WO2009133591A1 - Photocatalytic coating composition and substrate having coating film - Google Patents

Photocatalytic coating composition and substrate having coating film Download PDF

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Publication number
WO2009133591A1
WO2009133591A1 PCT/JP2008/001130 JP2008001130W WO2009133591A1 WO 2009133591 A1 WO2009133591 A1 WO 2009133591A1 JP 2008001130 W JP2008001130 W JP 2008001130W WO 2009133591 A1 WO2009133591 A1 WO 2009133591A1
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Prior art keywords
coating composition
film
resin
substrate
ion exchange
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PCT/JP2008/001130
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French (fr)
Japanese (ja)
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原田幸宣
上村裕一
松川輝紀
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株式会社ピアレックス・テクノロジーズ
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Priority to PCT/JP2008/001130 priority Critical patent/WO2009133591A1/en
Publication of WO2009133591A1 publication Critical patent/WO2009133591A1/en

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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
    • 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
    • C09D183/04—Polysiloxanes
    • 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
    • C09D129/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Coating compositions based on hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Coating compositions based on derivatives of such polymers
    • C09D129/10—Homopolymers or copolymers of unsaturated ethers
    • 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
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a photocatalyst coating composition, and a substrate with a coating formed by coating a substrate with a coating formed from the photocatalytic coating composition.
  • the surface becomes highly hydrophilic and the water wetting angle of the surface becomes 10 ° or less.
  • metal oxides having a photocatalytic function are known as photocatalysts. And when coating this on a base material, a glassy inorganic binder called silica sol is often used.
  • Patent Document 1 discloses a photocatalyst coating material containing silica sol and having excellent dispersion stability.
  • Patent Document 2 discloses a titanium oxide coating composition using silica sol as a binder and in which the binder does not deteriorate due to photocatalytic action.
  • Photocatalyst paints based on such photocatalysts may cause a chemical reaction when the photocatalyst comes into contact with the substrate, but usually, the coating surface of the paint is pre-coated with inorganic silica to form a barrier coat layer. This prevents the chemical reaction.
  • hydrophilic organic polymers are also used as binders for photocatalysts, but the photocatalytic function is that the organic polymer is decomposed and the coating film deteriorates because the organic matter is decomposed by exciting intense redox reactions. There was a problem of durability.
  • Patent Document 3 discloses a superpolymer composed mainly of a graft polymer composed of a repeating unit of polymer tetrafluoroethylene (Nafion (registered trademark of DuPont)) having a perfluorosulfonic acid group in the side chain.
  • a hydrophilic coating composition is disclosed. This coating composition is dissolved in, for example, alcohol, diluted, applied in a liquid state, for example, to the outer wall surface of the building, and the photocatalyst is fixed on the outer wall surface for a long period of time to keep the wall surface superhydrophilic. be able to.
  • the photocatalyst coating film is required to have flexibility, hardness, transparency and the like in addition to antifouling property and durability depending on the application and the characteristics of the substrate to be adhered.
  • the flexibility of the photocatalyst coating film so as not to impair the light transmittance. Transparency is required.
  • an object of the present invention is to provide a photocatalyst coating composition that can form a coating film having antifouling properties, flexibility, durability, and transparency.
  • the present invention provides a photocatalytic coating composition
  • a photocatalytic coating composition comprising a binder and a metal oxide having a photocatalytic function, wherein the binder comprises a perfluorosulfonic acid ion exchange resin and a perfluorocarboxylic acid ion.
  • a resin containing at least one ion exchange resin selected from exchange resins and at least one functional silane selected from alkoxysilane, chlorosilane, and silazane, or a hydrolyzate or condensate of functional silane is used. It was decided.
  • polytetrafluoroethylene having grafted sulfonic acid groups is preferable to use as the ion exchange resin.
  • a monomer of the functional silane or a 2 to 100-mer oligomer is preferably used.
  • metal oxide having a photocatalytic function examples include TiO 2 , ZnO, WO 3 , SnO 2 , SrTiO 3 , Bi 2 O 3 , and Fe 2 O 3 .
  • the photocatalyst coating composition of the present invention further includes inorganic ultraviolet absorbers such as zinc oxide, titanium oxide, and cerium oxide, organic ultraviolet absorbers such as benzotriazole, salicylic acid, and benzophenone, and light stability such as hindered amines.
  • inorganic ultraviolet absorbers such as zinc oxide, titanium oxide, and cerium oxide
  • organic ultraviolet absorbers such as benzotriazole, salicylic acid, and benzophenone
  • light stability such as hindered amines.
  • An agent may be added.
  • the substrate with a coating according to the present invention can be formed by coating the above-mentioned photocatalytic coating composition on a substrate and depositing the coating.
  • the ion exchange resin and the functional silane form a hybrid network structure or a hybrid chain structure.
  • AS acrylonitrile / styrene resin
  • ABS acrylonitrile / butadiene / styrene resin
  • a glass substrate can be used as the substrate.
  • the base material may be a metal plate or a metal plate coated with a paint containing a resin selected from a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, and a polyester resin.
  • the photocatalyst coating composition of the present invention includes at least one ion exchange resin selected from perfluorosulfonic acid ion exchange resins, perfluorocarboxylic acid ion exchange resins and mixtures thereof, alkoxysilane, chlorosilane, and silazane. Since at least one functional silane selected from the group consisting of hydrolyzate or condensate of functional silane and a metal oxide having a photocatalytic function is coated on the substrate, A coating film in which a photocatalytic metal oxide is dispersed in a binder is formed.
  • the binder in the coating composition contains an ion exchange resin and a functional silane.
  • the functional silane is hydrolyzed and polycondensed to form polysiloxane or polysilazane.
  • this coating film has flexibility, durability and transparency. Further, since the photocatalytic metal oxide is present on the surface of the coating film and the perfluorosulfonic acid group is also present, the antifouling property due to super hydrophilicity is exhibited over a long period of time.
  • a monomer of functional silane or a 2 to 100-mer oligomer is preferably used.
  • metal oxide having a photocatalytic function examples include TiO 2 , ZnO, WO 3 , SnO 2 , SrTiO 3 , Bi 2 O 3 , and Fe 2 O 3 .
  • inorganic ultraviolet absorbers such as zinc oxide, titanium oxide and cerium oxide
  • organic ultraviolet absorbers such as benzotriazole, salicylic acid and benzophenone
  • light stabilizers such as hindered amines
  • the substrate with a coating according to the present invention can be formed by coating the above-mentioned photocatalytic coating composition on a substrate and depositing the coating.
  • the base material acrylic, acrylic silicon, polyethylene, polycarbonate, polypropylene, polyurethane, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyamide, polyacetal, AS (acrylonitrile / styrene resin), ABS (acrylonitrile / butadiene / styrene resin)
  • AS acrylonitrile / styrene resin
  • ABS acrylonitrile / butadiene / styrene resin
  • the base material is a metal plate or a metal plate coated with a coating containing a resin selected from a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, and a polyester resin, the antifouling is achieved.
  • a coated metal plate having excellent properties and durability can be obtained.
  • the photocatalyst coating composition according to this embodiment is obtained by mixing and dispersing a metal oxide having a photocatalytic function in a binder. Usually, a solvent is further mixed with this mixture, and the binder is dissolved in the solvent.
  • a binder containing a perfluorosulfonic acid ion exchange resin, a perfluorocarboxylic acid ion exchange resin, or an ion exchange resin made of a mixture of both, and a functional silane is used.
  • the “functional silane” is alkoxysilane, chlorosilane, or silazane, but may be a hydrolyzate or condensate thereof.
  • a typical perfluorosulfonic acid ion exchange resin is polytetrafluoroethylene in which a sulfonic acid group is graft-polymerized, and its molecular structure is as follows. (Trademark) Similar structure, containing an ether bond, and having a sulfonic acid group in the side chain.
  • Rf is a single or plural kinds of alkyl vinyl ethers, and X and Y are arbitrary natural numbers.
  • Polytetrafluoroethylene graft-polymerized with sulfonic acid groups is generally widely used as a solid electrolyte for polymer solid fuel cells.
  • “Nafion (registered trademark)” by DuPont is used. And are sold in dispersion solutions (5%, 10%, 20% polymer concentration) dissolved in a solvent.
  • perfluorocarboxylic acid ion exchange resins include Flemion from Asahi Glass Co., Ltd. This basically has a structure similar to the above Nafion, and is synthesized as a copolymer of tetrafluoroethylene and a perfluoro vinyl ether containing a carboxylic acid group.
  • alkoxysilane examples include tetraethoxysilane, tetramethoxysilane, 3-aminopropyltriethoxysilane and the like.
  • chlorosilane examples include monochlorosilane compound SiR 3 Cl, dichlorosilane compound SiR 2 Cl 2 , trichlorosilane compound SiRCl 3 and the like (where R is CH 3 , C 6 H 6 , C n H 2n + 1, etc.). Alkyl group, n is a natural number).
  • Silazane is a series of compounds composed of silicon, nitrogen, hydrogen, and the like and having a Si—N—Si bond.
  • disilazan such as hexamethyldisilazane ((CH 3 ) 3 Si) 2 NH is used.
  • These functional silanes can be hydrolyzed and condensed under mild conditions to form polysiloxane or polysilazane.
  • a functional silane monomer may be used, or a functional silane dimer to 100-mer oligomer may be used.
  • the functional silane When the functional silane is contained in the photocatalyst coating composition, the functional silane gradually hydrolyzes and condenses, and changes into a hydrolyzate and a condensate of the functional silane.
  • the metal oxide having a photocatalytic function As the metal oxide having a photocatalytic function, those generally used as a photocatalyst can be used. Specific examples thereof include titanium oxide (TiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), tin oxide (SnO 2 ), strontium titanate (SrTiO 3 ), bismuth oxide (Bi 2 O 3 ), An example is iron oxide (Fe 2 O 3 ).
  • the solvent examples include a solvent capable of dissolving the above ion exchange resin, for example, methanol, ethanol, isopropanol, water, or a mixed solvent thereof.
  • the hydrophilicity of the coating film decreases, but the hardness of the coating film increases.
  • the hydrophilicity of the coating film increases, but the flexibility of the coating film decreases.
  • the photocatalytic coating composition by adjusting the ratio of the functional silane to the ion exchange resin and the ratio of the metal oxide having the photocatalytic function to the binder, a coating film having desired hydrophilicity, hardness, and flexibility is obtained. Obtainable.
  • the blending ratio of the functional silane to the ion exchange resin in the binder is preferably set to 3 to 5 times in terms of solid content, and the blending ratio of the metal oxide having a photocatalytic function to the binder is: It is preferably set within the range of 5 to 70% by weight in terms of solid content.
  • ion exchange resin 20% solution
  • 20 to 30 parts by weight of alkoxysilane 20 to 30 parts by weight of alkoxysilane
  • metal oxide particles having a photocatalytic function may be blended to constitute a photocatalyst coating composition.
  • the pH it is preferable to adjust the pH to a range of 3 to 7 by adding an alkali such as KOH or an amine such as ethanolamine to the photocatalyst coating composition. If pH exists in this range, it has moderate reactivity and stability with respect to a hydrolysis reaction and a polycondensation reaction.
  • an alkali such as KOH or an amine such as ethanolamine
  • a fluorine resin such as ETFE (a copolymer of tetrafluoroethylene C 2 F 4 and ethylene C 2 H 4 ) may be further added to the photocatalyst coating composition. By doing so, the effect which the adhesiveness with a base
  • ETFE a copolymer of tetrafluoroethylene C 2 F 4 and ethylene C 2 H 4
  • a super hydrophilic film-coated film is produced by preparing a PET film or a vinyl chloride film as a substrate, applying a photocatalyst coating composition to the film, and drying by heating or natural drying.
  • FIG. 1 is a schematic view showing a cross section of a film with a coating.
  • the film with film 10 is formed by coating a coating film 12 on the surface of a film 11 serving as a substrate.
  • the coating film 12 is configured by dispersing photocatalyst particles 13 (metal oxide having a photocatalytic function) in a binder layer 14 formed of an ion exchange resin and functional silane.
  • FIG. 2 is a diagram schematically showing the structure of the binder layer 14 formed of perfluorosulfonic acid ion exchange resin and alkoxysilane.
  • the binder in the coating composition contains an ion exchange resin and alkoxysilane, but in the coating film, the alkoxy groups of alkoxysilane are hydrolyzed and polycondensed.
  • siloxane is formed, and Si—OH groups formed by hydrolysis of alkoxysilane hydrogen bond with ether groups of perfluorosulfonic acid ion exchange resin (graft polymer). Therefore, in the binder layer 14 forming the coating film 12, a hybrid network structure or a hybrid chain structure in which an ion exchange resin and siloxane are mixed is formed.
  • this coating film 12 has flexibility, durability and transparency. Further, since the photocatalytic metal oxide particles 13 are present on the surface of the coating film 12 and perfluorosulfonic acid groups contained in the binder are also present, when the coating film 12 comes into contact with water, the water becomes sulfonic acid. They gather on the base and photocatalytic metal oxide particles 13 to exhibit super hydrophilicity, and the water droplets spread uniformly to form a thin water film.
  • the surface of the coating film 12 is kept super-hydrophilic for a long period of time, does not scatter and does not cloud light, and exhibits antifouling properties.
  • the coating composition according to the present embodiment includes the perfluorosulfonic acid ion exchange resin and the alkoxysilane, so that a hybrid network structure or a hybrid chain structure is formed in the binder layer 14.
  • the coated film 10 has the effect of combining durability and transparency in addition to super hydrophilicity.
  • the coated film 10 has both durability and transparency in addition to super hydrophilicity.
  • the photocatalytic metal oxide particles 13 are present on the surface of the coating film 12, when light hits the metal oxide particles 13, harmful substances present on the surface of the film are decomposed by a photocatalytic reaction.
  • PET polyethylene terephthalate
  • vinyl chloride film a polyethylene terephthalate (PET) film and a vinyl chloride film are used as the substrate, but the type of film is not particularly limited.
  • a glass plate or a metal plate such as a steel plate, or a metal plate coated with a paint containing a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, or a polyester resin. It can also be used as a substrate.
  • the shape of the substrate is not limited to a plate shape, and may be any shape, for example, a three-dimensional shape.
  • Example 1 70 parts by weight of ethanol solvent, 5 parts by weight of ethyl silicate 28 (manufactured by Colcoat, tetraethoxysilane (TEOS)), 20 parts by weight of Nafion DE2021 (manufactured by DuPont, 20% solution), and a crystalline titanium oxide slurry TKD702 (manufactured by Teika) TiO 2 : 16% solution) and 5 parts by weight were added and mixed to prepare a photocatalytic coating solution.
  • TEOS tetraethoxysilane
  • Example 2 68 parts by weight of ethanol solvent, 5 parts by weight of ethyl silicate 28 (manufactured by Colcoat), 20 parts by weight of Nafion DE2021 (manufactured by DuPont, 20% solution), and crystalline titanium oxide slurry TKD702 (manufactured by Teika, TiO 2 : 16% solution)
  • a hydroxyphenyltriazine-based UV absorber TINUVIN400 manufactured by Ciba Specialty Chemicals
  • a hindered amine light stabilizer TINUVIN123 manufactured by Ciba Specialty Chemicals
  • a photocatalytic coating solution was prepared. (Comparative Example 2) To 90 parts by weight of ethanol solvent, 10 parts by weight of ethyl silicate 28 (manufactured by Colcoat) and 5 parts by weight of crystalline titanium oxide slurry TKD702 (manufactured by Teika, TiO 2 : 16% solution) are added and mixed to form a photocatalytic coating solution. Adjusted.
  • the photocatalyst coating liquids according to Examples 1 and 2 and Comparative Examples 1 and 2 obtained as described above were respectively applied to a PET film having a thickness of 50 ⁇ m.
  • a film with a photocatalyst film was obtained by coating at a coating amount of 20 g / m 2 using a 20 bar coater and drying at 80 ° C. for 3 minutes.
  • the film thickness of the photocatalyst film was about 1 ⁇ m.
  • a strength confirmation test Using the obtained film with a photocatalyst coating, a strength confirmation test, a transparency confirmation test, and an ultraviolet transmittance confirmation test were performed as follows. ⁇ Strength confirmation test of film with photocatalyst coating> As a strength test, an adhesion test, a surface hardness test, and an elongation test were performed.
  • the adhesion test is performed in accordance with a cross-cut tape peeling test specified in JIS K 5600, and the surface hardness test is performed in accordance with a scratch hardness (pencil method) test specified in JIS K 5600, and an elongation test.
  • the test results are shown in Table 1.
  • Example 1 in which TEOS and Nafion are mixed as a binder, the surface hardness of the photocatalyst-covered film is higher and the adhesiveness is superior to Comparative Example 1 in which the binder is Nafion alone. I understand that.
  • the surface hardness of the photocatalyst-covering film is also higher in Example 1 than Comparative Example 1 and higher than that of the PET film substrate.
  • Comparative Example 2 where the binder is composed only of ethyl silicate, the adhesion and surface hardness of the photocatalyst-covering film are good, but the elongation percentage is low. In addition, the crack generate
  • the photocatalyst-covered film of Example 1 has a transmittance close to that of the PET film, and has higher transparency than that coated with the photocatalyst coating composition of Comparative Example 1.
  • the photocatalyst-covering film according to Example 1 has good adhesion, surface hardness, elongation, and transparency because Nafion and TEOS form a hybrid network structure or chain structure. it is conceivable that.
  • Example 2 where the ultraviolet absorber was added, the ultraviolet transmittance of the photocatalyst-coated film was reduced by about 30% compared to Example 1 where no ultraviolet absorber was added.
  • Example 2 As a method for testing the self-cleaning performance of the photocatalytic material, there is a wet degradation performance test by evaluating the degradation of JIS 1703-2 methylene blue reagent. In accordance with this test method, a decomposition performance confirmation test was performed on Example 1 and Comparative Example 1. The results are shown in Table 4.
  • the degradation activity index is 5 or more in this test, it is said to have a photocatalytic function, but as shown in Table 4, the degradation activity index is 9.0 for both Example 1 and Comparative Example 1, It turns out that it has a photocatalytic function.
  • Example 3 60 parts by weight of ethanol solvent, 5 parts by weight of ethyl silicate 28 (Colcoat), 30 parts by weight of Nafion DE2021 (DuPont, 20% solution) and 5 parts by weight of crystalline titanium oxide slurry TKD702 (Taika, TiO 2 : 16% solution) Were added and mixed to prepare a photocatalytic coating solution.
  • the photocatalyst coating liquids of Example 3 and Comparative Example 4 obtained as described above were designated A polyester steel sheet with a photocatalyst coating was obtained by applying a coating amount of 30 g / m 2 on a polyester baked steel sheet using a 10 bar coater and drying at 100 ° C. for 5 minutes.
  • the film thickness of the photocatalyst film was 2 to 3 ⁇ m.
  • the obtained photocatalyst-coated polyester steel sheet was subjected to an adhesion test and a surface hardness test as follows.
  • ⁇ Strength confirmation test of polyester steel sheet with photocatalyst coating> The adhesion test was performed in accordance with a cross-cut tape peeling test specified in JIS K 5600, and the surface hardness test was performed in accordance with a scratch hardness (pencil method) test specified in JIS K 5600. Table 5 shows the test results.
  • the photocatalyst-covering film according to Example 3 has good adhesion and surface hardness because Nafion and TEOS form a hybrid network structure or chain structure.

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Abstract

It is intended to provide a photocatalytic coating composition capable of forming a coating film which is excellent in antifouling properties and durability as well as in flexibility, hardness and transparency. A photocatalytic coating composition wherein a metal oxide having a photocatalytic function is blended with a binder and dispersed therein and a solvent is further added so that the binder is dissolved in the solvent. As the binder, use is made of one containing an ion exchange resin comprising a perfluorosulfonic acid-based ion exchange resin, a perfluorocarboxylic acid-based ion exchange resin or a mixture of them and a silane compound selected from an alkoxysilane, a hydrolyzate thereof and a condensed product of the same.

Description

光触媒コーティング組成物および被膜付基体Photocatalyst coating composition and coated substrate
　本発明は、光触媒コーティング組成物、および光触媒コーティング組成物で形成された被膜が基材に被着されてなる被膜付基体に関する。 The present invention relates to a photocatalyst coating composition, and a substrate with a coating formed by coating a substrate with a coating formed from the photocatalytic coating composition.
　最近、耐汚染性や抗菌性に優れた光触媒機能を有する金属酸化物を配合した光触媒組成物が注目されている。 Recently, a photocatalyst composition containing a metal oxide having a photocatalytic function excellent in contamination resistance and antibacterial properties has been attracting attention.
　光触媒をフィルムや鋼板などの基材にコーティングすると、表面が高親水化されて、表面の水濡れ角が１０°以下を呈するようになる。 When a photocatalyst is coated on a substrate such as a film or a steel plate, the surface becomes highly hydrophilic and the water wetting angle of the surface becomes 10 ° or less.
　これは、光触媒の価電子帯上端と伝導帯下端とのエネルギ－ギャップ以上のエネルギ－を有する光が光触媒に照射されると、光触媒の価電子帯中の電子が励起されて伝導電子と正孔が生成して表面に極性が付与されることによる。 This is because when the photocatalyst is irradiated with light having energy greater than the energy gap between the upper end of the valence band of the photocatalyst and the lower end of the conduction band, the electrons in the valence band of the photocatalyst are excited. Is generated and the surface is given polarity.
　従って、このような光触媒を、フィルム、鋼板、ガラスなどの基材にコーティングすることによって、物体表面の親水性が向上するので、耐汚染性が発揮される他、結露が防止され、静電気を除去できる効果も期待できる。 Therefore, by coating such a photocatalyst on a substrate such as a film, steel plate, or glass, the hydrophilicity of the surface of the object is improved, so that contamination resistance is exhibited, condensation is prevented, and static electricity is removed. Expected effects.
　一般に、光触媒としては光触媒機能を有する金属酸化物が知られている。そして、これを基材にコーティングする際には、シリカゾルと称するガラス質の無機バインダが多く用いられている。 Generally, metal oxides having a photocatalytic function are known as photocatalysts. And when coating this on a base material, a glassy inorganic binder called silica sol is often used.
 例えば、特許文献１には、シリカゾルを含み、分散安定性に優れた光触媒塗料が開示されている。 For example, Patent Document 1 discloses a photocatalyst coating material containing silica sol and having excellent dispersion stability.
　また特許文献２には、シリカゾルを結着剤として使用して、結着剤が光触媒作用により劣化しない酸化チタン塗料組成物が開示されている。 Patent Document 2 discloses a titanium oxide coating composition using silica sol as a binder and in which the binder does not deteriorate due to photocatalytic action.
　このような光触媒を主成分とする光触媒塗料は、光触媒が基材と接触すると化学反応を起こすおそれがあるが、通常、塗料の塗布面にあらかじめ無機系シリカなどを下塗りしてバリアコート層を形成しておくことによって、この化学反応を防止している。 Photocatalyst paints based on such photocatalysts may cause a chemical reaction when the photocatalyst comes into contact with the substrate, but usually, the coating surface of the paint is pre-coated with inorganic silica to form a barrier coat layer. This prevents the chemical reaction.
　一方、光触媒のバインダとして親水性の有機ポリマーも用いられているが、光触媒機能は、激烈な酸化還元反応を励起して有機物を分解するために、有機ポリマーが分解されて塗膜が劣化するという耐久性の問題があった。 On the other hand, hydrophilic organic polymers are also used as binders for photocatalysts, but the photocatalytic function is that the organic polymer is decomposed and the coating film deteriorates because the organic matter is decomposed by exciting intense redox reactions. There was a problem of durability.
　これに対して、特許文献３には、パーフルオロスルホン酸基を側鎖に有する高分子４フッ化エチレン（Ｎａｆｉｏｎ（デュポン社の登録商標））の繰り返し単位からなるグラフトポリマーを主成分とした超親水性塗料組成物が開示されている。この塗料組成物を、例えばアルコールに溶解して希釈し、液状状態にして例えば建造物の外壁面に塗布することによって、当該外壁面に長期間にわたって光触媒を定着させて壁面を超親水性に保つことができる。
特開平１１－３４３４２６号公報 特開２０００－７３２９７号公報 特開２００６－４５３７０号公報 On the other hand, Patent Document 3 discloses a superpolymer composed mainly of a graft polymer composed of a repeating unit of polymer tetrafluoroethylene (Nafion (registered trademark of DuPont)) having a perfluorosulfonic acid group in the side chain. A hydrophilic coating composition is disclosed. This coating composition is dissolved in, for example, alcohol, diluted, applied in a liquid state, for example, to the outer wall surface of the building, and the photocatalyst is fixed on the outer wall surface for a long period of time to keep the wall surface superhydrophilic. be able to.
Japanese Patent Laid-Open No. 11-343426 JP 2000-73297 A JP 2006-45370 A
　ところで、光触媒コーティング膜は、用途や被着基材の特性によって、防汚性や耐久性に加えて、柔軟性、硬度、透明性なども要求される。例えば、透明フィルム上に光触媒被膜を被着させて光透過性を有する被膜付フィルムを作製しようとする場合には、特に、光透過性を損なわないように、光触媒コーティング膜に対して柔軟性や透明性が要求される。 By the way, the photocatalyst coating film is required to have flexibility, hardness, transparency and the like in addition to antifouling property and durability depending on the application and the characteristics of the substrate to be adhered. For example, when it is intended to produce a film with a light transmittance by depositing a photocatalyst film on a transparent film, in particular, the flexibility of the photocatalyst coating film so as not to impair the light transmittance. Transparency is required.
　本発明は、上記課題に鑑み、光触媒コーティング組成物において、防汚性と共に、柔軟性、耐久性、透明性を備えたコーティング膜を形成できるものを提供することを目的とする。 In view of the above problems, an object of the present invention is to provide a photocatalyst coating composition that can form a coating film having antifouling properties, flexibility, durability, and transparency.
　上記の目的を達成するため、本発明は、バインダに光触媒機能を有する金属酸化物を配合してなる光触媒コーティング組成物において、バインダとして、パーフルオロスルホン酸系イオン交換樹脂及びパーフルオロカルボン酸系イオン交換樹脂から選択される少なくとも１種のイオン交換樹脂と、アルコキシシラン、クロロシラン、シラザンから選択される少なくとも1種の機能性シラン、もしくは機能性シランの加水分解物または縮合物とを含むものを用いることとした。 In order to achieve the above object, the present invention provides a photocatalytic coating composition comprising a binder and a metal oxide having a photocatalytic function, wherein the binder comprises a perfluorosulfonic acid ion exchange resin and a perfluorocarboxylic acid ion. A resin containing at least one ion exchange resin selected from exchange resins and at least one functional silane selected from alkoxysilane, chlorosilane, and silazane, or a hydrolyzate or condensate of functional silane is used. It was decided.
　上記イオン交換樹脂として、スルホン酸基がグラフト重合されたポリ４フッ化エチレンを用いることが好ましい。 It is preferable to use polytetrafluoroethylene having grafted sulfonic acid groups as the ion exchange resin.
　上記機能性シランとしては、当該機能性シランのモノマー、あるいは２～１００量体オリゴマーを用いることが好ましい。 As the functional silane, a monomer of the functional silane or a 2 to 100-mer oligomer is preferably used.
　光触媒機能を有する金属酸化物として、ＴｉＯ2，ＺｎＯ，ＷＯ3，ＳｎＯ2，ＳｒＴｉＯ3，Ｂｉ2Ｏ3，Ｆｅ2Ｏ3が挙げられる。 Examples of the metal oxide having a photocatalytic function include TiO 2 , ZnO, WO 3 , SnO 2 , SrTiO 3 , Bi 2 O 3 , and Fe 2 O 3 .
　本発明の光触媒コーティング組成物には、さらに、酸化亜鉛、酸化チタン、酸化セリウム等の無機系紫外線吸収剤、ベンゾトリアゾール系、サリチル酸系、ベンゾフェノン系等の有機紫外線吸収剤、ヒンダードアミン系等の光安定化剤を添加してもよい。 The photocatalyst coating composition of the present invention further includes inorganic ultraviolet absorbers such as zinc oxide, titanium oxide, and cerium oxide, organic ultraviolet absorbers such as benzotriazole, salicylic acid, and benzophenone, and light stability such as hindered amines. An agent may be added.
　本発明に係る被膜付基体は、上記の光触媒コーティング組成物を、基材にコーティングして被膜を被着させることによって形成することができる。 The substrate with a coating according to the present invention can be formed by coating the above-mentioned photocatalytic coating composition on a substrate and depositing the coating.
　ここで被膜において、イオン交換樹脂と、機能性シランとが、ハイブリッド網目構造またはハイブリッド鎖状構造を形成していることが好ましい。 Here, in the coating, it is preferable that the ion exchange resin and the functional silane form a hybrid network structure or a hybrid chain structure.
　また上記基材として、アクリル，アクリルシリコン，ポリエチレン，ポリカーボネート，ポリプロピレン，ポリウレタン，ポリスチレン，ポリエチレンテレフタレート，ポリ塩化ビニル，ポリアミド，ポリアセタール，ＡＳ（アクリロニトリル／スチレン樹脂），ＡＢＳ（アクリロニトリル／ブタジエン／スチレン樹脂）から選択される樹脂で形成されたフィルムまたは成型品を用いることができる。 As the base material, acrylic, acrylic silicon, polyethylene, polycarbonate, polypropylene, polyurethane, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyamide, polyacetal, AS (acrylonitrile / styrene resin), ABS (acrylonitrile / butadiene / styrene resin) A film or a molded product formed of the selected resin can be used.
　あるいは、上記基材として、ガラス基材を用いることもできる。 Alternatively, a glass substrate can be used as the substrate.
　上記基材は、金属板、あるいは、金属板に、フッ素樹脂，アクリル樹脂，アクリルシリコン樹脂，ウレタン樹脂，ポリエステル樹脂から選択される樹脂が含有された塗料を塗布したものであってもよい。 The base material may be a metal plate or a metal plate coated with a paint containing a resin selected from a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, and a polyester resin.
　本発明の光触媒コーティング組成物には、パーフルオロスルホン酸系イオン交換樹脂、パーフルオロカルボン酸系イオン交換樹脂およびこれらの混合物から選択された少なくとも１種のイオン交換樹脂と、アルコキシシラン、クロロシラン、シラザンから選択される少なくとも１種の機能性シラン、もしくは機能性シランの加水分解物あるいは縮合物と、光触媒機能を有する金属酸化物とが含まれるので、この光触媒コーティング組成物を基材にコーティングすると、光触媒性の金属酸化物がバインダに分散されたコーティング膜が形成される。 The photocatalyst coating composition of the present invention includes at least one ion exchange resin selected from perfluorosulfonic acid ion exchange resins, perfluorocarboxylic acid ion exchange resins and mixtures thereof, alkoxysilane, chlorosilane, and silazane. Since at least one functional silane selected from the group consisting of hydrolyzate or condensate of functional silane and a metal oxide having a photocatalytic function is coated on the substrate, A coating film in which a photocatalytic metal oxide is dispersed in a binder is formed.
　そして、コーティング組成物中のバインダには、イオン交換樹脂と機能性シランが混在するが、コーティング被膜においては、機能性シランどうしが加水分解して重縮合することによってポリシロキサンあるいはポリシラザンなどが形成されるとともに、加水分解で形成されるＳｉ－ＯＨ基、Ｓｉ－ＮＨ2が、グラフトポリマーに含まれるエーテル基と水素結合する。従って、コーティング膜が形成された状態では、バインダ層において、グラフトポリマー及びポリシロキサン（あるいはポリシラザン）などが混在したハイブリッド網目構造もしくはハイブリッド鎖状構造が形成される。 The binder in the coating composition contains an ion exchange resin and a functional silane. In the coating film, the functional silane is hydrolyzed and polycondensed to form polysiloxane or polysilazane. At the same time, the Si—OH group and Si—NH 2 formed by hydrolysis hydrogen bond with the ether group contained in the graft polymer. Therefore, in the state where the coating film is formed, a hybrid network structure or a hybrid chain structure in which the graft polymer and polysiloxane (or polysilazane) are mixed is formed in the binder layer.
　このような構造によって、このコーティング膜は、柔軟性と耐久性と透明性を兼ね備える。また、コーティング膜の表面には、光触媒性の金属酸化物が存在し、また、パーフルオロスルホン酸基も存在するので、長期間にわたって超親水性による防汚性が発揮される。 Owing to such a structure, this coating film has flexibility, durability and transparency. Further, since the photocatalytic metal oxide is present on the surface of the coating film and the perfluorosulfonic acid group is also present, the antifouling property due to super hydrophilicity is exhibited over a long period of time.
　上記イオン交換樹脂として、スルホン酸基がグラフト重合されたポリ４フッ化エチレンを用いれば、優れた「超親水性」を持つコーティング膜が得られる。 When a polytetrafluoroethylene having grafted sulfonic acid groups is used as the ion exchange resin, a coating film having excellent “super hydrophilicity” can be obtained.
　上記機能性シランとしては、機能性シランのモノマーあるいは２～１００量体オリゴマーを用いることが好ましい。 As the functional silane, a monomer of functional silane or a 2 to 100-mer oligomer is preferably used.
　光触媒機能を有する金属酸化物として、ＴｉＯ2，ＺｎＯ，ＷＯ3，ＳｎＯ2，ＳｒＴｉＯ3，Ｂｉ2Ｏ3，Ｆｅ2Ｏ3が挙げられる。 Examples of the metal oxide having a photocatalytic function include TiO 2 , ZnO, WO 3 , SnO 2 , SrTiO 3 , Bi 2 O 3 , and Fe 2 O 3 .
　上記光触媒コーティング組成物に、さらに、酸化亜鉛、酸化チタン、酸化セリウム等の無機系紫外線吸収剤、ベンゾトリアゾール系、サリチル酸系、ベンゾフェノン系等の有機紫外線吸収剤、ヒンダードアミン系等の光安定化剤から選択されるものを添加すれば、塗膜に紫外線防止機能が付与される。 In addition to the above-mentioned photocatalyst coating composition, inorganic ultraviolet absorbers such as zinc oxide, titanium oxide and cerium oxide, organic ultraviolet absorbers such as benzotriazole, salicylic acid and benzophenone, and light stabilizers such as hindered amines If the selected one is added, an ultraviolet ray preventing function is imparted to the coating film.
　本発明に係る被膜付基体は、上記の光触媒コーティング組成物を、基材にコーティングして被膜を被着させることによって形成することができる。 The substrate with a coating according to the present invention can be formed by coating the above-mentioned photocatalytic coating composition on a substrate and depositing the coating.
　ここで、上記基材として、アクリル，アクリルシリコン，ポリエチレン，ポリカーボネート，ポリプロピレン，ポリウレタン，ポリスチレン，ポリエチレンテレフタレート，ポリ塩化ビニル，ポリアミド，ポリアセタール，ＡＳ（アクリロニトリル／スチレン樹脂），ＡＢＳ（アクリロニトリル／ブタジエン／スチレン樹脂）から選択される樹脂で形成されたフィルムまたは成型品を用いることができ、透明性、柔軟性のすぐれた被膜付基体が得られる。 Here, as the base material, acrylic, acrylic silicon, polyethylene, polycarbonate, polypropylene, polyurethane, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyamide, polyacetal, AS (acrylonitrile / styrene resin), ABS (acrylonitrile / butadiene / styrene resin) A film or molded product formed of a resin selected from the above can be used, and a coated substrate with excellent transparency and flexibility can be obtained.
　基材として、ガラス基材を用いても透明性の優れた膜付基体が得られる。 Even when a glass substrate is used as the substrate, a substrate with a film having excellent transparency can be obtained.
　上記基材としては、金属板、あるいは、金属板に、フッ素樹脂，アクリル樹脂，アクリルシリコン樹脂，ウレタン樹脂，ポリエステル樹脂から選択される樹脂が含有された塗料を塗布したものを用いれば、防汚性、耐久性の優れた被膜付金属板が得られる。 If the base material is a metal plate or a metal plate coated with a coating containing a resin selected from a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, and a polyester resin, the antifouling is achieved. A coated metal plate having excellent properties and durability can be obtained.
実施の形態にかかる被膜付フィルムの断面を示す模式図である。It is a schematic diagram which shows the cross section of the film with a film concerning embodiment. パーフルオロスルホン酸系イオン交換樹脂とアルコキシシランで形成されたバインダ層の構造を模式的に示す図である。It is a figure which shows typically the structure of the binder layer formed with the perfluorosulfonic acid type ion exchange resin and alkoxysilane.
符号の説明Explanation of symbols
　１０　被膜付フィルム
　１１　フィルム
　１２　コーティング被膜
　１３　光触媒性の金属酸化物粒子
　１４　バインダ層 DESCRIPTION OF SYMBOLS 10 Film with film 11 Film 12 Coating film 13 Photocatalytic metal oxide particle 14 Binder layer
　[光触媒コーティング組成物]
　本実施形態にかかる光触媒コーティング組成物は、バインダに光触媒機能を有する金属酸化物を配合して混合分散させたものである。通常、この混合物にさらに溶媒が混合されて、上記バインダが溶媒に溶解している。 [Photocatalytic coating composition]
The photocatalyst coating composition according to this embodiment is obtained by mixing and dispersing a metal oxide having a photocatalytic function in a binder. Usually, a solvent is further mixed with this mixture, and the binder is dissolved in the solvent.
　上記バインダとしては、パーフルオロスルホン酸系イオン交換樹脂、あるいはパーフルオロカルボン酸系イオン交換樹脂、あるいは両者の混合物からなるイオン交換樹脂と、機能性シランとを含むものを用いる。ここで「機能性シラン」は、アルコキシシラン，クロロシラン、あるいはシラザンであるが、それらの加水分解物あるいは縮合物であってもよい。 As the binder, a binder containing a perfluorosulfonic acid ion exchange resin, a perfluorocarboxylic acid ion exchange resin, or an ion exchange resin made of a mixture of both, and a functional silane is used. Here, the “functional silane” is alkoxysilane, chlorosilane, or silazane, but may be a hydrolyzate or condensate thereof.
　（イオン交換樹脂）
　パーフルオロスルホン酸系イオン交換樹脂として代表的なものは、スルホン酸基がグラフト重合されたポリ４フッ化エチレンであって、その分子構造は、化１に示すように、主鎖がテフロン（登録商標）類似の構造であり、エーテル結合が含まれており、側鎖にスルホン酸基を有している。 (Ion exchange resin)
A typical perfluorosulfonic acid ion exchange resin is polytetrafluoroethylene in which a sulfonic acid group is graft-polymerized, and its molecular structure is as follows. (Trademark) Similar structure, containing an ether bond, and having a sulfonic acid group in the side chain.
Figure JPOXMLDOC01-appb-C000001
Figure JPOXMLDOC01-appb-C000001
　化１中、Ｒｆは、単一または複数種類のアルキルビニルエーテルであり、Ｘ，Ｙは任意の自然数である。 In Chemical Formula 1, Rf is a single or plural kinds of alkyl vinyl ethers, and X and Y are arbitrary natural numbers.
　このスルホン酸基がグラフト重合されたポリ４フッ化エチレンは、一般的には、高分子固体型燃料電池の固体電解質として広く利用されており、具体例として、デュポン社の「ナフィオン（登録商標）」が挙げられ、溶媒に溶解した分散溶液（５％,１０％，２０％のポリマ－濃度）で販売されている。 Polytetrafluoroethylene graft-polymerized with sulfonic acid groups is generally widely used as a solid electrolyte for polymer solid fuel cells. As a specific example, “Nafion (registered trademark)” by DuPont is used. And are sold in dispersion solutions (5%, 10%, 20% polymer concentration) dissolved in a solvent.
 パーフルオロカルボン酸系イオン交換樹脂の具体例としては、旭硝子社のフレミオンが挙げられる。これは基本的に上記ナフィオンに似た構造を持ち、テトラフルオロエチレンとカルボン酸基を含有するパーフルオロ型ビニルエーテルの共重合体として合成される。 Specific examples of perfluorocarboxylic acid ion exchange resins include Flemion from Asahi Glass Co., Ltd. This basically has a structure similar to the above Nafion, and is synthesized as a copolymer of tetrafluoroethylene and a perfluoro vinyl ether containing a carboxylic acid group.
　　（機能性シラン）
　アルコキシシランとしては、テトラエトキシシラン、テトラメトキシシラン、３-アミノプロピルトリエトキシシラン等が挙げられる。 (Functional silane)
Examples of the alkoxysilane include tetraethoxysilane, tetramethoxysilane, 3-aminopropyltriethoxysilane and the like.
　クロルシランとしては、モノクロロシラン化合物ＳｉＲ3Ｃｌ、ジクロロシラン化合物ＳｉＲ2Ｃｌ2、トリクロロシラン化合物ＳｉＲＣｌ3等が挙げられる（ここでＲは、ＣＨ3，Ｃ6Ｈ6，ＣnＨ2n+1などのアルキル基、ｎは自然数）。 Examples of chlorosilane include monochlorosilane compound SiR 3 Cl, dichlorosilane compound SiR 2 Cl 2 , trichlorosilane compound SiRCl 3 and the like (where R is CH 3 , C 6 H 6 , C n H 2n + 1, etc.). Alkyl group, n is a natural number).
　シラザンは、ケイ素と窒素と水素等からなり、Ｓｉ－Ｎ－Ｓｉ結合を有する一連の化合物であって、具体例として、ヘキサメチルジシラザン（(ＣＨ3)3Ｓｉ)2ＮＨをはじめとするジシラザン(Ｒ3Ｓｉ)2ＮＨ、シクロシラザン(Ｒ2ＳｉＮＨ)n、ポリシクロシラザン［ＲＳｉ(ＮＨ)1.5］nが挙げられる（ｎは自然数）。 Silazane is a series of compounds composed of silicon, nitrogen, hydrogen, and the like and having a Si—N—Si bond. As a specific example, disilazan such as hexamethyldisilazane ((CH 3 ) 3 Si) 2 NH is used. (R 3 Si) 2 NH, cyclosilazane (R 2 SiNH) n , and polycyclosilazane [RSi (NH) 1.5 ] n (n is a natural number).
　これらの機能性シランは、穏和な条件下で加水分解－縮合し、ポリシロキサンあるいはポリシラザンを形成することができる。 These functional silanes can be hydrolyzed and condensed under mild conditions to form polysiloxane or polysilazane.
　本実施形態に係る光触媒コーティング組成物において、機能性シランのモノマーを用いてもよいし、機能性シランの２～１００量体オリゴマーを用いてもよい。 In the photocatalytic coating composition according to this embodiment, a functional silane monomer may be used, or a functional silane dimer to 100-mer oligomer may be used.
　機能性シランが光触媒コーティング組成物に含まれている場合、当該機能性シランは徐々に加水分解並びに縮合して、機能性シランの加水分解物並びに縮合物に変化する。 When the functional silane is contained in the photocatalyst coating composition, the functional silane gradually hydrolyzes and condenses, and changes into a hydrolyzate and a condensate of the functional silane.
　（光触媒）
　光触媒機能を有する金属酸化物としては、一般的に、光触媒として用いられているものを用いることができる。その具体例としては、酸化チタン（ＴｉＯ2），酸化亜鉛（ＺｎＯ），酸化タングステン（ＷＯ3），酸化スズ（ＳｎＯ2），チタン酸ストロンチウム（ＳｒＴｉＯ3），酸化ビスマス（Ｂｉ2Ｏ3），酸化鉄（Ｆｅ2Ｏ3）が挙げられる。 (photocatalyst)
As the metal oxide having a photocatalytic function, those generally used as a photocatalyst can be used. Specific examples thereof include titanium oxide (TiO 2 ), zinc oxide (ZnO), tungsten oxide (WO 3 ), tin oxide (SnO 2 ), strontium titanate (SrTiO 3 ), bismuth oxide (Bi 2 O 3 ), An example is iron oxide (Fe 2 O 3 ).
　（光触媒コーティング組成物の製法、コーティング方法）
　イオン交換樹脂と、機能性シランと、光触媒機能を有する金属酸化物とを配合する。この他、溶媒も必要に応じて配合し、混合することによって、光触媒コーティング組成物を製造する。 (Production method of photocatalyst coating composition, coating method)
An ion exchange resin, a functional silane, and a metal oxide having a photocatalytic function are blended. In addition, a photocatalytic coating composition is produced by blending and mixing a solvent as necessary.
　溶媒としては、上記のイオン交換樹脂を溶解させることのできる溶媒、例えば、メタノール、エタノール、イソプロパノール、水あるいは、これらの混合溶媒が挙げられる。 Examples of the solvent include a solvent capable of dissolving the above ion exchange resin, for example, methanol, ethanol, isopropanol, water, or a mixed solvent thereof.
　バインダ中においてイオン交換樹脂に対する機能性シランの配合比率が大きくなるほど、コーティング膜の親水性は低くなるが、コーティング膜の硬度は高くなる。 As the blending ratio of the functional silane to the ion exchange resin in the binder increases, the hydrophilicity of the coating film decreases, but the hardness of the coating film increases.
　また、バインダに対する光触媒機能を有する金属酸化物の配合比率を大きくするほど、コーティング膜の親水性は高くなるが、コーティング膜の柔軟性は低下する。 Also, as the compounding ratio of the metal oxide having a photocatalytic function with respect to the binder is increased, the hydrophilicity of the coating film increases, but the flexibility of the coating film decreases.
 従って、光触媒コーティング組成物において、イオン交換樹脂に対する機能性シランの比率、並びにバインダに対する光触媒機能を有する金属酸化物の比率を調整することによって、所望の親水性および硬度、柔軟性を有するコーティング膜を得ることができる。 Therefore, in the photocatalytic coating composition, by adjusting the ratio of the functional silane to the ion exchange resin and the ratio of the metal oxide having the photocatalytic function to the binder, a coating film having desired hydrophilicity, hardness, and flexibility is obtained. Obtainable.
　尚、機能性シランや金属酸化物の添加量を変化させても、コーティング膜の光触媒機能や透明性が大きく損なわれることはない。 Note that even if the amount of functional silane or metal oxide added is changed, the photocatalytic function and transparency of the coating film are not significantly impaired.
　光触媒コーティング組成物において、バインダ中のイオン交換樹脂に対する機能性シランの配合比率は、固形分換算で３～５倍に設定することが好ましく、バインダに対する光触媒機能を有する金属酸化物の配合比率は、固形分換算で５～７０重量％の範囲内に設定することが好ましい。 In the photocatalyst coating composition, the blending ratio of the functional silane to the ion exchange resin in the binder is preferably set to 3 to 5 times in terms of solid content, and the blending ratio of the metal oxide having a photocatalytic function to the binder is: It is preferably set within the range of 5 to 70% by weight in terms of solid content.
 たとえば、イオン交換樹脂(２０％溶液)を３０重量部、アルコキシシランを２０～３０重量部、光触媒機能を有する金属酸化物の粒子を５重量部配合して光触媒コーティング組成物を構成すればよいが、この範囲に限定されるものではない。 For example, 30 parts by weight of ion exchange resin (20% solution), 20 to 30 parts by weight of alkoxysilane, and 5 parts by weight of metal oxide particles having a photocatalytic function may be blended to constitute a photocatalyst coating composition. However, it is not limited to this range.
 また、光触媒コーティング組成物には、ＫＯＨなどのアルカリあるいはエタノールアミンなどのアミン類などを加えて、ｐＨ３～７の範囲に調整することが好ましい。ｐＨがこの範囲にあれば、加水分解反応および重縮合反応に対して適度な反応性並びに安定性を有する。 In addition, it is preferable to adjust the pH to a range of 3 to 7 by adding an alkali such as KOH or an amine such as ethanolamine to the photocatalyst coating composition. If pH exists in this range, it has moderate reactivity and stability with respect to a hydrolysis reaction and a polycondensation reaction.
　光触媒コーティング組成物には、さらにＥＴＦＥ（テトラフルオロエチレンＣ2Ｆ4とエチレンＣ2Ｈ4の共重合体）などのフッ素樹脂を添加してもよい。そうすることによって、基体との密着性がさらに向上する効果が期待できる。 A fluorine resin such as ETFE (a copolymer of tetrafluoroethylene C 2 F 4 and ethylene C 2 H 4 ) may be further added to the photocatalyst coating composition. By doing so, the effect which the adhesiveness with a base | substrate further improves can be anticipated.
　　[光触媒被膜付基体]
　以上のような光触媒コーティング組成物を、ゾルゲル法で基体の表面上にコーティングすることによって、基体表面に超親水性被膜が被着される。ここでは、光触媒コーティング組成物のバインダとして、パーフルオロスルホン酸系イオン交換樹脂とアルコキシシランを用いることとして説明する。 [Substrate with photocatalyst coating]
By coating the photocatalyst coating composition as described above on the surface of the substrate by the sol-gel method, a superhydrophilic film is deposited on the surface of the substrate. Here, it demonstrates as using a perfluorosulfonic acid type ion exchange resin and alkoxysilane as a binder of a photocatalyst coating composition.
　例えば、基体としてＰＥＴフィルム、あるいは塩ビフィルムを準備し、このフィルムに光触媒コーティング組成物を塗布して、加熱乾燥もしくは自然乾燥させることにより、超親水性の被膜付フィルムが作製される。 For example, a super hydrophilic film-coated film is produced by preparing a PET film or a vinyl chloride film as a substrate, applying a photocatalyst coating composition to the film, and drying by heating or natural drying.
　図１は、被膜付フィルムの断面を示す模式図である。 FIG. 1 is a schematic view showing a cross section of a film with a coating.
　被膜付フィルム１０は、基体となるフィルム１１の表面上にコーティング被膜１２が被着されて形成されている。 The film with film 10 is formed by coating a coating film 12 on the surface of a film 11 serving as a substrate.
　コーティング被膜１２は、光触媒粒子１３（光触媒機能を有する金属酸化物）が、イオン交換樹脂と機能性シランで形成されたバインダ層１４中に分散されて構成されている。 The coating film 12 is configured by dispersing photocatalyst particles 13 (metal oxide having a photocatalytic function) in a binder layer 14 formed of an ion exchange resin and functional silane.
　図２は、パーフルオロスルホン酸系イオン交換樹脂とアルコキシシランで形成されたバインダ層１４の構造を模式的に示す図である。 FIG. 2 is a diagram schematically showing the structure of the binder layer 14 formed of perfluorosulfonic acid ion exchange resin and alkoxysilane.
　この図２に示すように、コーティング組成物中のバインダには、イオン交換樹脂とアルコキシシランなどが混在するが、コーティング被膜においては、アルコキシシランのアルコキシ基どうしが、加水分解して重縮合することによってシロキサンが形成されるとともに、アルコキシシランが加水分解されて形成されるＳｉ－ＯＨ基が、パーフルオロスルホン酸系イオン交換樹脂（グラフトポリマー）のエーテル基と水素結合する。従って、コーティング膜１２を形成するバインダ層１４においては、イオン交換樹脂及びシロキサンが混在したハイブリッド網目構造もしくはハイブリッド鎖状構造が形成されている。 As shown in FIG. 2, the binder in the coating composition contains an ion exchange resin and alkoxysilane, but in the coating film, the alkoxy groups of alkoxysilane are hydrolyzed and polycondensed. As a result, siloxane is formed, and Si—OH groups formed by hydrolysis of alkoxysilane hydrogen bond with ether groups of perfluorosulfonic acid ion exchange resin (graft polymer). Therefore, in the binder layer 14 forming the coating film 12, a hybrid network structure or a hybrid chain structure in which an ion exchange resin and siloxane are mixed is formed.
　それによって、このコーティング被膜１２は、柔軟性と耐久性と透明性を兼ね備える。また、コーティング被膜１２の表面には、光触媒性の金属酸化物粒子１３が存在するとともに、バインダに含まれるパーフルオロスルホン酸基も存在するので、コーティング被膜１２が水に接触すると、水がスルホン酸基や光触媒性の金属酸化物粒子１３に集まって、超親水性を呈し、水滴は一様に広がり薄い水の膜となる。 Thereby, this coating film 12 has flexibility, durability and transparency. Further, since the photocatalytic metal oxide particles 13 are present on the surface of the coating film 12 and perfluorosulfonic acid groups contained in the binder are also present, when the coating film 12 comes into contact with water, the water becomes sulfonic acid. They gather on the base and photocatalytic metal oxide particles 13 to exhibit super hydrophilicity, and the water droplets spread uniformly to form a thin water film.
　そのため、コーティング被膜１２の表面は、長期間にわたって超親水性に保たれ、光の散乱がなく曇らない上に、防汚性が発揮される。 Therefore, the surface of the coating film 12 is kept super-hydrophilic for a long period of time, does not scatter and does not cloud light, and exhibits antifouling properties.
　よって、表面に汚れなどが付着したとしても、雨水やシャワー水などで簡単に汚れを落とすことができる。 Therefore, even if dirt or the like adheres to the surface, it can be easily removed with rain water or shower water.
　このように、本実施形態にかかるコーティング組成物には、パーフルオロスルホン酸系イオン交換樹脂とアルコキシシランとが含まれていることによって、バインダ層１４にハイブリッド網目構造もしくはハイブリッド鎖状構造が形成され、それに起因して、被膜付フィルム１０は、超親水性に加えて、耐久性，透明性を合わせ持つ効果を奏する。 As described above, the coating composition according to the present embodiment includes the perfluorosulfonic acid ion exchange resin and the alkoxysilane, so that a hybrid network structure or a hybrid chain structure is formed in the binder layer 14. As a result, the coated film 10 has the effect of combining durability and transparency in addition to super hydrophilicity.
　すなわち、コーティング組成物に含まれるイオン交換樹脂とアルコキシシランの相乗作用によって、被膜付フィルム１０が、超親水性に加えて、耐久性，透明性を合わせ持つことになる。 That is, due to the synergistic action of the ion exchange resin and alkoxysilane contained in the coating composition, the coated film 10 has both durability and transparency in addition to super hydrophilicity.
 さらに、コーティング被膜１２の表面に、光触媒性の金属酸化物粒子１３が存在するので、金属酸化物粒子１３に光が当たると、光触媒反応により被膜表面に存在する有害物質を分解する。 Furthermore, since the photocatalytic metal oxide particles 13 are present on the surface of the coating film 12, when light hits the metal oxide particles 13, harmful substances present on the surface of the film are decomposed by a photocatalytic reaction.
 なお、このような超親水性に加えて、耐久性，透明性の効果は、コーティング組成物において、パーフルオロスルホン酸系イオン交換樹脂の代わりにパーフルオロカルボン酸系イオン交換樹脂を用いた場合、並びにアルコキシシランの代わりに、クロロシランあるいはシラザンを用いた場合にも基本的に同様に得ることができる。 In addition to such super-hydrophilicity, durability and transparency effects can be obtained when a perfluorocarboxylic acid ion exchange resin is used instead of a perfluorosulfonic acid ion exchange resin in the coating composition. In addition, when chlorosilane or silazane is used instead of alkoxysilane, the same can be basically obtained.
 また、上記説明では、基体としてポリエチレンテレフタレート（ＰＥＴ）フィルム、塩ビフィルムを用いることとしたが、フィルムの種類も特に限定されない。 In the above description, a polyethylene terephthalate (PET) film and a vinyl chloride film are used as the substrate, but the type of film is not particularly limited.
 また、フィルム以外にも、ガラス板、あるいは鋼板をはじめとする金属板、あるいは金属板に、フッ素樹脂，アクリル樹脂，アクリルシリコン樹脂，ウレタン樹脂，あるいはポリエステル樹脂が含有された塗料を塗布したものを、基体として用いることもできる。 In addition to the film, a glass plate or a metal plate such as a steel plate, or a metal plate coated with a paint containing a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, or a polyester resin. It can also be used as a substrate.
 また、基体の形状は、板状には限らず任意であって、例えば立体的形状であってもよい。 The shape of the substrate is not limited to a plate shape, and may be any shape, for example, a three-dimensional shape.
　[被膜付フィルムに関する実施例]
 以下のようにして、実施例並びに比較例にかかる光触媒コーティング組成物を調整し、被膜付フィルムを作製した。
（実施例１）
 エタノール溶媒７０重量部に、エチルシリケート２８（コルコート製、テトラエトキシシラン（TEOS））５重量部と、ナフィオンDE２０２１（デュポン製、２０％溶液）２０重量部と、結晶性酸化チタンスラリーＴＫＤ７０２（テイカ製、ＴｉＯ2：１６％溶液）５重量部とを加えて混合し、光触媒性コーティング液を調整した。
（比較例１）
　ナフィオンＤＥ２０２１（デュポン製、２０％溶液）２０重量部と、結晶性酸化チタンスラリーＴＫＤ７０２（テイカ製、ＴｉＯ2：１６％溶液）５重量部と、イソプロピルアルコール７５重量部とを加えて混合し、光触媒性コーティング液を調整した。
（実施例２)
　エタノール溶媒６８重量部にエチルシリケート２８（コルコート製）５重量部と、ナフィオンDE２０２１（デュポン製、２０％溶液）２０重量部と、結晶性酸化チタンスラリーＴＫＤ７０２（テイカ製、ＴｉＯ2：１６％溶液）５重量部と、ヒドロキシフェニルトリアジン系紫外線吸収剤ＴＩＮＵＶＩＮ４００（チバ・スペシャリティ・ケミカルズ製）1重量部と、ヒンダードアミン系光安定化剤ＴＩＮＵＶＩＮ１２３（チバ・スペシャリティ・ケミカルズ製）１重量部とを加えて混合し、光触媒性コーティング液を調整した。
（比較例２)
　エタノール溶媒９０重量部に、エチルシリケート２８（コルコート製）１０重量部と、結晶性酸化チタンスラリーＴＫＤ７０２（テイカ製、ＴｉＯ2：１６％溶液）５重量部とを加えて混合し、光触媒性コーティング液を調整した。 [Examples of coated film]
The photocatalyst coating composition concerning an Example and a comparative example was adjusted as follows, and the film with a film was produced.
Example 1
70 parts by weight of ethanol solvent, 5 parts by weight of ethyl silicate 28 (manufactured by Colcoat, tetraethoxysilane (TEOS)), 20 parts by weight of Nafion DE2021 (manufactured by DuPont, 20% solution), and a crystalline titanium oxide slurry TKD702 (manufactured by Teika) TiO 2 : 16% solution) and 5 parts by weight were added and mixed to prepare a photocatalytic coating solution.
(Comparative Example 1)
20 parts by weight of Nafion DE2021 (manufactured by DuPont, 20% solution), 5 parts by weight of crystalline titanium oxide slurry TKD702 (manufactured by Teika, TiO 2 : 16% solution), and 75 parts by weight of isopropyl alcohol are added and mixed to form a photocatalyst The coating liquid was adjusted.
(Example 2)
68 parts by weight of ethanol solvent, 5 parts by weight of ethyl silicate 28 (manufactured by Colcoat), 20 parts by weight of Nafion DE2021 (manufactured by DuPont, 20% solution), and crystalline titanium oxide slurry TKD702 (manufactured by Teika, TiO 2 : 16% solution) Add 5 parts by weight, 1 part by weight of a hydroxyphenyltriazine-based UV absorber TINUVIN400 (manufactured by Ciba Specialty Chemicals) and 1 part by weight of a hindered amine light stabilizer TINUVIN123 (manufactured by Ciba Specialty Chemicals) and mix. A photocatalytic coating solution was prepared.
(Comparative Example 2)
To 90 parts by weight of ethanol solvent, 10 parts by weight of ethyl silicate 28 (manufactured by Colcoat) and 5 parts by weight of crystalline titanium oxide slurry TKD702 (manufactured by Teika, TiO 2 : 16% solution) are added and mixed to form a photocatalytic coating solution. Adjusted.
　以上のようにして得られた実施例１，２および比較例１，２にかかる光触媒コーティング液を、それぞれ、厚さ５０μｍのＰＥＴフィルム上に、Ｎｏ．２０のバーコータを用いて塗布量２０g／m2で塗布し、８０℃で３分間乾燥することによって光触媒被膜付フィルムを得た。光触媒被膜の膜厚は約１μｍであった。 The photocatalyst coating liquids according to Examples 1 and 2 and Comparative Examples 1 and 2 obtained as described above were respectively applied to a PET film having a thickness of 50 μm. A film with a photocatalyst film was obtained by coating at a coating amount of 20 g / m 2 using a 20 bar coater and drying at 80 ° C. for 3 minutes. The film thickness of the photocatalyst film was about 1 μm.
　得られた光触媒被膜付フィルムを用いて、以下のように、強度確認試験、透明度確認試験および紫外線透過率確認試験を行った。
＜光触媒被膜付フィルムの強度確認試験＞
　強度試験として、密着性試験、表面硬度試験、伸び試験を行った。 Using the obtained film with a photocatalyst coating, a strength confirmation test, a transparency confirmation test, and an ultraviolet transmittance confirmation test were performed as follows.
<Strength confirmation test of film with photocatalyst coating>
As a strength test, an adhesion test, a surface hardness test, and an elongation test were performed.
　密着性試験は、ＪＩＳ　Ｋ　５６００に規定される碁盤目テープ剥離試験に準拠して行い、表面硬度試験は、ＪＩＳ　Ｋ　５６００に規定される引っかき硬度（鉛筆法）試験に準拠して行い、伸び試験はＪＩＳ　Ｋ　７１２７に規定される引張特性の試験方法に準拠して行った。その試験結果を表１に示す。 The adhesion test is performed in accordance with a cross-cut tape peeling test specified in JIS K 5600, and the surface hardness test is performed in accordance with a scratch hardness (pencil method) test specified in JIS K 5600, and an elongation test. Was conducted in accordance with a test method for tensile properties defined in JIS K 7127. The test results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１の結果より、バインダとしてＴＥＯＳとナフィオンとが混合されている実施例１では、バインダがナフィオン単独である比較例１よりも、光触媒覆付フィルムの表面硬度が高く、密着性に優れていることが分かる。また光触媒覆付フィルムの表面硬度についても、実施例１では、比較例１より高く、ＰＥＴフィルム基材と比べても高い。 From the results of Table 1, in Example 1 in which TEOS and Nafion are mixed as a binder, the surface hardness of the photocatalyst-covered film is higher and the adhesiveness is superior to Comparative Example 1 in which the binder is Nafion alone. I understand that. The surface hardness of the photocatalyst-covering film is also higher in Example 1 than Comparative Example 1 and higher than that of the PET film substrate.
　一方、バインダがエチルシリケートだけからなる比較例２では、光触媒覆付フィルムの密着性および表面硬度は良好であるが、伸び率は低い。なお、比較例２の光触媒覆付フィルムの屈曲時にクラックが発生した。 On the other hand, in Comparative Example 2 where the binder is composed only of ethyl silicate, the adhesion and surface hardness of the photocatalyst-covering film are good, but the elongation percentage is low. In addition, the crack generate | occur | produced at the time of the bending of the photocatalyst covering film of the comparative example 2.
　＜光触媒被膜付フィルムの透明度確認試験＞
　分光光度計（ウルトラスキャンＸＥ：ハンターラブ社）によりヘイズを測定した。 <Transparency confirmation test of photocatalyst-coated film>
Haze was measured with a spectrophotometer (Ultrascan XE: Hunterlab).
　その結果を表２に示す。 The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　表２の結果より、実施例１の光触媒覆付フィルムでは、透過率がＰＥＴフィルムの透過率に近く、比較例１の光触媒コーティング組成物を被膜したものと比べて透明度が高いことがわかる。 From the results in Table 2, it can be seen that the photocatalyst-covered film of Example 1 has a transmittance close to that of the PET film, and has higher transparency than that coated with the photocatalyst coating composition of Comparative Example 1.
 以上のように実施例１にかかる光触媒覆付フィルムが、密着性、表面硬度、伸び率、透明度ともに良好であるのは、ナフィオンとＴＥＯＳとがハイブリッド網目構造または鎖状構造を形成しているためと考えられる。 As described above, the photocatalyst-covering film according to Example 1 has good adhesion, surface hardness, elongation, and transparency because Nafion and TEOS form a hybrid network structure or chain structure. it is conceivable that.
　＜光触媒被膜付フィルムの紫外線透過率確認試験＞
　実施例１，２の光触媒覆付フィルムについて、紫外分光光度計（ＵＶ－２４５０：島津製作所）により、紫外線波長３５０ｎｍでの紫外線透過率を測定した。その結果を表３に示す。 <Ultraviolet transmittance confirmation test of film with photocatalyst coating>
For the photocatalyst-covered films of Examples 1 and 2, the ultraviolet transmittance at an ultraviolet wavelength of 350 nm was measured with an ultraviolet spectrophotometer (UV-2450: Shimadzu Corporation). The results are shown in Table 3.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表３の結果より、紫外線吸収剤を添加した実施例２では、紫外線吸収剤を添加していない実施例１と比べて、光触媒被膜付フィルムの紫外線透過率が３０％程度低下していることが分かる。
＜光触媒被膜付フィルムの分解性能確認試験＞
 光触媒材料のセルフクリーニング性能試験方法として、ＪＩＳ１７０３－２メチレンブルー試薬の分解を評価することによる湿式分解性能試験がある。この試験方法に準拠して実施例１および比較例１について分解性能確認試験を行った。その結果を表４に示す。 From the results in Table 3, in Example 2 where the ultraviolet absorber was added, the ultraviolet transmittance of the photocatalyst-coated film was reduced by about 30% compared to Example 1 where no ultraviolet absorber was added. I understand.
<Decomposition performance confirmation test of film with photocatalyst coating>
As a method for testing the self-cleaning performance of the photocatalytic material, there is a wet degradation performance test by evaluating the degradation of JIS 1703-2 methylene blue reagent. In accordance with this test method, a decomposition performance confirmation test was performed on Example 1 and Comparative Example 1. The results are shown in Table 4.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
 本試験で分解活性指数が５以上であれば、光触媒機能を有するとされているが、表４に示されるように、実施例１および比較例１ともに分解活性指数が９．０であって、光触媒機能を有していることが分かる。 If the degradation activity index is 5 or more in this test, it is said to have a photocatalytic function, but as shown in Table 4, the degradation activity index is 9.0 for both Example 1 and Comparative Example 1, It turns out that it has a photocatalytic function.
　　[光触媒被覆付ポリエステル鋼板に関する実施例]
 (実施例３)
　エタノール溶媒６０重量部にエチルシリケート２８（コルコート）５重量部と、ナフィオンDE２０２１（デュポン、２０％溶液）３０重量部と結晶性酸化チタンスラリーＴＫＤ７０２（テイカ、ＴｉＯ2：１６％溶液）５重量部とを加えて混合し、光触媒性コーティング液を調整した。 [Examples of photocatalyst-coated polyester steel sheet]
Example 3
60 parts by weight of ethanol solvent, 5 parts by weight of ethyl silicate 28 (Colcoat), 30 parts by weight of Nafion DE2021 (DuPont, 20% solution) and 5 parts by weight of crystalline titanium oxide slurry TKD702 (Taika, TiO 2 : 16% solution) Were added and mixed to prepare a photocatalytic coating solution.
　（比較例３）
　ナフィオンＤＥ２０２１（デュポン、２０％溶液）３０重量部と結晶性酸化チタンスラリーＴＫＤ７０２（テイカ、ＴｉＯ2：１６％溶液）5重量部と、イソプロピルアルコール６５重量部を加えて混合し、光触媒性コーティング液を調整した。 (Comparative Example 3)
30 parts by weight of Nafion DE2021 (DuPont, 20% solution), 5 parts by weight of crystalline titanium oxide slurry TKD702 (Taika, TiO 2 : 16% solution) and 65 parts by weight of isopropyl alcohol are added and mixed to prepare a photocatalytic coating solution. It was adjusted.
　以上のように得られた実施例３，比較例４の光触媒コーティング液を、Ｎｏ．１０のバーコータを用いて、ポリエステル焼付鋼板上に塗布量３０g／m2で塗布し、１００℃５分間乾燥することによって光触媒被膜付ポリエステル鋼板を得た。光触媒被膜の膜厚は２～3μｍであった。 The photocatalyst coating liquids of Example 3 and Comparative Example 4 obtained as described above were designated A polyester steel sheet with a photocatalyst coating was obtained by applying a coating amount of 30 g / m 2 on a polyester baked steel sheet using a 10 bar coater and drying at 100 ° C. for 5 minutes. The film thickness of the photocatalyst film was 2 to 3 μm.
　得られた光触媒被膜付ポリエステル鋼板について、以下のように密着性試験、表面硬度試験を行った。
＜光触媒被膜付ポリエステル鋼板の強度確認試験＞
密着性試験は、ＪＩＳ　Ｋ　５６００に規定される碁盤目テープ剥離試験に準拠して、表面硬度試験は、ＪＩＳ　Ｋ　５６００に規定される引っかき硬度（鉛筆法）試験に準拠して行った。表５にその試験結果を示す。 The obtained photocatalyst-coated polyester steel sheet was subjected to an adhesion test and a surface hardness test as follows.
<Strength confirmation test of polyester steel sheet with photocatalyst coating>
The adhesion test was performed in accordance with a cross-cut tape peeling test specified in JIS K 5600, and the surface hardness test was performed in accordance with a scratch hardness (pencil method) test specified in JIS K 5600. Table 5 shows the test results.
Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005
　表５の結果より、バインダがナフィオンのみからなる比較例３では、光触媒被膜付ポリエステル鋼板の密着性試験において、塗膜が部分的に剥離したのに対して、バインダとしてＴＥＯＳとナフィオンとが混合されている実施例３では、光触媒被膜付ポリエステル鋼板の密着性が良好であった。また表面硬度についても、実施例３の光触媒被膜付ポリエステル鋼板では、ポリエステル鋼板よりも表面硬度が高いことがわかる。 From the results of Table 5, in Comparative Example 3 in which the binder is composed only of Nafion, the coating film was partially peeled in the adhesion test of the polyester steel sheet with a photocatalyst coating, whereas TEOS and Nafion were mixed as the binder. In Example 3, the adhesion of the photocatalyst-coated polyester steel sheet was good. Moreover, also about the surface hardness, it turns out that the surface hardness is higher in the polyester steel plate with a photocatalyst film of Example 3 than a polyester steel plate.
 以上のように実施例３にかかる光触媒覆付フィルムが、密着性、表面硬度ともに良好であるのも、ナフィオンとＴＥＯＳとがハイブリッド網目構造または鎖状構造を形成しているためと考えられる。 As described above, the photocatalyst-covering film according to Example 3 has good adhesion and surface hardness because Nafion and TEOS form a hybrid network structure or chain structure.

Claims (12)

  1. 　バインダに光触媒機能を有する金属酸化物を配合してなる光触媒コーティング組成物であって、
    　前記バインダは、
    　パーフルオロスルホン酸系イオン交換樹脂及びパーフルオロカルボン酸系イオン交換樹脂から選択される少なくとも１種のイオン交換樹脂と、
    　アルコキシシラン、クロロシラン、シラザンから選択される少なくとも1種の機能性シラン、もしくは、当該機能性シランの加水分解物または縮合物とを含むことを特徴とする光触媒コーティング組成物。     A photocatalytic coating composition comprising a binder and a metal oxide having a photocatalytic function,
    The binder is
    At least one ion exchange resin selected from perfluorosulfonic acid ion exchange resins and perfluorocarboxylic acid ion exchange resins;
    A photocatalytic coating composition comprising at least one functional silane selected from alkoxysilane, chlorosilane, and silazane, or a hydrolyzate or condensate of the functional silane.
  2. 　前記イオン交換樹脂は、
    　スルホン酸基がグラフト重合されたポリ４フッ化エチレンであることを特徴とする請求項１記載の光触媒コーティング組成物。     The ion exchange resin is
    2. The photocatalytic coating composition according to claim 1, wherein the sulfonic acid group is polytetrafluoroethylene graft-polymerized.
  3.  前記機能性シランは、モノマーであることを特徴とする請求項１記載の光触媒コーティング組成物。 The photocatalytic coating composition according to claim 1, wherein the functional silane is a monomer.
  4. 　前記機能性シランは、２～１００量体オリゴマーであることを特徴とする請求項１記載の光触媒コーティング組成物。 2. The photocatalytic coating composition according to claim 1, wherein the functional silane is a 2 to 100-mer oligomer.
  5. 　前記金属酸化物は、
    　ＴｉＯ2，ＺｎＯ，ＷＯ3，ＳｎＯ2，ＳｒＴｉＯ3，Ｂｉ2Ｏ3，Ｆｅ2Ｏ3から選択される少なくとも１種であることを特徴とする請求項１記載の光触媒コーティング組成物。     The metal oxide is
    TiO 2, ZnO, WO 3, SnO 2, SrTiO 3, Bi 2 O 3, Fe 2 O 3 photocatalytic coating composition according to claim 1, wherein the at least one selected from the.
  6. 　無機系紫外線吸収剤、有機系紫外線吸収剤および光安定化剤から選択される少なくとも１種が添加されていることを特徴とする請求項１記載の光触媒コーティング組成物。 2. The photocatalytic coating composition according to claim 1, wherein at least one selected from an inorganic ultraviolet absorber, an organic ultraviolet absorber, and a light stabilizer is added.
  7. 　請求項１～６のいずれか記載の光触媒コーティング組成物で形成された被膜が、基材に被着されてなる被膜付基体。 A film-coated substrate, wherein a film formed of the photocatalytic coating composition according to any one of claims 1 to 6 is attached to a substrate.
  8. 　前記イオン交換樹脂と、前記機能性シランとが、
     ハイブリッド網目構造またはハイブリッド鎖状構造を形成していることを特徴とする請求項７記載の被膜付基体。     The ion exchange resin and the functional silane are
    8. The coated substrate according to claim 7, wherein a hybrid network structure or a hybrid chain structure is formed.
  9. 　前記基材は、
    　アクリル，アクリルシリコン，ポリエチレン，ポリカーボネート，ポリプロピレン，ポリウレタン，ポリスチレン，ポリエチレンテレフタレート，ポリ塩化ビニル，ポリアミド，ポリアセタール，ＡＳ（アクリロニトリル／スチレン樹脂），ＡＢＳ（アクリロニトリル／ブタジエン／スチレン樹脂）から選択される樹脂で形成されたフィルムまたは成型品であることを特徴とする請求項７記載の被膜付基体。     The substrate is
    Made of resin selected from acrylic, acrylic silicone, polyethylene, polycarbonate, polypropylene, polyurethane, polystyrene, polyethylene terephthalate, polyvinyl chloride, polyamide, polyacetal, AS (acrylonitrile / styrene resin), ABS (acrylonitrile / butadiene / styrene resin) 8. The coated substrate according to claim 7, wherein the coated substrate is a film or a molded product.
  10. 　前記基材は、ガラス基材であることを特徴とする請求項７記載の被膜付基体。 The coated substrate according to claim 7, wherein the substrate is a glass substrate.
  11. 　前記基材は、金属板からなることを特徴とする請求項７記載の被膜付基体。 The coated substrate according to claim 7, wherein the substrate is made of a metal plate.
  12. 　前記基材は、
    　前記金属板に、フッ素樹脂，アクリル樹脂，アクリルシリコン樹脂，ウレタン樹脂，ポリエステル樹脂から選択される樹脂が含有された塗料が塗布されてなることを特徴とする請求項１１記載の被膜付基体。     The substrate is
    The coated substrate according to claim 11, wherein a coating containing a resin selected from a fluororesin, an acrylic resin, an acrylic silicon resin, a urethane resin, and a polyester resin is applied to the metal plate.
PCT/JP2008/001130 2008-04-30 2008-04-30 Photocatalytic coating composition and substrate having coating film WO2009133591A1 (en)

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JP2013022799A (en) * 2011-07-20 2013-02-04 Konica Minolta Holdings Inc Gas barrier film, and method of manufacturing the gas barrier film
JP2018076443A (en) * 2016-11-10 2018-05-17 サカタインクス株式会社 Alkoxysilane hydrolysis composition, and method for producing the same

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* Cited by examiner, † Cited by third party
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JP2013022799A (en) * 2011-07-20 2013-02-04 Konica Minolta Holdings Inc Gas barrier film, and method of manufacturing the gas barrier film
JP2018076443A (en) * 2016-11-10 2018-05-17 サカタインクス株式会社 Alkoxysilane hydrolysis composition, and method for producing the same

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