 ⁇ -acryloxypropyltrimethoxysilane, manufactured by Shin-Etsu Silicone
  • Irgacure registered trademark
  • Example 5 (Effect of fine particle silica) [Example 5] 2.27 g of KBM-403 ( ⁇ -glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone) was added to 21.67 g of the photocatalyst suspension having a solid content of 2.5% by mass obtained in Production Example 1. Then, 0.86 g of T-50 was added and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
  • KBM-403 ⁇ -glycidoxypropyltriethoxysilane, manufactured by Shin-Etsu Silicone
  • Example 6 To the photocatalyst-containing coating solution obtained in Example 5, 0.9 g of IPA-ST (particulate silica, particle size 10 to 15 nm, suspended in isopropyl alcohol at 30% by mass, manufactured by Nissan Chemical Industries, Ltd.) ), 1.8 g (Example 7) or 3.6 g (Example 8) was added and mixed for 5 minutes to obtain a photocatalyst-containing coating solution.
  • IPA-ST particle silica, particle size 10 to 15 nm, suspended in isopropyl alcohol at 30% by mass, manufactured by Nissan Chemical Industries, Ltd.
  • Example 9 instead of IPA-ST, 1.8 g (Example 9) of IPA-ST-UP (chain silica, particle size 40-100 nm, suspended in isopropyl alcohol at 15% by mass, manufactured by Nissan Chemical Industries, Ltd.) A photocatalyst-containing coating solution was obtained in the same manner as in Examples 6 to 8, except that 3.6 g (Example 10) or 7.2 g (Example 11) was mixed.
  • Example 12 In place of IPA-ST, Celnax (registered trademark) CX-Z210 (double oxide containing antimony oxide, particle size 15 nm, suspended in isopropyl alcohol at 21% by mass, manufactured by Nissan Chemical Industries, Ltd.) A photocatalyst-containing coating solution was obtained in the same manner as in Examples 6 to 8, except that 29 g (Example 12), 2.57 g (Example 13), or 5.14 g (Example 14) were mixed.
  • Celnax registered trademark
  • CX-Z210 double oxide containing antimony oxide, particle size 15 nm, suspended in isopropyl alcohol at 21% by mass, manufactured by Nissan Chemical Industries, Ltd.
  • a photocatalyst-containing coating solution was obtained in the same manner as in Example 6 except that .67 g was used.
  • the solid content concentration obtained in Production Example 1 was 0.25% by mass (Example 21), 0.5% by mass (Example 22), 1.0% by mass (Example 23), or 2.5% by mass.
  • 9.41 g of the hydrolyzed KBM-403 mixed solution was added to 21.67 g of each photocatalyst suspension of Example 24 and stirred for 5 minutes to obtain a photocatalyst-containing coating solution.
  • Example 28 The solid content obtained in Production Example 1 was 1.0% by mass (Example 28: titanium oxide content in the final solid content was 6.6% by mass), 0.5% by mass (Example 29: in the final solid content)
  • KBM-5103 2 was added to 21.67 g of the photocatalyst suspension having a titanium oxide content of 3.4 mass%) or 0.25 mass% (Example 30: titanium oxide content of 1.6 mass% in the final solid content). .27 g was added and stirred for 5 minutes, 0.86 g of T-50 was added and stirred for 5 minutes, 0.23 g of Irgacure 907 was added and stirred for 5 minutes, and a photocatalyst-containing coating solution was obtained.

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Abstract

L'objectif de la présente invention est de fournir une structure support de photocatalyseur présentant une activité photocatalytique suffisante sans provoquer de dégradations dans un matériau de base. Le liquide de revêtement contenant un photocatalyseur contient de fines particules d'un matériau de photocatalyseur, au moins un agent de couplage à base de silane choisi parmi un agent de couplage époxy silane et un agent de couplage silane acrylique, et/ou un produit d'hydrolyse-condensation de l'agent de couplage à base de silane, un agent de couplage métallique qui ne contient pas de silicium en tant qu'élément métallique, et un solvant, le total de l'agent de couplage à base de silane et le produit d'hydrolyse-condensation de l'agent de couplage à base de silane étant présents selon un rapport d'au moins 300 parties en masse, par rapport à 100 parties en masse des fines particules du matériau de photocatalyseur.
PCT/JP2016/002168 2015-05-12 2016-04-25 Liquide de revêtement contenant un photocatalyseur et structure support de photocatalyseur WO2016181622A1 (fr)

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JP2017517604A JP6467502B2 (ja) 2015-05-12 2016-04-25 光触媒含有塗布液及び光触媒担持構造体

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JP2015-097195 2015-05-12
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WO2016181622A1 true WO2016181622A1 (fr) 2016-11-17

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WO2018221702A1 (fr) 2017-05-31 2018-12-06 古河電気工業株式会社 Structure de photocatalyseur, composition de structure de photocatalyseur, matériau de revêtement de photocatalyseur, procédé de production de structure de photocatalyseur et procédé de décomposition d'aldéhydes
CN110546220A (zh) * 2017-05-09 2019-12-06 Sika技术股份公司 用于以更高热稳定性粘合的水性预处理
US11161101B2 (en) 2017-05-31 2021-11-02 Furukawa Electric Co., Ltd. Catalyst structure and method for producing the catalyst structure
US11547987B2 (en) 2017-05-31 2023-01-10 Furukawa Electric Co., Ltd. Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method
US11648542B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648538B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648543B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11655157B2 (en) 2017-05-31 2023-05-23 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11654422B2 (en) 2017-05-31 2023-05-23 Furukawa Electric Co., Ltd. Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization
US11666894B2 (en) 2017-05-31 2023-06-06 Furukawa Electric Co., Ltd. Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water
US11680211B2 (en) 2017-05-31 2023-06-20 Furukawa Electric Co., Ltd. Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization
US11684909B2 (en) 2017-05-31 2023-06-27 Furukawa Electric Co., Ltd. Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon
CN116716039A (zh) * 2023-08-11 2023-09-08 北京助天科技集团有限公司 一种光催化辐射制冷涂料、制备方法及应用
US12030041B2 (en) 2017-05-31 2024-07-09 Furukawa Electric Co., Ltd. Structured catalyst for steam reforming, reforming apparatus provided with structured catalyst for steam reforming, and method for manufacturing structured catalyst for steam reforming

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JP2005282026A (ja) * 2004-03-29 2005-10-13 Yokota Riyouhan Kk 防汚性に優れたブラインド
JP2007268761A (ja) * 2006-03-30 2007-10-18 Nippon Steel Corp 表面処理金属
JP2007332262A (ja) * 2006-06-14 2007-12-27 Nippon Soda Co Ltd 機能性物質含有有機無機複合体
JP2010043188A (ja) * 2008-08-13 2010-02-25 Achilles Corp 光触媒性塗膜形成用塗料、光触媒性塗膜及び該光触媒性塗膜を備える積層体

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110546220A (zh) * 2017-05-09 2019-12-06 Sika技术股份公司 用于以更高热稳定性粘合的水性预处理
US11648543B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11654422B2 (en) 2017-05-31 2023-05-23 Furukawa Electric Co., Ltd. Structured catalyst for catalytic cracking or hydrodesulfurization, catalytic cracking apparatus and hydrodesulfurization apparatus including the structured catalyst, and method for producing structured catalyst for catalytic cracking or hydrodesulfurization
US11547987B2 (en) 2017-05-31 2023-01-10 Furukawa Electric Co., Ltd. Structured catalyst for oxidation for exhaust gas purification, method for producing same, automobile exhaust gas treatment device, catalytic molding, and gas purification method
US11648542B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11648538B2 (en) 2017-05-31 2023-05-16 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
WO2018221702A1 (fr) 2017-05-31 2018-12-06 古河電気工業株式会社 Structure de photocatalyseur, composition de structure de photocatalyseur, matériau de revêtement de photocatalyseur, procédé de production de structure de photocatalyseur et procédé de décomposition d'aldéhydes
US11655157B2 (en) 2017-05-31 2023-05-23 National University Corporation Hokkaido University Functional structural body and method for making functional structural body
US11161101B2 (en) 2017-05-31 2021-11-02 Furukawa Electric Co., Ltd. Catalyst structure and method for producing the catalyst structure
US11666894B2 (en) 2017-05-31 2023-06-06 Furukawa Electric Co., Ltd. Structured catalyst for CO shift or reverse shift and method for producing same, CO shift or reverse shift reactor, method for producing carbon dioxide and hydrogen, and method for producing carbon monoxide and water
US11680211B2 (en) 2017-05-31 2023-06-20 Furukawa Electric Co., Ltd. Structured catalyst for hydrodesulfurization, hydrodesulfurization device including the structured catalyst, and method for producing structured catalyst for hydrodesulfurization
US11684909B2 (en) 2017-05-31 2023-06-27 Furukawa Electric Co., Ltd. Structured catalyst for methanol reforming, methanol reforming device, method for producing structured catalyst for methanol reforming, and method for producing at least one of olefin or aromatic hydrocarbon
US12030041B2 (en) 2017-05-31 2024-07-09 Furukawa Electric Co., Ltd. Structured catalyst for steam reforming, reforming apparatus provided with structured catalyst for steam reforming, and method for manufacturing structured catalyst for steam reforming
CN116716039B (zh) * 2023-08-11 2023-12-26 北京助天科技集团有限公司 一种光催化辐射制冷涂料、制备方法及应用
CN116716039A (zh) * 2023-08-11 2023-09-08 北京助天科技集团有限公司 一种光催化辐射制冷涂料、制备方法及应用

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