WO2010104146A1 - コーティング組成物、塗膜、積層体、及び積層体の製造方法 - Google Patents
コーティング組成物、塗膜、積層体、及び積層体の製造方法 Download PDFInfo
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- WO2010104146A1 WO2010104146A1 PCT/JP2010/054111 JP2010054111W WO2010104146A1 WO 2010104146 A1 WO2010104146 A1 WO 2010104146A1 JP 2010054111 W JP2010054111 W JP 2010054111W WO 2010104146 A1 WO2010104146 A1 WO 2010104146A1
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- 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
- C09D5/006—Anti-reflective coatings
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/02—Emulsion paints including aerosols
- C09D5/024—Emulsion paints including aerosols characterised by the additives
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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
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
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- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
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- G02B1/18—Coatings for keeping optical surfaces clean, e.g. hydrophobic or photo-catalytic films
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- G02B5/08—Mirrors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02S—GENERATION OF ELECTRIC POWER BY CONVERSION OF INFRARED RADIATION, VISIBLE LIGHT OR ULTRAVIOLET LIGHT, e.g. USING PHOTOVOLTAIC [PV] MODULES
- H02S40/00—Components or accessories in combination with PV modules, not provided for in groups H02S10/00 - H02S30/00
- H02S40/10—Cleaning arrangements
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/40—Solar thermal energy, e.g. solar towers
- Y02E10/46—Conversion of thermal power into mechanical power, e.g. Rankine, Stirling or solar thermal engines
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/24967—Absolute thicknesses specified
- Y10T428/24975—No layer or component greater than 5 mils thick
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/254—Polymeric or resinous material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y10T428/259—Silicic material
Definitions
- the present invention relates to a coating composition, a coating film, a laminate, and a method for producing the laminate.
- a coating composition a coating film, a laminated body, its manufacturing method, a solar cell module using these, a reflector apparatus, and a solar thermal power generation system.
- Typical solar power generation methods include a centralized method (central tower method), a distributed method (parabolic trough), and a dish / sterling method. Therefore, it is important to collect light without loss. However, as a factor that greatly affects the efficiency, a decrease in reflectance due to contamination of the reflector is particularly problematic. Similarly, a solar cell whose light-receiving surface is protected by a protective cover made of glass, weather resistant resin film, or the like also has a reduced light transmittance because the protective cover is contaminated with dust during long-term use. There is a similar problem that the energy conversion efficiency is reduced.
- Patent Document 1 discloses that an anatase-type titanium oxide-containing layer is coated with a coating solution in which tungstic acid dissolved in ammonia water and distilled water are added, and baked at 700 ° C. Has been disclosed to form a surface layer by forming a layer made of tungsten oxide. Attempts have also been made to improve antifouling properties by blending not only inorganic components but also organic components.
- Patent Document 1 Conventional coating compositions including Patent Document 1 still have room for improvement.
- Patent Document 1 since only an inorganic component is blended, there is a problem that cracks are easily generated and peeled off when a coating film is formed on the surface of a large reflector used in a solar cell module or the like. is there.
- the present invention has been made in view of the above circumstances, and provides a coating composition that is excellent in antifouling properties, transparency, and hydrophilicity and can maintain surface hydrophilicity even at high temperatures when used as a coating film.
- One of the purposes is to do.
- the present inventors have included (A) metal oxide particles having a number average particle diameter of 1 nm to 400 nm and (B) polymer particles, and the inclusion of an aqueous phase component.
- the present inventors have found that the above problems can be solved by using a coating composition having an amount of a predetermined amount or less, and have completed the present invention.
- the present invention is as follows. [1] (A) a metal oxide having a number average particle size of 1 nm to 400 nm, (B) polymer particles, The coating composition whose content rate of the water phase component in the said (B) component represented by following formula (I) is 20 mass% or less.
- the component (B) (B1) component: a hydrolyzable silicon compound; (B2) component: vinyl monomer, (B3) component: an emulsifier, (B4) component: water,
- the coating composition according to any one of [1] to [3], wherein the number average particle diameter of the component (B) is 10 nm to 800 nm.
- the component (b2) is a vinyl monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group.
- the mass ratio of the component (b2) to the component (B) ((b2) / (B)) is 0.01 / 1 to 1/1, according to any one of [2] to [5] The coating composition as described.
- the mass ratio of the component (b2) to the component (A) ((b2) / (A)) is 0.01 / 1 to 1/1, according to any one of [2] to [6] The coating composition as described. [8] Any one of [1] to [7], wherein the component (B) has a core / shell structure including a core layer and one or more shell layers covering the core layer. A coating composition according to claim 1. [9] In the core layer, a mass ratio ((b2) / (b1)) of the component (b2) to the component (b1) is 0.01 / 1 to 1/1.
- the mass ratio of the component (b2) to the component (b1) ((b2) / (b1)) is 0.01 / 1 to 5/1.
- Coating composition [10]
- the component (B) is polymer emulsion particles obtained by polymerizing the polymerization stock solution in the presence of seed particles that form the core layer, The seed particles are at least one selected from the group consisting of the component (b1), the component (b2), and the component (b5): another vinyl monomer copolymerizable with the component (b2).
- the coating composition according to any one of [2] to [9], obtained by polymerizing the above.
- R 1 may have a hydrogen atom, or a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group or an epoxy group, and having 1 to 10 carbon atoms.
- N is an integer of 2 to 8)
- the component (A) is Component (A1): silica having a number average particle diameter of 1 nm to 400 nm, (A2) component: an infrared absorber having a number average particle size of 1 nm to 2000 nm, and a mass ratio of the total content of the component (A1) and the component (A2) to the content of the component (B) ( (A1 + A2) / (B)) is 60/100 to 1000/100, The mass ratio of the content of the component (A2) to the total content of the component (B) and the component (A1) ((A2) / (A1 + B)) is 0.05 / 100 to 40/100.
- the coating composition according to any one of [1] to [15].
- the component (A) is Component (A1): silica having a number average particle diameter of 1 nm to 400 nm, (A3) component: a photocatalyst having a number average particle diameter of 1 nm to 2000 nm, and a mass ratio of the total content of the component (A1) and the component (A3) to the content of the component (B) ((A1 + A3 ) / (B)) is 60/100 to 480/100, The mass ratio of the content of the component (A1) to the total content of the component (A1) and the component (A3) ((A1) / (A1 + A3)) is 85/100 to 99/100. [1] The coating composition according to any one of [16].
- a coating film comprising: A coating film having a water contact angle of 30 ° or less on the film surface when the component (B2) having a fractional molecular weight of 50,000 or less extracted from the component (B) by ultrafiltration is formed into a film.
- a coating film comprising: When the component (B2) having a molecular weight cut-off of 50,000 or less extracted from the component (B) by ultrafiltration is used as a film, the water contact angle on the film surface exceeds 30 °, and the content is 5 The coating film which is less than mass%.
- Coating film. [29] A substrate; A coating film formed by applying the coating composition according to any one of [1] to [22], formed on at least one surface of the substrate, or any of [23] to [28] A coating film according to claim 1, A laminate comprising: [30] The laminate according to [29], wherein the light transmittance of the laminate is higher than the light transmittance of the substrate.
- each layer constituting the coating film is 10 nm to 800 nm, The laminate according to [32] or [33], wherein the total thickness ( ⁇ dn) of the coating film is 100 nm to 4000 nm.
- the ratio ((Rc) / (Rb)) of the reflectance (Rc) of the surface opposite to the substrate of the coating film to the reflectance (Rb) of the surface of the coating film side of the substrate is 98. % Or more, The laminate according to any one of [29] to [35].
- the laminated body as described in any one.
- the laminate according to [42] which is a protective member for the solar cell module.
- the present invention it is possible to provide a coating composition that is excellent in antifouling property, transparency and hydrophilicity when formed into a coating film, and can maintain surface hydrophilicity even at high temperatures.
- the present embodiment a mode for carrying out the present invention (hereinafter simply referred to as “the present embodiment”) will be described in detail.
- the following embodiments are exemplifications for explaining the present invention, and are not intended to limit the present invention to the following contents.
- the present invention can be implemented with appropriate modifications within the scope of the gist thereof.
- (meth) acryl means “acryl” and “methacryl” corresponding thereto
- (meth) acrylate means “acrylate” and corresponding methacrylate
- (meth) acrylate means “acrylate” and corresponding methacrylate ”
- (meth) acrylate ” means “acryloyl” and its corresponding methacryloyl ”.
- the coating composition of the present embodiment is (A) metal oxide particles having a number average particle diameter of 1 nm to 400 nm, (B) polymer particles,
- the content rate of the water phase component in the said (B) component represented by following formula (I) is 20 mass% or less.
- Content of water phase component (%) (Dry mass of filtrate obtained by filtering component (B) with a molecular weight cut off of 50,000) ⁇ (100 ⁇ total solid mass) / (mass of the filtrate ⁇ the mass of the filtrate) Liquid dry mass) ⁇ 100 / total solid content mass (I)
- the present inventors have found that the main cause of the increase in the contact angle of the film surface when the coating film is formed is that the aqueous phase component (hydrophobic component) flows out from the inside of the coating film. From this finding, it was found that the hydrophilicity of the coating film surface can be maintained by defining the distribution ratio to the aqueous medium with the content of the aqueous phase component in the component (B) in the above range.
- the “coating film” referred to in the present embodiment is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.
- the surface contact angle at 20 ° C. when this aqueous phase component is formed into a film is preferably 30 ° C. or less.
- the content is preferably 5% by mass or less.
- the surface contact angle refers to an angle formed by the dry film and the tangent of a water droplet present on the surface, and can be measured by a droplet method.
- “hydrophilic” means that the contact angle of water (23 ° C.) with respect to the surface of the measurement object is preferably 60 ° or less, more preferably 30 ° or less, and still more preferably 20 ° or less. It means to become.
- the coating composition of the present embodiment includes (A) component: a metal oxide having a number average particle size of 1 nm to 400 nm. Thereby, it can be set as the coating film with high coating transparency and hydrophilicity.
- the component (A) is considered to act as a curing agent for the component (B) by interacting with the component (B) (however, the function is not limited thereto). The interaction is not particularly limited.
- the functional group for example, a hydroxyl group
- the functional group for example, a hydroxyl group
- the functional group for example, a carboxyl group, an amide group, an amino group, and the like
- Examples thereof include a hydrogen bond with an ether group and the like, and a chemical bond (for example, condensation) between the functional group that the component (A) generally has and the component (B).
- the particle diameter of the component (A) means a number average particle diameter (may be a mixture of primary particles and secondary particles, or only one of primary particles and secondary particles).
- the thickness is 1 nm to 400 nm, preferably 1 nm to 100 nm, more preferably 3 nm to 80 nm, and still more preferably 5 nm to 50 nm.
- the number average particle diameter of a component By making the number average particle diameter of a component into the said range, it can contribute to optical characteristics etc., such as a coating film obtained and a laminated body. In particular, setting the number average particle diameter to 100 nm or less can greatly improve the light transmittance of the resulting coating film or laminate.
- the number average particle diameter in the present embodiment (hereinafter, sometimes simply abbreviated as “particle diameter”) is measured according to the method of Examples described later.
- the metal oxide used for the component (A) is not particularly limited, and a known metal oxide can be used.
- silicon dioxide, aluminum oxide, antimony oxide, titanium oxide One or more selected from the group consisting of indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, and cerium oxide are preferable.
- silicon dioxide (silica), aluminum oxide (alumina), antimony oxide, and complex oxides thereof One or more selected from the above are more preferable.
- the component (A) having a large number of surface hydroxyl groups can form a continuous phase. Therefore, the hydroxyl group density on the coating film surface is increased and the hydrophilicity of the coating film itself is increased. Oxides are more preferred.
- the metal oxide of a component may be used individually by 1 type, and may be used in combination of 2 or more type.
- the form of the component (A) is not particularly limited, and examples thereof include powders, dispersions, and sols.
- the term “dispersion liquid” and “sol” as used herein means that the component (A) is 0.01 to 80% by mass, preferably 0.1 to 50% by mass in water, a hydrophilic organic solvent or a mixed solvent thereof. Means a state of being dispersed as at least one of primary particles or secondary particles.
- hydrophilic organic solvent examples include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, and ethers such as tetrahydrofuran and dioxane.
- Alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol
- ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone
- ethers such as tetrahydrofuran and dioxane.
- Amides such as dimethylacetamide and dimethylformamide, dimethyl sulfoxide and nitrobenzene, and mixtures of two or more thereof.
- a suitable one can be selected as the component (A).
- the properties that can be imparted to the coating composition or the coating film include antireflection properties, solvent resistance, antistatic properties, heat resistance, hard coat properties, photocatalytic activity, and the like.
- suitable components contents, physical properties such as number average particle diameter, and the like.
- two or more metal oxides can be used in combination. Typical examples from such a viewpoint include (A1) silica, (A2) infrared absorber, (A3) photocatalyst, and (A4) conductive metal oxide.
- the component (A1) may be silica (so-called silicon dioxide), and the production method is not particularly limited, and may be produced by a precipitation method, a dry method, or the like. From the viewpoint of handleability, colloidal silica is more preferable.
- the component (A1) is colloidal silica, it can be prepared and used by a sol-gel method, and a commercially available product can also be used.
- colloidal silica is prepared by the sol-gel method, Werner Stover et al; Colloid and Interface Sci.
- Colloidal silica is a dispersion of water or a water-soluble solvent of silica having silicon dioxide as a basic unit, and its number average particle diameter is preferably 1 nm to 400 nm, more preferably 1 nm to 200 nm, still more preferably 1 nm. It is ⁇ 100 nm, more preferably 5 nm to 30 nm. If the number average particle diameter is 1 nm or more, the storage stability of the coating film and the coating composition described later is better, and if it is 100 nm or less, the transparency of the coating film becomes better.
- Colloidal silica having a particle size in the above range can be used in the state of an aqueous dispersion, whether acidic or basic, and depending on the stable region of the aqueous dispersion of component (B) mixed together.
- the pH can be appropriately selected.
- acidic colloidal silica using water as a dispersion medium examples include commercially available products such as SNOWTEX (trademark) -O, SNOWTEX-OS, SNOWTEX-OL, manufactured by Nissan Chemical Industries, and Adelite (trademark, manufactured by Asahi Denka Kogyo Co., Ltd.). ) AT-20Q, Clevosol (trademark) 20H12, Clevosol 30CAL25 manufactured by Clariant Japan, and the like.
- Examples of basic colloidal silica include silica stabilized by addition of alkali metal ions, ammonium ions, or amines. More specifically, as a commercial product, Snowtex-20, Snowtex-30, Snowtex-C, Snowtex-C30, Snowtex-CM40, Snowtex-N, Snowtex-N30, manufactured by Nissan Chemical Industries, Ltd. Snowtex-K, Snowtex-XL, Snowtex-YL, Snowtex-ZL, Snowtex PS-M, Snowtex PS-L, etc., Adelite AT-20, Adelite AT-30, Adelite made by Asahi Denka Kogyo Co., Ltd.
- colloidal silica using a water-soluble solvent as a dispersion medium commercially available products such as MA-ST-M (a methanol dispersion type having a number average particle diameter of 20 nm to 25 nm) and IPA-ST (number average) are available as commercial products.
- MA-ST-M a methanol dispersion type having a number average particle diameter of 20 nm to 25 nm
- IPA-ST number average
- Isopropyl alcohol dispersion type with a particle size of 10 nm to 15 nm EG-ST (ethylene glycol dispersion type with a number average particle size of 10 nm to 15 nm), EG-ST-ZL (ethylene glycol dispersion with a number average particle size of 70 nm to 100 nm) Type), NPC-ST (ethylene glycol monopropyl ether dispersion type having a number average particle diameter of 10 nm to 15 nm), and the like.
- Colloidal silica may be used alone or in combination of two or more.
- the metal oxide of the component (A) may contain colloidal silica as a main component, it may contain alumina, sodium aluminate or the like as a minor component.
- an inorganic base such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or ammonia
- an organic base such as tetramethylammonium
- the main component means a component contained in the metal oxide by 50% by mass or more, preferably 70% by mass or more.
- the infrared absorber as component (A2) is an organic substance, an inorganic substance, or a mixture thereof having an absorption band in the infrared region (wavelength of 800 nm or more).
- Examples of the infrared absorber include inorganic fine particles and organic fine particles.
- the inorganic fine particles the fine particles coated with cerium oxide, zinc oxide, and silica, indium oxide doped with tin (ITO), tin oxide doped with antimony (ATO), oxidized with fluorine doped Transparent conductive fine particles such as tin (FTO), noble metal fine particles such as silver, gold, platinum, rhodium and palladium, formula MxWyOz (where M element is H, He, alkali metal, alkaline earth metal, rare earth element, Mg) , Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb One or more elements selected from the group consisting of B, F, P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, and I Represent, Represents tungsten
- these infrared absorbers are relatively stable and can be made into fine particles, they are preferable because they can absorb wavelengths in the infrared region while suppressing scattering in the visible light region.
- at least one selected from the group consisting of ITO, ATO, cerium oxide, zinc oxide, and the agent coated with silica is more preferable.
- the organic fine particles are pigments having a maximum absorption wavelength in the near-infrared (800 nm to 1100 nm) wavelength band
- the type and composition thereof are not limited.
- a diimonium-based near-infrared absorbing dye is preferable.
- Diimonium-based near-infrared absorbing dyes have a strong absorption with a molar extinction coefficient of about 100,000 in the near-infrared region with a wavelength of 850 nm to 1100 nm and a slight absorption in the visible light region with a wavelength of 400 nm to 500 nm.
- the visible light permeability is superior to other near infrared absorbing dyes.
- One or more dyes selected from the group consisting of phthalocyanine dyes, organometallic complex dyes, and cyanine dyes having an absorption maximum at a wavelength of 750 nm to 950 nm and no absorption in the visible light region may be used. Two or more kinds may be used in combination.
- conductive polymers represented by polyaniline, polypyrrole, polythiophene, polyvinyl sulfonic acid and the like can also be used.
- a color pigment can be used alone or in combination as the component (A2).
- a colored pigment having a solar reflectance of 13% or more as defined in JIS A5759-1998 is preferable.
- white pigments such as titanium white and zinc oxide pigments; iron pigments; Red pigments such as iron pigments and quinacridone pigments; yellow pigments such as iron oxide pigments, iron hydroxide pigments, lead chromate pigments, and azo pigments; blue pigments such as phthalocyanine blue and complex oxide pigments Pigments; green pigments such as chrome green and phthalocyanine green pigments.
- Infrared absorbers are ideally non-absorbing in the infrared wavelength of sunlight, particularly in the wavelength region corresponding to the absorption band of silicon, but the average reflectance in the visible ultraviolet region wavelength of 300 nm to 780 nm is 25% or less.
- the average reflectance in the infrared region wavelength of 780 nm to 2500 nm is preferably 15% or more.
- the component (A2) when the component (A2) is included, it is preferable that absorption is 0.1% or more in a wavelength region of 1000 nm to 2500 nm.
- the wavelength region of 1000 nm to 2500 nm is a wavelength region where infrared rays are efficiently converted into heat, and it is preferable that absorption is 0.1% or more in this wavelength region, and more preferably 10% or more.
- this wavelength region also overlaps with the absorption region of silicon, the addition amount can be adjusted according to the infrared absorption ability of the infrared absorber.
- the number average particle diameter is preferably 10 nm to 2000 nm, more preferably 10 nm to 1500 nm, and still more preferably 10 nm to 1000 nm.
- the number average particle size is 10 nm or more, dispersion stability can be maintained, and when the number average particle size is 2000 nm or less, even when the amount of the component (A2) is large, the scattered light is not increased and the power generation efficiency of the solar cell is improved. It does not decline.
- the surface of the infrared absorber is coated uniformly or non-uniformly with silica used as the component (A1) (A2)
- An infrared absorber is preferred.
- the compounding stability with the component (A1) and the weather resistance of the infrared absorber (A2) can be further improved.
- the method of coating the infrared absorber with (A1) silica is not particularly limited, and a known method can be adopted.
- the infrared absorber is dispersed in water, dispersed with a high-pressure morphizer, and then stirred. It can be obtained by adding tetraethoxysilane or water glass and controlling the temperature while appropriately adjusting the pH.
- the form of the component (A2) is not particularly limited, and examples thereof include powders, dispersions, and sols.
- the term “dispersion” and “sol” as used herein means that the component (A2) is in a concentration of 0.01 to 80% by mass, preferably 0.1 to 50% by mass in water and / or a hydrophilic organic solvent. It means a state of being dispersed as primary particles and / or secondary particles.
- the number average particle diameter of the component (A2) observed in the dispersion or sol can contribute to the optical properties of the resulting coating film.
- setting the number average particle diameter to 100 nm or less can greatly improve the transparency of the resulting coating film.
- the photocatalyst as the component (A3) refers to a compound that expresses at least one of photocatalytic activity and hydrophilicity by light irradiation (hereinafter sometimes simply referred to as “photocatalyst”).
- photocatalyst a compound that expresses at least one of photocatalytic activity and hydrophilicity by light irradiation
- the surface of the obtained coating film is excellent in the degradation activity (organic matter decomposability) and contamination resistance of the contaminating organic substance.
- a photocatalyst for example, TiO 2 , ZnO, SrTiO 3 , BaTiO 3 , BaTiO 4 , BaTi 4 O 9 , K 2 NbO 3 , Nb 2 O 5 , Fe 2 O 3 , Ta 2 O 5 , K 3 Ta 3 Si 2 O 3 , WO 3 , SnO 2 , Bi 2 O 3 , BiVO 4 , NiO, Cu 2 O, RuO 2 , CeO 2 , and at least one element selected from the group consisting of Ti, Nb, Ta, and V Layered oxides (for example, JP-A-62-274452, JP-A-2-172535, JP-A-7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8 -89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10-24416 No.
- TiO 2 titanium oxide
- any of anatase type, rutile type and brookite type can be used.
- a conductive metal oxide can be used as the component (A4).
- conductive metal oxides include tin-doped indium oxide (ITO), antimony-doped tin oxide (ATO), tin oxide, and zinc oxide.
- ITO tin-doped indium oxide
- ATO antimony-doped tin oxide
- zinc oxide zinc oxide.
- aluminum oxide, antimony oxide, indium oxide, tin oxide, zirconium oxide, lead oxide, iron oxide, calcium silicate, magnesium oxide, niobium oxide, cerium oxide, etc. are used in combination. You can also
- a component is a polymer particle.
- Polymer particles are particles in which a monomer component having an unsaturated bond is a polymer that has been polymerized by the intervention of radicals, cations, anions, and the like.
- the content rate of the water phase component of (B) represented by Formula (I) is 20 mass% or less.
- the water phase component (B) component 20% by mass or less, it is possible to maintain excellent hydrophilicity even at high temperatures while being excellent in transparency and hydrophilicity.
- Content of water phase component (%) (Dry mass of filtrate obtained by filtering component (B) with a molecular weight cut off of 50,000) ⁇ (100 ⁇ total solid mass) / (mass of the filtrate ⁇ the mass of the filtrate) Liquid dry mass) ⁇ 100 / total solid content mass (I)
- the content of the water phase component in the component (B) is preferably 15% by mass or less, more preferably 10% by mass or less, so that the antifouling property, transparency and hydrophilicity are excellent, and only at high temperatures. And excellent hydrophilicity can be maintained even under high humidity, and even under high temperature and high humidity.
- the component (B) is preferably emulsion particles.
- a sea-island structure can be formed with (A) component and (B) component.
- the metal oxide is localized on the outermost surface of the coating film, and good hydrophilicity can be expressed by a hydrophilic group such as a hydroxyl group of the metal oxide.
- the emulsion particles are not particularly limited, and examples thereof include acrylic emulsion, styrene emulsion, acrylic styrene emulsion, acrylic silicon emulsion, silicon emulsion, and fluororesin emulsion.
- Component (B) is a polymerization stock solution containing (b1) component: hydrolyzable silicon compound, (b2) component: vinyl monomer, (b3) component: emulsifier, and (b4) component: water.
- component (B) a compound in which a hydroxyl group derived from the component (b1) and a polymerization product of the component (b2) are combined by hydrogen bonding or the like can be suitably used.
- Examples of the component (b1) include a compound represented by the following formula (4), a condensation product thereof, a silane coupling agent, and the like.
- W is an alkoxy group having 1 to 20 carbon atoms, a hydroxyl group, an acetoxy group having 1 to 20 carbon atoms, a halogen atom, a hydrogen atom, an oxime group having 1 to 20 carbon atoms, an enoxy group, an aminoxy group, and an amide. It represents at least one group selected from the group consisting of groups.
- R is a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or alkyl group having 1 to 20 carbon atoms or 1 carbon atom.
- x is an integer from 1 to 4
- a silane coupling agent means a silane derivative in which a functional group having reactivity with an organic substance such as a vinyl polymerizable group, an epoxy group, an amino group, a methacryl group, a mercapto group, or an isocyanate group exists in the molecule.
- the compound represented by the formula (4) include tetraalkoxysilanes such as tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetraisopropoxysilane, tetra-n-butoxysilane; Trimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, n-butyltrimethoxysilane, n-butyltriethoxysilane, n-pentyltrimethoxysilane, n-hexyltrimethoxysilane, n-heptyltrimethoxysilane
- a silicon alkoxide having a phenyl group for example, phenyltrimethoxysilane, phenyltriethoxysilane, diphenyldimethoxysilane, etc.
- a silicon alkoxide having a phenyl group is used, the polymerization stability in the presence of water and an emulsifier is good, which is preferable.
- the component (b1) may contain a silane coupling agent having a thiol group or a component (b1-1): a hydrolyzable silicon compound having a vinyl polymerizable group.
- a silane coupling agent having a thiol group or a component (b1-1): a hydrolyzable silicon compound having a vinyl polymerizable group.
- silane coupling agent having a thiol group examples include 3-mercaptopropyltrimethoxysilane and 3-mercaptopropyltriethoxysilane.
- Examples of the component (b1-1) include 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) ) Vinyl polymerizable properties such as acryloyloxypropyltri-n-propoxysilane, 3- (meth) acryloyloxypropyltriisopropoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, 2-trimethoxysilylethyl vinyl ether Examples thereof include a silane coupling agent having a group.
- silane coupling agents can generate chemical bonds by copolymerization or chain transfer reaction with the component (b2) described later. For this reason, when a silane coupling agent having a vinyl polymerizable group or a thiol group is used by mixing or combining with the component (b1) described above, the polymerization product of the component (b1) and the component (b2) described later are used. The polymerization product can be complexed by chemical bonding.
- Examples of the “vinyl polymerizable group” in the component (b1-1) include a vinyl group and an allyl group. Among these, a 3- (meth) acryloxypropyl group is preferable.
- the component (b1) may contain a component (b1-2): a cyclic siloxane oligomer.
- a component (b1-2) a cyclic siloxane oligomer.
- R ′ is a hydrogen atom, a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an unsubstituted or substituted carbon group. It represents at least one selected from the group consisting of an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted with a halogen atom.
- m is an integer, and 2 ⁇ m ⁇ 20. Of these, cyclic dimethylsiloxane oligomers such as octamethylcyclotetrasiloxane are preferred from the viewpoint of reactivity.
- the weight average molecular weight in terms of polystyrene of the condensation product is preferably 200 to 5000, more preferably 300 to 1000.
- the mass ratio of the content of the component (b1) to the content of the component (B) ((b1) / (B)) is preferably 0.01 / 100 to 80/100, more preferably from the viewpoint of polymerization stability. Is 0.1 / 100 to 70/100.
- the mass ratio ((b1-1) / (B)) of the content of the component (b1-1) to the content of the component (B) is preferably 0.01 / 100 to 20 / from the viewpoint of polymerization stability. 100, more preferably 0.5 / 100 to 10/100.
- the mass ratio ((b1-1) / (b2)) of the content of the component (b1-1) to the content of the component (b2) is preferably 0.1 / 100 to 100 / from the viewpoint of polymerization stability. 100, more preferably 0.5 / 100 to 50/100.
- the mass ratio ((b1-2) / (B)) of the content of the component (b1-2) to the content of the component (B) is preferably 0.01 / 100 to 20/100 from the viewpoint of hydrophilicity. More preferably, it is 0.5 / 100 to 5/100.
- the mass ratio of the content of the component (b1-2) to the content of the component (b2) ((b1-2) / (b2)) is preferably 0.5 / 100 to 50 / from the viewpoint of polymerization stability. 100, more preferably 1.0 / 100 to 20/100.
- the component is a vinyl monomer.
- the component (b2) is preferably a vinyl monomer having at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, an amide group, an amino group, and an ether group.
- a vinyl monomer having such a functional group it can chemically bond (for example, condensation) with a functional group possessed by another component other than the component (B) (for example, the metal oxide of the component (A)). It becomes easy and the interaction can be enhanced.
- hydroxyl group-containing vinyl monomer mentioned as the component (b2) include various kinds such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate.
- Hydroxyalkyl (meth) acrylates various hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether or 4-hydroxybutyl vinyl ether; various hydroxyl group-containing allyl ethers such as 2-hydroxyethyl allyl ether; Monoesters of polyoxyalkylene glycols obtained from various polyether polyols typified by various unsaturated carboxylic acids typified by (meth) acrylic acid; various hydroxyl group-containing monomers described above And adducts of various lactones typified by ⁇ -caprolactone; adducts of various epoxy group-containing unsaturated monomers typified by glycidyl (meth) acrylate and various acids typified by acetic acid; Adducts of various unsaturated carboxylic acids typified by (meth) acrylic acid and various monoepoxy compounds other than epoxides of ⁇ -olefins typified by “Cardura E” (trade name,
- carboxyl group-containing vinyl monomer examples include (meth) acrylic acid, 2-carboxyethyl (meth) acrylate, crotonic acid, itaconic acid, maleic acid or fumaric acid.
- amino group-containing vinyl monomer listed as the component (b2) include, for example, 2-dimethylaminoethyl (meth) acrylate, 2-diethylaminoethyl (meth) acrylate, 2-di-n-propylaminoethyl ( Various tertiary amino group-containing (meth) such as (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, 4-dimethylaminobutyl (meth) acrylate or N- [2- (meth) acryloyloxy] ethylmorpholine Acrylic esters; various tertiary amino group-containing aromatic vinyl monomers such as vinylpyridine, N-vinylcarbazole, N-vinylquinoline; N- (2-dimethylamino) ethyl (meth) acrylamide, N- (2-diethylamino) ethyl (meth) acrylamide, N- 2-d
- ether group-containing vinyl monomer (b2) examples include polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene higher fatty acid ester, polyoxyethylene-polyoxypropylene block copolymer
- vinyl monomers such as vinyl ethers, allyl ethers or (meth) acrylic acid esters having various polyether chains such as coalesced in the side chain.
- ether group-containing vinyl monomer a commercially available product can be used as the ether group-containing vinyl monomer.
- the number of oxyethylene units in the polyoxyethylene chain is preferably 2 to 30. If it is less than 2, the flexibility of the coating film tends to be insufficient, and if it exceeds 30, the coating film becomes soft and tends to be inferior in blocking resistance.
- amide group-containing vinyl monomer mentioned as the component (b2) include, for example, N-alkyl or N-alkylene substituted (meth) acrylamide. More specifically, for example, N-methylacrylamide, N-methylmethacrylamide, N-ethylacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide, N, N-diethylacrylamide, N-ethylmethacrylamide N-methyl-N-ethylacrylamide, N-methyl-N-ethylmethacrylamide, N-isopropylacrylamide, Nn-propylacrylamide, N-isopropylmethacrylamide, Nn-propylmethacrylamide, N-methyl- Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpyrrolidine, N-methacryloylpyrrolidine, N-acryloylpiperidine, N-methacryloylpiperidine,
- the component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both from the viewpoint of further improving hydrogen bonding properties with other components.
- a vinyl monomer having a tertiary amide group is preferable from the viewpoint of hydrogen bonding strength.
- the mass ratio ((b2) / (B)) of the content of the component (b2) to the content of the component (B) is preferably from 0.01 / 1 to 1/1.
- the ratio is 1/1 to 0.5 / 1, more preferably 0.2 / 1 to 0.4 / 1.
- the mass ratio of the content of the component (b2) to the content of the component (A1) ((b2) / (A1)) is 0.01 /% from the viewpoint of hydrogen bonding with the component (A1) and blending stability. It is 1 to 1/1, preferably 0.1 / 1 to 1/1, and more preferably 0.2 / 1 to 0.7 / 1.
- component (b3) examples include an acid emulsifier such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, and acidic emulsifier.
- an acid emulsifier such as alkylbenzene sulfonic acid, alkyl sulfonic acid, alkyl sulfosuccinic acid, polyoxyethylene alkyl sulfuric acid, polyoxyethylene alkyl aryl sulfuric acid, polyoxyethylene distyryl phenyl ether sulfonic acid, and acidic emulsifier.
- Anionic surfactants such as alkali metal (Li, Na, K etc.) salts, ammonium salts of acidic emulsifiers, fatty acid soaps; quaternary ammonium salts such as alkyltrimethylammonium bromide, alkylpyridinium bromide, imidazolinium laurate, pyridinium Salt, imidazolinium salt type cationic surfactant; polyoxyethylene alkyl aryl ether, polyoxyethylene sorbitan fatty acid ester, polyoxyethyleneoxypropylene block Polymers, nonionic surface active agent polyoxyethylene distyryl phenyl ether, and the like. These may be used individually by 1 type and may be used in combination of 2 or more type.
- a reaction having a radical polymerizable double bond from the viewpoint of improving the water dispersion stability of the obtained component (B) and improving the long-term antifouling property of the obtained coating film.
- a functional emulsifier examples include vinyl monomers having a sulfonic acid group or a sulfonate group, vinyl monomers having a sulfate ester group, and vinyls having nonionic groups such as alkali metal salts, ammonium salts, and polyoxyethylene thereof. Examples thereof include a monomer and a vinyl monomer having a quaternary ammonium salt.
- a vinyl monomer having a sulfonic acid group or a sulfonate group for example, it has a radical polymerizable double bond and is partially substituted by a substituent such as an ammonium salt, sodium salt or potassium salt of the sulfonic acid group.
- the vinyl monomer having a sulfate ester group for example, it has a radical polymerizable double bond and is partially substituted by a substituent such as ammonium salt, sodium salt or potassium salt of the sulfate ester group.
- a substituent such as ammonium salt, sodium salt or potassium salt of the sulfate ester group.
- the compound having a succinic acid group partially substituted with a substituent such as ammonium salt, sodium salt or potassium salt of sulfonic acid group include allylsulfosuccinate. More specifically, for example, Eleminol JS-2 (trade name, manufactured by Sanyo Kasei Co., Ltd.), Latemul S-120, S-180A or S-180 (trade name, manufactured by Kao Corporation) and the like can be mentioned.
- Examples of compounds having an alkyl ether group having 2 to 4 carbon atoms or a polyalkyl ether group having 2 to 4 carbon atoms, partially substituted by a substituent such as an ammonium salt, sodium salt or potassium salt of a sulfonic acid group examples include Aqualon HS-10 or KH-1025 (Daiichi Kogyo Seiyaku Co., Ltd., trade name), Adekaria Soap SE-1025N or SR-1025 (Asahi Denka Kogyo Co., Ltd. trade name), and the like.
- vinyl monomer having a nonionic group examples include ⁇ - [1-[(allyloxy) methyl] -2- (nonylphenoxy) ethyl] - ⁇ -hydroxypolyoxyethylene (trade name: Adekari Soap NE). -20, NE-30, NE-40, etc., manufactured by Asahi Denka Kogyo Co., Ltd.), polyoxyethylene alkylpropenyl phenyl ether (trade names: Aqualon RN-10, RN-20, RN-30, RN-50, etc., first (Manufactured by Pharmaceutical Industry Co., Ltd.).
- the amount of the component (b3) used is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (B) from the viewpoint of polymerization stability.
- the component (B) is a polymer obtained by polymerizing the component (b1) and the component (b2) in the polymerization stock solution containing the components (b1) to (b3) and the component (b4) (that is, water). Combined emulsion particles.
- the amount of component (b4) used is preferably 30 to 99.9% by mass as the content in the polymerization stock solution from the viewpoint of polymerization stability.
- the polymerization stock solution is preferably further mixed with component (b5): another vinyl monomer copolymerizable with component (b2).
- component (b5) means that the properties of the polymerization product to be produced (glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, hydrolyzable silicon compound as component (b1) From the viewpoint of controlling the compatibility with the polymerization product, etc.).
- component (b5) examples include acrylic acid esters, methacrylic acid esters, aromatic vinyl compounds, vinyl cyanides, epoxy group-containing vinyl monomers, carbonyl group-containing vinyl monomers, anionic vinyl monomers. And a monomer containing a functional group such as
- the proportion of the component (b5) in the total vinyl monomer is preferably 0.001 to 30% by mass, and more preferably 0.05 to 10% by mass.
- Use of component (b5) in this range means that glass transition temperature, molecular weight, hydrogen bonding force, polarity, dispersion stability, weather resistance, compatibility with polymerized product of hydrolyzable silicon compound as component (b1) From the viewpoint of controlling the above and the like.
- a chain transfer agent can be mixed in the polymerization stock solution.
- the chain transfer agent include alkyl mercaptans such as n-octyl mercaptan, n-dodecyl mercaptan and t-dodecyl mercaptan; aromatic mercaptans such as benzyl mercaptan and dodecyl benzyl mercaptan; thiocarboxylic acids such as thiomalic acid or Examples thereof include salts thereof or alkyl esters thereof, or polythiols, diisopropylxanthogen disulfide, di (methylenetrimethylolpropane) xanthogen disulfide and thioglycol, and allyl compounds such as ⁇ -methylstyrene dimer.
- the amount of these chain transfer agents used is preferably 0.001 to 30 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total amount of all vinyl monomers. Use of a chain transfer agent in this range is preferred from the viewpoint of polymerization stability.
- a dispersion stabilizer can be mixed in the polymerization stock solution.
- the dispersion stabilizer is not particularly limited, and for example, various water-soluble oligomers selected from the group consisting of polycarboxylic acids and sulfonates, polyvinyl alcohol, hydroxyethyl cellulose, starch, maleated polybutadiene, maleated alkyd resin, poly Synthetic or natural water-soluble or water-dispersible polymer materials such as acrylic acid (salt), polyacrylamide, water-soluble or water-dispersible acrylic resin and the like can be mentioned. These may be used individually by 1 type and may be used in combination of 2 or more type.
- the amount of the dispersion stabilizer used is preferably 10 parts by mass or less, more preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the component (B) polymer emulsion particles.
- the above polymerization stock solution is preferably polymerized in the presence of a polymerization catalyst.
- a polymerization catalyst examples include hydrogen halides such as hydrochloric acid and hydrofluoric acid, carboxylic acids such as acetic acid, trichloroacetic acid, trifluoroacetic acid and lactic acid, sulfonic acids such as sulfuric acid and p-toluenesulfonic acid, and alkylbenzene.
- Acid emulsifiers such as sulfonic acid, alkylsulfonic acid, alkylsulfosuccinic acid, polyoxyethylene alkylsulfuric acid, polyoxyethylene alkylarylsulfuric acid, polyoxyethylene distyrylphenyl ether sulfonic acid, acidic or weakly acidic inorganic salt, phthalic acid, Acidic compounds such as phosphoric acid and nitric acid; sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide, tributylamine, diazabicycloundecene, ethylenediamine , Basic compounds such as diethylenetriamine, ethanolamines, ⁇ -aminopropyltrimethoxysilane, ⁇ - (2-aminoethyl) -aminopropyltrimethoxysilane; tin compounds such as dibutylt
- acidic emulsifiers having an action as an emulsifier as well as a polymerization catalyst, particularly alkylbenzenesulfonic acid having 5 to 30 carbon atoms (dodecylbenzene) Sulfonic acid etc. are preferred.
- a radical polymerization catalyst that causes radical polymerization by heat or a reducing substance to cause addition polymerization of a vinyl monomer is suitable.
- radical polymerization catalysts include water-soluble or oil-soluble persulfates, peroxides, and azobis compounds, and these are preferred.
- radical polymerization catalyst for example, potassium persulfate, sodium persulfate, ammonium persulfate, hydrogen peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, 2,2-azobisisobutyro Nitriles, 2,2-azobis (2-diaminopropane) hydrochloride, 2,2-azobis (2,4-dimethylvaleronitrile) and the like.
- the amount of the polymerization catalyst used is preferably 0.001 to 5 parts by mass with respect to 100 parts by mass of the total vinyl monomer.
- a reducing agent such as sodium bisulfite, ferrous chloride, ascorbate, Rongalite in combination with the radical polymerization catalyst. is there.
- the polymerization of the component (b1) and the polymerization of the component (b2) can be performed separately, but if performed at the same time, a micro organic / inorganic composite by hydrogen bonding or the like is achieved. It is preferable because it is possible.
- so-called emulsion polymerization in which the emulsifier polymerizes the component (b1) and the component (b2) in the presence of a sufficient amount of water to form micelles is suitable.
- emulsion polymerization for example, the component (b1) and the component (b2), and further the component (b3) as necessary or in an emulsified state, in a batch or divided or continuously in a reaction vessel.
- the polymerization may be carried out at a higher pressure or lower temperature conditions.
- the components (b1) to (b4) are added so that the total solid content is 0.1 to 70% by mass, preferably 1 to 55% by mass. It is preferable to mix.
- the total solid content mass (% by mass) can be obtained based on the following formula (II) by obtaining a dry mass obtained by putting the component (B) in an oven heated to 100 ° C. for 2 hours and drying it.
- Total solid mass (mass%) dry mass / mass of component (B) ⁇ 100 (II)
- the seed polymerization method is a method in which emulsion particles (seed particles) are previously present in an aqueous phase for polymerization.
- the pH in the polymerization system when performing the seed polymerization method is preferably 1.0 to 10.0, more preferably 1.0 to 6.0.
- the pH can be adjusted using a pH buffer such as disodium phosphate, borax, sodium hydrogen carbonate, ammonia or the like.
- the component (b1) and the component (b2) are optionally added in the presence of a solvent.
- a method of adding water after polymerization until the polymerization product becomes an emulsion can also be applied.
- the component (B) has a core / shell structure including a core layer and one or more shell layers covering the core layer from the viewpoint of improving the substrate adhesion of the obtained coating film. It is preferable.
- a method for forming the core / shell structure multistage emulsion polymerization in which emulsion polymerization is performed in multiple stages is very useful.
- the core / shell structure can be observed, for example, by morphological observation using a transmission electron microscope or the like, or analysis by viscoelasticity measurement.
- the component (B) is a polymer emulsion particle obtained by polymerizing the component (b1) and the component (b2) in the polymerization stock solution containing the seed particles that form the core layer.
- the multistage emulsion polymerization is, for example, as the first stage, in the presence of the component (b3) and the component (b4), and at least selected from the group consisting of the component (b1), the component (b2), and the component (b5).
- One or more components are polymerized to form seed particles, and as a second step, a polymerization stock solution containing components (b1) and (b2), and optionally (b5) components in the presence of the seed particles. Is added for polymerization (two-stage polymerization method).
- polymerization may be carried out by adding a polymerization stock solution further containing the component (b1) and the component (b2) and, if necessary, the component (b5). it can.
- a polymerization stock solution further containing the component (b1) and the component (b2) and, if necessary, the component (b5). It can.
- Such a method is also suitable from the viewpoint of polymerization stability.
- the mass ratio of the solid content mass (M1) in the polymerization stock solution used in the first stage to the solid content mass (M2) in the polymerization stock solution added in the second stage is preferably 9/1 to 1/9, more preferably 8/2 to 2/8, from the viewpoint of polymerization stability.
- the particle size distribution (volume average particle size / number average particle size) of the seed particles does not change greatly, and the particle size is increased by the second stage polymerization. It is preferred to have an increased structure.
- the volume average particle diameter can be measured in the same manner as the number average particle diameter.
- the mass ratio of the content of the component (b2) to the content of the component (b1) ((b2) / (b1)) is 0.01 / 1 to 1 / 1 is preferable.
- the mass ratio of the content of the component (b2) to the content of the component (b1) ((b2) / (b1)) is preferably 0.01 / 1 to 5/1. .
- the mass ratio ((b2) / (b1)) is 0.01 / 1 or more, the polymerization stability tends to be more excellent, and when it is 1/1 or less, durability and flexibility are obtained. Further improve.
- the interaction with the component (A) can be increased, and 5/1 or less. Therefore, the interaction can be moderately suppressed and sufficient stability tends to be obtained.
- the glass transition temperature (Tg) of the core layer of the core / shell structure is preferably 0 ° C. or lower.
- Tg can be measured with a differential scanning calorimeter (DSC).
- the number average particle diameter of the component (B) is preferably 10 nm to 800 nm.
- the number average particle size of component (B) is more preferably 10 nm to 100 nm.
- the ratio ((SA) / (SB)) of the surface area (SA) of the component (A) and the surface area (SB) of the component (B) is preferably in the range of 0.001 to 1000.
- the surface area of each component can be calculated from the particle diameter, the mass, and the specific gravity of the component (A) and the component (B), assuming that the particle shape is a true sphere.
- additive components that are usually added to and blended with paints and molding resins, such as light stabilizers, ultraviolet absorbers, and thickeners, depending on the application and method of use.
- a hindered amine light stabilizer is preferably used.
- a radical polymerizable light stabilizer having a radical polymerizable double bond in the molecule is preferable.
- an ultraviolet absorber an organic type ultraviolet absorber can be mentioned, for example. Examples of such organic ultraviolet absorbers include benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers. Among these, it is preferable to use a radical polymerizable ultraviolet absorber having a radical polymerizable double bond in the molecule. Moreover, a benzotriazole type ultraviolet absorber and a triazine type ultraviolet absorber having high ultraviolet absorbing ability are preferable.
- the light stabilizer is preferably used in combination with an organic ultraviolet absorber. Using both together can contribute to improving the weather resistance of the resulting coating film. Moreover, these organic ultraviolet absorbers, light stabilizers, and various additive components can be simply blended with the component (A1), the component (A2) and the component (B), or the component (B). It is also possible to coexist when synthesizing.
- the coating composition of the present embodiment preferably further contains a hydrolyzable silicon compound as component (C) for the purpose of improving the strength and antifouling property of the resulting coating film.
- a hydrolyzable silicon-containing compound used as the component (C) a hydrolyzable silicon-containing compound (c1) represented by the following formula (1) and a hydrolyzable silicon-containing compound represented by the following formula (2)
- One or more selected from the group consisting of (c2) and a hydrolyzable silicon compound (c3) represented by the following formula (3) can be used.
- R 1 may have a hydrogen atom or a halogen group, a hydroxy group, a mercapto group, an amino group, a (meth) acryloyl group, or an epoxy group, and has 1 to 10 carbon atoms.
- X represents a hydrolyzable group, and n is an integer of 0 to 3.
- the hydrolyzable group is not particularly limited as long as a hydroxyl group is generated by hydrolysis, and examples thereof include a halogen atom, an alkoxy group, an acyloxy group, an amino group, a phenoxy group, and an oxime group.
- X Si—R 2 n —SiX 3 (2)
- R 2 represents an alkylene group having 1 to 6 carbon atoms or a phenylene group.
- n is 0 or 1.
- R 3 represents an alkyl group having 1 to 6 carbon atoms.
- n is an integer of 2 to 8.
- hydrolyzable silicon compounds (c1) and (c2) include tetramethoxysilane, tetraethoxysilane, tetra (n-propoxy) silane, tetra (i-propoxy) silane, tetra (n-butoxy) silane, Tetra (i-butoxy) silane, tetra-sec-butoxysilane, tetra-tert-butoxysilane, trimethoxysilane, triethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, Propyltrimethoxysilane, propyltriethoxysilane, isobutyltriethoxysilane, cyclohexyltrimethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, dime
- hydrolyzable silicon compound (c3) represented by the formula (3) examples include a partial hydrolysis condensate of tetramethoxysilane (for example, trade name “M silicate 51” manufactured by Tama Chemical Industries, Colcoat) Trade name “MSI51” manufactured by Mitsubishi Chemical Corporation, trade names “MS51” and “MS56” manufactured by Mitsubishi Chemical Corporation), partially hydrolyzed condensate of tetoethoxysilane (trade names “Silicate 35” manufactured by Tama Chemical Industries, Ltd.) Silicate 45 ”, trade names“ ESI40 ”and“ ESI48 ”manufactured by Colcoat Co.), a co-hydrolyzed condensate of tetramethoxysilane and tetraethoxysilane (trade name“ FR-3 ”manufactured by Tama Chemical Industries, Ltd.), A product name “EMSi48” manufactured by Colcoat Co., Ltd.).
- the mass ratio ((A1 + A2) / B) of the total content of the component (A1) and the component (A2) to the content of the component (B) is not particularly limited, but the total light transmittance and infrared absorption From the viewpoint, it is preferably 60/100 to 1000/100, more preferably 100/100 to 500/100, and still more preferably 120/100 to 300/100.
- the mass ratio ((A2) / (B + A1)) of the content of the component (A2) to the total content of the component (B) and the component (A1) is preferably from the viewpoint of the total light transmittance of the coating film.
- 05/100 to 40/100 more preferably 0.1 / 100 to 20/100, and still more preferably 0.1 / 100 to 10/100.
- the mass ratio of the component (b2) to the component (B) ((b2) / (B)) is preferably 0.01 / 1 to 1/1, more preferably 0, from the viewpoint of polymerization stability.
- the ratio is 1/1 to 0.8 / 1, more preferably 0.2 / 1 to 0.5 / 1.
- the mass ratio of the component (b2) to the component (A) ((b2) / (A)) is preferably 0.01 / 1 to 1/1 / from the viewpoint of increasing the hydrogen bonding strength with the metal oxide. 1, more preferably 0.05 / 1 to 0.8 / 1, and still more preferably 0.1 / 1 to 0.4 / 1.
- the mass ratio of the content of the component (A2) to the total content of the component (B) and the component (A1) ((A2 ) / (A1 + B)) is 40/100 or less, the transparency of the coating film can be increased and the decrease in light transmittance due to scattering can be suppressed.
- the coating film Infrared absorption on the surface can be increased, temperature rise of silicon can be suppressed, and power generation efficiency can be improved.
- the mass ratio of the component (A) to the component (B) ((A) / (B)) is preferably 110/100 to 480/100, more preferably from the viewpoint of hydrophilicity and film formability. 110/100 to 300/100, more preferably 150/100 to 250/100. By setting such a ratio, the antifouling property, transparency and hydrophilicity can be further improved, as well as impact resistance and durability, and the hydrophilicity of the coating surface under high temperature, high humidity, or high temperature and high humidity. It can be excellent.
- the mass ratio of the component (C) to the component (A) ((C) / (A)) is preferably 1/100 to 150/100, more preferably 10/100 to 120/100, still more preferably 40. / 100 to 120/100.
- (C) / (A1) is 1/100 or more, there is a tendency that hydrophilicity can be maintained even under high temperature and high humidity conditions.
- (C) / (A) is 150/100 or less, a coating film is obtained. In some cases, the impact resistance tends to be improved.
- the component (A) preferably contains silica having a number average particle size of 1 nm to 400 nm as the component (A1) and an infrared absorber having a number average particle size of 1 nm to 2000 nm as the component (A2).
- the component (A1) can exist by forming a continuous phase between the particles of the component (B) while interacting with the component (B).
- silica particles with high hydrophilicity are present on the outermost surface of the coating film, so that high hydrophilicity can be obtained immediately after formation of the coating film regardless of light irradiation, as well as heat resistance, transparency, and weather resistance. The property can be improved.
- the mass ratio ((A1 + A2) / (B)) of the total content of the component (A1) and the component (A2) to the content of the component (B) is 60/100 to 1000/100.
- the mass ratio of the content of the component (A2) to the total content of the component (B) and the component (A1) ((A2) / (A1 + B)) is 0.05 / 100 to 40 / 100 is preferable.
- the component (A) preferably contains (A1) component: silica having a number average particle size of 1 nm to 400 nm and (A3) component: a photocatalyst having a number average particle size of 1 nm to 2000 nm.
- the component (A1) can exist by forming a continuous phase between the particles of the component (B) while interacting with the component (B).
- silica particles with high hydrophilicity are present on the outermost surface of the coating film, so that high hydrophilicity is obtained immediately after the formation of the coating film regardless of light irradiation, and transparency and weather resistance are further improved. It can improve.
- the mass ratio ((A1 + A3) / (B)) of the total content of the component (A1) and the component (A3) to the content of the component (B) is 60/100 to 480/100.
- the mass ratio of the content of the component (A1) to the total content of the component (A1) and the component (A3) ((A1) / (A1 + A3)) is 85/100 to 99/100. More preferably.
- the coating film obtained from the coating composition of the present embodiment is excellent in antifouling property, transparency, hydrophilicity and durability (impact resistance), and further, at high temperature, high humidity, or high temperature and high humidity.
- it can be set as the coating film which can maintain surface hydrophilicity, it can be used suitably for various uses.
- it can be suitably used as a coating composition for antireflection, solvent resistance, antistatic, heat resistance, and hard coat.
- the coating composition of the present embodiment does not have an excessively long curing time, and the restriction on the types of substrates that can be used can be relaxed. Furthermore, since the obtained coating film can also have the advantage of being excellent in light resistance, friction resistance and durability, it can also be suitably used as an antireflection coating composition.
- Various display panels such as liquid crystal display panels, cold cathode ray tube panels and plasma displays, displays such as signboards displayed outdoors, and electric bulletin boards prevent reflection of external light and prevent reflection to improve image quality It can be suitably used as a film.
- Examples of preferred embodiments of the antireflection coating composition and various members using the same include the following. By further satisfying the following conditions, not only antifouling properties, transparency and hydrophilicity, but also antireflection performance can be imparted to the coating film.
- the component (A) a metal oxide having a number average particle diameter of 1 nm to 400 nm
- the component (B) polymer emulsion particles having a number average particle diameter of 10 nm to 800 nm
- the component (B) is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing the components (b1) to (b4).
- the coating composition for antireflection has a mass ratio of the component (A) to the component (B) ((A) / (B)) of 50/100 to 450/100.
- the component (A) it is more preferable to use at least one selected from the group consisting of (A1) silica, (A3) photocatalyst, and (A4) conductive metal oxide. Advantages of using each of these components are as described above. In addition to this, when (A3) a photocatalyst is used, photocatalytic activity and hydrophilicity can be expressed by light irradiation, and the surface of the coating film is contaminated with organic substances. It is possible to more remarkably exhibit excellent decomposition activity and stain resistance.
- the mass ratio (b2) / (B) of the component (b2) to the component (B) is preferably 0.1 / 1 to 0.5 / 1.
- the mass ratio (b2) / (A) between the component (b2) and the component (A) is preferably 0.1 / 1 to 1/1.
- the component (B) preferably has a core / shell structure comprising a core layer and one or more shell layers covering the core layer. .
- the mass ratio (b2) / (b1) between the component (b2) and the component (b1) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer, The mass ratio (b2) / (b1) between the component (b2) and the component (b1) is preferably 0.1 / 1 to 5/1.
- the component (B) is obtained by polymerizing the polymerization stock solution in the presence of the seed particles forming the core layer, and the seed particles are the components (b1), (b2), And those obtained by polymerizing at least one selected from the group consisting of vinyl monomers copolymerizable with component (b2).
- the component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both.
- the particle size of the component (B) is preferably 120 to 450 nm.
- it is preferable that the component (C) described above is further included.
- An antireflective composite comprising the antireflective coating composition can be obtained.
- a display comprising the antireflection composite can be obtained.
- An exterior display member comprising the antireflection composite can be obtained.
- the coating composition of the present embodiment tends to interact with the component (A) and the component (B), not only the antifouling property, transparency and hydrophilicity of the resulting coating film are obtained. Moreover, since the advantage that it is excellent in a weather resistance etc. can also be provided, it can also be used suitably as a coating composition for solvent resistance. Since industrially produced articles are generally washed with a solvent such as alcohol in the manufacturing process, product assembly, and attachment process, solvent resistance is required. For example, in the case of an optical component such as an optical lens, surface dirt is wiped off with isopropyl alcohol or the like. However, if there is no solvent resistance at that time, the surface dissolves and optical properties such as transparency are obtained. Will fall. Therefore, it can be suitably used as a coating composition for imparting solvent resistance to such articles.
- Examples of preferred embodiments of the solvent-resistant coating composition and various members using the same include the following. By further satisfying the following conditions, not only transparency, hydrophilicity, antifouling properties, etc., but also solvent resistance can be imparted to the coating film.
- the solvent-resistant coating composition having a mass ratio of the component (A) to the component (B) ((A) / (B)) of 50/100 to 300/100 is preferable.
- the mass ratio of the component (b2) to the component (B) ((b2) / (B)) is preferably 0.1 / 1 to 0.5 / 1.
- the mass ratio of the component (b2) to the component (A) ((b2) / (A)) is preferably 0.1 / 1 to 1/1.
- the component (B) preferably has a core / shell structure comprising a core layer and one or more shell layers covering the core layer. .
- the mass ratio of the (b2) component to the (b1) component ((b2) / (b1)) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer, The mass ratio of the component (b2) to the component (b1) ((b2) / (b1)) is preferably 0.1 / 1 to 5/1.
- the component (B) is obtained by polymerizing a polymerization stock solution in the presence of seed particles forming the core layer, and the seed particles are the component (b1), (b2 And a component obtained by polymerizing at least one selected from the group consisting of vinyl monomers copolymerizable with the component (b2).
- the component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both.
- the number average particle diameter of the component (B) is preferably 20 to 250 nm.
- a solvent-resistant composite formed from the solvent-resistant coating composition can be obtained.
- a solvent-resistant composite comprising the solvent-resistant coating composition can be obtained.
- a display comprising the solvent-resistant composite can be obtained.
- an electroconductive metal oxide can be used as (A) component, antistatic ability can also be provided to a coating film. Thereby, it can also be used as an antistatic coating composition.
- the antistatic coating composition and various members using the same include the following.
- the component (A) it is more preferable to use at least one selected from the group consisting of (A1) silica, (A3) photocatalyst, and (A4) conductive metal oxide.
- the advantages of using these components are as described above, but by further satisfying the following conditions, not only antifouling properties, transparency, hydrophilicity, etc., but also antistatic performance can be imparted to the coating film. .
- the component (A) a metal oxide having a number average particle diameter of 1 nm to 400 nm
- component (B) polymer emulsion particles having a number average particle diameter of 10 nm to 800 nm, Including
- the component (B) is polymer emulsion particles obtained by polymerizing a polymerization stock solution containing the components (b1) to (b4).
- the antistatic coating composition having a mass ratio of the component (A) to the component (B) ((A) / (B)) of 150/100 to 450/100 is preferable.
- the mass ratio of the component (b2) to the component (B) ((b2) / (B)) is preferably 0.1 / 1 to 0.5 / 1.
- the mass ratio of the component (b2) to the component (A) ((b2) / (A)) is preferably 0.1 / 1 to 1/1.
- the component (B) preferably has a core / shell structure comprising a core layer and one or more shell layers covering the core layer. .
- the mass ratio (b2) / (b1) between the component (b2) and the component (b1) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer,
- the mass ratio (b2) / (b1) between the component (b2) and the component (b1) is preferably 0.1 / 1 to 5/1.
- the component (B) is obtained by polymerizing a polymerization stock solution in the presence of seed particles that form the core layer. It is preferably obtained by polymerizing at least one selected from the group consisting of a vinyl monomer copolymerizable with the component b1), the component (b2), and the component (b2).
- the component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both.
- the number average particle size of the component (B) is preferably 50 to 350 nm.
- an antistatic coating composition further comprising the component (C),
- the mass ratio of the component (A) to the component (B) ((A) / (B)) is 150/100 to 350/100,
- the mass ratio of the component (A) to the component (C) ((C) / (A)) is preferably 0.5 / 100 to 110/100.
- An antistatic composite comprising the above antistatic coating composition can be obtained.
- (A2) infrared absorber can be used as (A) component, heat resistance performance and heat insulation performance can also be provided to a coating film. Thereby, it can also be used as a thermal barrier coating composition.
- the component (A) at least one selected from the group consisting of (A1) silica, (A2) infrared absorber, (A3) photocatalyst, and (A4) conductive metal oxide is used. Is more preferable.
- the advantages of using each of these components are as described above. By further satisfying the following conditions, not only transparency, hydrophilicity, antifouling properties, etc., but also heat resistance and heat shielding performance are imparted to the coating film. Can do.
- the component (A1) silica having a number average particle diameter of 1 nm to 400 nm
- the component (A2) an infrared absorber having a number average particle size of 1 nm to 2000 nm
- a heat resistant coating composition comprising, as a component, polymer emulsion particles having a number average particle diameter of 10 nm to 800 nm.
- the component (A2) is at least one selected from the group consisting of indium oxide doped with tin, tin oxide doped with antimony, cerium oxide, zinc oxide, and the agent coated with silica.
- the component (B) is obtained by polymerizing the component (b1) and the component (b2) in a polymerization stock solution containing the components (b1) to (b4).
- the polymer emulsion particles obtained are preferred.
- the mass ratio of the total content ((A1 + A2) / (B)) of the component (A1) and the component (A2) to the content of the component (B) is 60/100 to 1000/100
- the mass ratio of the content of the component (A2) to the total content of the component (B) and the component (A1) ((A2) / (B + A1)) is 0.05 / 100 to 40/100. Is preferred.
- the mass ratio ((b2) / (B)) of the content of the component (b2) to the content of the component (B) is 0.1 / 1 to 0.5. / 1 is preferable.
- the mass ratio of the content of the component (b2) to the content of the component (A1) ((b2) / (A1)) is 0.1 / 1 to 1/1.
- the component (B) preferably has a core / shell structure comprising a core layer and one or more shell layers covering the core layer.
- the mass ratio of the content of the component (b2) to the content of the component (b1) ((b2) / (b1)) is 0.01 / 1 to 1/1.
- the mass ratio of the content of the component (b2) to the content of the component (b1) ((b2) / (b1)) is 0.1 / 1 to 5/1. It is preferable.
- the component (B) is obtained by polymerizing the component (b1) and the component (b2) in the polymerization stock solution containing seed particles that form the core layer.
- Polymer emulsion particles are at least one selected from the group consisting of the component (b1), the component (b2) and the component (b5): other vinyl monomers copolymerizable with the component (b2). Particles obtained by polymerizing the components are preferred.
- the component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both.
- it further comprises a component (C),
- the mass ratio of the content of the component (C) to the content of the component (A1) ((C) / (A1)) is preferably 1/100 to 100/100.
- the number average particle diameter of the component (B) is preferably 10 to 100 nm.
- the component (A1) is preferably colloidal silica having a number average particle diameter of 1 nm to 400 nm.
- the component (A2) has an absorption of 0.1% or more in a wavelength range of 1000 nm to 2500 nm.
- It can be set as the member for solar cells provided with a base material and the coating film formed by apply
- the coating composition of the present embodiment does not have an excessively long curing time, and the restriction on the types of substrates that can be used can be relaxed. Furthermore, since the obtained coating film can also have the advantage of being excellent in light resistance, friction resistance and durability, it can also be suitably used as a coating composition for hard coat.
- the following are mentioned as an example of the preferable aspect of the coating composition for hard-coats, and the various members using the same. By further satisfying the following conditions, not only antifouling properties, transparency, hydrophilicity, etc., but also hard coat performance can be imparted to the coating film.
- the component (A) a metal oxide having a particle size of 1 nm to 400 nm
- the component (B) polymer emulsion particles having a particle size of 10 nm to 800 nm, Including
- the component (B) is a polymer emulsion particle obtained by polymerizing a polymerization stock solution containing the components (b1) to (b4). It is preferable that the coating composition for hard coat has a mass ratio of the component (A) to the component (B) ((A) / (B)) of 50/100 to 350/100.
- the mass ratio of the component (b2) to the component (B) ((b2) / (B)) is preferably 0.1 / 1 to 0.5 / 1.
- the mass ratio of the component (b2) to the component (A) ((b2) / (A)) is preferably 0.1 / 1 to 1/1.
- the component (B) has a core / shell structure comprising a core layer and one or more shell layers covering the core layer. preferable.
- the mass ratio of the (b2) component to the (b1) component ((b2) / (b1)) is 0.01 / 1 to 1/1, and in the outermost layer of the shell layer,
- the mass ratio (b2) / (b1) of the component (b2) to the component (b1) is preferably 0.1 / 1 to 5/1.
- the component (B) is obtained by polymerizing the polymerization stock solution in the presence of the seed particles forming the core layer, and the seed particles are the components (b1), (b2), And those obtained by polymerizing at least one selected from the group consisting of vinyl monomers copolymerizable with component (b2).
- the component (b2) is preferably a vinyl monomer having a secondary amide group, a tertiary amide group, or both.
- the number average particle diameter of the component (B) is preferably 50 to 250 nm.
- the mass ratio of the component (A) to the component (B) ((A) / (B)) is 50/100 to 350/100, The mass ratio of the component (A) to the component (C) ((C) / (A)) is preferably 5/100 to 90/100.
- a coating film can be obtained from the coating composition of the present embodiment.
- the formation method of the coating film of this Embodiment is not limited, A well-known method can also be employ
- a coating composition can be formed by applying a coating composition dispersed in water, an organic solvent, or the like onto an object to be formed (for example, a substrate) and then drying. In more detail, it can also be set as the coating film of several layers by repeating the process which apply
- the coating composition is first applied to a substrate or the like and dried to obtain a single layer, and then the coating composition is applied onto the layer (ie, overcoated) and dried to obtain another layer. Can be used, and this can be repeated as necessary. Thus, a coating film in which a plurality of layers are laminated can be obtained.
- Another aspect of the coating film of the present embodiment is a coating film containing metal oxide particles (A) and polymer particles (B) surrounded by the component (A),
- the water contact angle on the film surface is 30 ° or less.
- the surface contact angle with water at 20 ° C. when the component (B2) having a molecular weight cut-off of 50,000 or less extracted from the component (B) is made into a dry film may be larger than 30 °.
- the composition of the component (B) and the component (B2) is not particularly limited. For example, you may employ
- the surface contact angle refers to an angle formed by the dry film and the tangent of a water droplet present on the surface, and can be measured by a droplet method.
- the content of the component (B2) is preferably 5% by mass or less.
- the distribution ratio to the aqueous medium is set to a specific range, so that it is high even under high temperature, high humidity, and even high temperature and high humidity. Surface hydrophilicity can be maintained.
- the coating film of the present embodiment can have a structure in which the metal oxide particles (A) surround the polymer particles (B), and it is preferable to take a so-called sea-island structure as a dispersion form thereof.
- the component (A) can be a sea phase and the component (B) can be an island phase.
- the component (A) preferably exists while forming a continuous phase between the particles of the component (B) while interacting with the component (B). In this case, the reflectance, weather resistance, and antifouling properties of the resulting coating composition can be further improved.
- the component (B) is preferably the above-described emulsion particles, and the emulsion particles are preferably the above-described polymer emulsion particles (B1).
- emulsion particles or polymer emulsion particles those described above can be used.
- a coating film having a surface water contact angle at 20 ° C. of 20 ° can be obtained.
- the water contact angle on the surface of the coating film after the high temperature and high humidity test which is allowed to stand for 24 hours under the conditions of 90 ° C. and 90% humidity is 20 ° or less.
- the water contact angle on the surface of the coating film after the high temperature and high humidity test is measured by the method described in Examples described later.
- a known high-temperature and high-humidity tester such as SH-661 manufactured by ESPEC can be used.
- distilled water can be placed in a sealed container, and the sealed container can be heated at a predetermined temperature to form saturated steam and used for evaluation.
- FIG. 1 is a schematic cross-sectional view of an example of the laminated body of the present embodiment.
- the laminated body 1 of this Embodiment is equipped with the base material 10 and the coating film 12 obtained by apply
- FIG. 1 is a schematic cross-sectional view of an example of the laminated body of the present embodiment.
- the laminated body 1 of this Embodiment is equipped with the base material 10 and the coating film 12 obtained by apply
- the method of forming a coating film using the coating composition of the present embodiment is not particularly limited, and examples thereof include a method of forming a coating film by applying the coating composition on a substrate and drying it.
- the solid content concentration of the coating composition is preferably 0.01 to 60% by mass, and more preferably 1 to 40% by mass.
- the viscosity (20 ° C.) of the coating composition is preferably 0.1 to 100,000 mPa ⁇ s, more preferably 1 to 10,000 mPa ⁇ s.
- the coating method of the coating composition on the substrate is not particularly limited.
- the laminate of the present embodiment can be subjected to heat treatment, ultraviolet irradiation, or the like as desired after forming a coating film on a substrate, for example.
- the temperature of the heat treatment is not particularly limited, but is preferably 20 ° C to 500 ° C, more preferably 40 ° C to 250 ° C.
- the coating film may be a single layer or may have two or more layers. It is preferable to use a plurality of layers because a plurality of functions can be imparted to the laminate.
- Examples of a method for forming a laminate having a plurality of coating films include the above-described method of overcoating.
- the substrate is not particularly limited, but preferably includes one selected from the group consisting of glass, acrylic resin, polycarbonate resin, cyclic polyolefin resin, polyethylene terephthalate resin, and ethylene-fluoroethylene copolymer.
- suitable materials can be appropriately selected according to desired physical properties. For example, from the viewpoint of transparency, weather resistance, and weight reduction, at least one selected from the group consisting of glass, acrylic resin, polycarbonate resin, cyclic olefin resin, polyethylene terephthalate resin, and ethylene-fluoroethylene copolymer, or a composite thereof It is preferable to use a material.
- a weathering agent or the like may be further kneaded into the acrylic resin, polycarbonate resin, cyclic polyolefin resin, polyethylene terephthalate resin, or ethylene-fluoroethylene copolymer.
- the substrate may be a single layer or a plurality of layers.
- the thickness of the coating film is preferably 0.05 ⁇ m to 100 ⁇ m, more preferably 0.1 ⁇ m to 10 ⁇ m. From the viewpoint of transparency, the thickness is preferably 100 ⁇ m or less, and in order to exhibit functions such as weather resistance and antifouling properties, the thickness is preferably 0.05 ⁇ m or more.
- the thickness (dn) of each layer is preferably 10 nm to 800 nm, and the total thickness ( ⁇ dn) of the coating film is more preferably 100 nm to 4000 nm.
- the ratio of the thickness within the above range, a light transmittance higher than that of the substrate or the single-layer coating film can be obtained.
- the thickness (dn) of any one of the plurality of layers is 10 nm or more, the film thickness can be easily controlled, and even when the coating film is formed on the uneven substrate surface, the coating film Can be effectively suppressed.
- the thickness (dn) of any layer is 800 nm or less, the light transmittance can be maintained high.
- the total thickness ( ⁇ dn) of a plurality of layers depends on the thickness of a single layer constituting the plurality of layers. If the total thickness ( ⁇ dn) is 100 nm or more, the thickness of the single layer is secured. Therefore, the film thickness can be easily controlled. Moreover, when the total thickness ( ⁇ dn) of the plurality of layers is 4000 nm or less, a high light transmittance can be exhibited as compared with a coating film consisting of only a single layer having the same film thickness.
- the thickness (dn) of each layer is 10 nm to 800 nm
- a method for obtaining a laminate having a total thickness of the coating film ( ⁇ dn) of 100 nm to 4000 nm is, for example, Examples thereof include a method of suppressing the solid content concentration in the coating composition of the present embodiment as the raw material to 1 to 10% by mass, for example. By pressing the solid content concentration within the above range, the total thickness of the coating film can be set within the above range.
- the present inventors set the layer thickness (dn and ⁇ dn) of the coating film within the above range, It has been found that a light transmittance higher than that of the substrate and the single layer coating can be obtained. Further, it has been found that the light transmittance can be more effectively improved by diluting the coating composition as a raw material of the coating film with water so that the solid content concentration is preferably 1 to 10% by mass. It was. Although these reasons are not clarified in detail, the following can be considered as one of the reasons.
- the component (A), the component (B), etc. are considered to have a concentration and pH at which the solid particles can exist in a stable dispersion state, and preferably rapidly using a diluting solvent such as water or alcohol. By diluting, it is presumed that the dispersion state becomes unstable and forms a certain type of aggregate or soft aggregate.
- a coating film composed of a plurality of layers is formed using a coating composition in which a certain type of aggregate or soft agglomerate is stably formed, the porosity of the coating film increases, and light transmission It is thought that the rate has improved.
- the light transmittance of the laminate is higher than the light transmittance of the substrate.
- the energy output of energy converters such as a solar cell
- the light transmittance in this Embodiment is measured according to the method as described in the Example mentioned later.
- the light transmittance of the substrate is preferably 30% to 99%, more preferably 70% to 99%, and still more preferably 80% to 99%. By setting the light transmittance of the substrate in the above range, a solar cell with high output can be obtained practically.
- the light transmittance can be measured according to JIS K7105.
- the refractive index of the coating film is 0.1 or more lower than the refractive index of the substrate. Thereby, the light transmittance can be increased.
- the refractive index of the outermost layer on the side on which sunlight enters is lower by 0.1 or more than the refractive index of a layer adjacent to the outermost layer. Thereby, since a refractive index falls in steps toward the base material from the incident side of sunlight, the reflection to the coating-film surface can be suppressed and light transmittance can be improved.
- the reflectance is measured according to the method described in Examples described later.
- the difference in refractive index between the coating film and the substrate is preferably 0.2 or less.
- the refractive index of the coating film according to this embodiment is preferably 1.30 to 1.48, and more preferably 1.34 to 1.43. Moreover, it is preferable that both the refractive index of a coating film and the refractive index of an outermost layer are in the said range.
- the refractive index of the coating film and the outermost layer can be selected depending on the type, thickness, and shape of the substrate used, but the coating film strength is improved by setting the refractive index of the coating film to 1.30 or more. When the refractive index of the coating film is 1.48 or less, light scattering can be suppressed, and in particular, the haze value tends to be reduced.
- the ratio (Rb / Rc) of the reflectance (Rc) of the surface (S1) opposite to the substrate in the coating film to the reflectance (Rb) of the coating film side surface (S2) in the substrate is 98%.
- the above is preferable, 99.5% or more is more preferable, and 99.7% or more is further preferable (see FIG. 1).
- the reduction rate ((Rb ⁇ Rc) / Rb) of the reflectance (Rc) with respect to the reflectance (Rb) is preferably 2% or less, preferably 0.5% or less, and 0.3% or less. Is more preferable.
- the base material When a coating is obtained by recoating a coating film with a certain film thickness, the base material is absorbed by light absorption by the coating film itself, light scattering at the interface between the coating film and the coating film, and between the coating films.
- the reflectance (Rc) of the coating film tends to be lower than the reflectance (Rb). This tendency is particularly remarkable when a substrate having a high reflectance (Rb) is used.
- the reduction rate of the reflectance (Rc) with respect to the reflectance (Rb) is 2% or less even when the coating film is repeatedly laminated by the repeated coating of the coating film. It is possible to suppress it.
- the reflectance may be further reduced, but the reduction rate is preferably 2% or less in consideration of energy efficiency.
- the reflectance (Rb) is preferably 80% or more. Thereby, sunlight can be collected efficiently and the power generation cost of the apparatus can be suppressed.
- the manufacturing method of the laminate of the present embodiment may be a method for forming a coating film on a substrate, and a known method may be employed.
- a known method may be employed.
- at least one surface of the base material is coated with the coating composition of the present embodiment to form a coating film, and the coating film is heated to 70 ° C. or more, 0.1 kPa or more.
- the manufacturing method which has the process of performing the pressurization process of these, or both.
- the method described above can be employed as a method for obtaining the coating film of the present embodiment.
- a coating film can be made denser by performing the process which heat-processes 70 degreeC or more, the pressurization process of 0.1 kPa or more, or both with respect to the obtained coating film.
- the method for the heat treatment is not particularly limited, and can be performed using a known device or the like.
- the method for the pressure treatment is not particularly limited, and can be performed using a known apparatus or the like.
- the laminated body of this Embodiment can be used suitably as a member for energy converters.
- the energy conversion device include a power generation device using sunlight.
- the member which can be used for the electric power generation using sunlight for example is said, More specifically, the member used for a solar cell module, the member used for a solar thermal power generation system, etc. are mentioned. More specifically, a cover glass that is a protective member on the surface of the solar cell module, a back sheet that is a protective member on the back surface, a sealing material, a formwork such as an aluminum frame, a Fresnel lens of a concentrating solar cell, solar thermal power generation It can be used as a light reflecting mirror used in the above.
- the laminate of the present embodiment is suitable as a protective member for a solar cell module.
- a large-scale solar cell module is installed and used in a desert, etc.
- sand that has been risend by the wind adheres to the protective member of the solar cell module, so that the surface of the member is damaged, transparency or antifouling property There arises a problem that the effect of the decrease.
- the coating film of the laminate of this embodiment is excellent in antifouling property, transparency, hydrophilicity, durability (impact resistance), and can maintain surface hydrophilicity even under high temperature and high humidity. It is also possible to easily wash away sand, dust and the like with rainwater.
- FIG. 2 is a simplified cross-sectional view of one aspect of the solar cell of the present embodiment.
- the solar cell module 2 according to the present embodiment includes a protection member 20, a back sheet 22 disposed to face the protection member 20, and a power generation element 24 disposed between the protection member 20 and the back sheet 22. And comprising. Further, the power generating element 24 is sealed with a sealing material 26. In the solar cell module 2, sunlight L enters from the protective member 20 side and reaches the power generation element 24.
- the protective member 20 is a protective member that protects the power generation element 24 and the like.
- the protective member 20 has a coating film 204 formed on the surface of the substrate.
- the protective member 20 functions as a light-transmitting substrate that transmits sunlight, and is excellent in the above-described antifouling property and infrared shielding property, an increase in the module temperature of the solar cell can be suppressed.
- the protective member 20 is preferably used so that the surface on which the coating film 204 is formed is the surface side of the solar cell module 2.
- the protective member 20 preferably has performance for ensuring long-term reliability in outdoor exposure of the solar cell module 2, such as weather resistance, water repellency, contamination resistance, and mechanical strength. Moreover, in order to utilize sunlight effectively, it is preferable that it is a highly transparent member with a small optical loss.
- the material of the substrate 202 is not particularly limited, and the above-described materials can be used. More specifically, a glass substrate; a polyester resin, a fluororesin, an acrylic resin, a resin film made of a cyclic olefin (co) polymer, an ethylene-vinyl acetate copolymer, or the like is preferable. Among these, weather resistance, A glass substrate is more preferable from the viewpoint of balance between impact properties and cost.
- the total light transmittance of light having a wavelength of 350 to 1400 nm is preferably 80% or more, more preferably 90% or more.
- a white plate glass with little absorption in the infrared region but even a blue plate glass usually has little influence on the output characteristics of the solar cell module if the thickness is 3 mm or less.
- tempered glass can be obtained by heat treatment to increase the mechanical strength of the glass substrate, but float plate glass without heat treatment may be used.
- the resin film is preferably a polyester resin from the viewpoint of transparency, strength, cost, etc., and more preferably a polyethylene terephthalate resin.
- a fluororesin having particularly good weather resistance is also preferably used.
- ethylene tetrafluoride-ethylene copolymer ETFE
- polyvinyl fluoride resin PVDF
- PVDF polyvinylidene fluoride resin
- TFE polytetrafluoroethylene-6
- FEP fluorinated propylene copolymer
- CTFE poly (trifluorotrifluoroethylene resin)
- a polyvinylidene fluoride resin is preferable from the viewpoint of weather resistance, but an ethylene tetrafluoride-ethylene copolymer is preferable from the viewpoint of achieving both weather resistance and mechanical strength.
- the above-described coating film can be used.
- the method described above can also be used for forming the coating film 204 on the substrate 202.
- seat 22 since it is located in the outermost layer of a solar cell module, it is preferable to have various characteristics, such as a weather resistance and mechanical strength, like the above-mentioned protective member 20. Therefore, you may comprise a back seat
- a polyester resin and a glass substrate can be preferably used, and among these, a polyethylene terephthalate resin (PET) is more preferable from the viewpoint of weather resistance and cost.
- PET polyethylene terephthalate resin
- a reinforcing plate may be attached for the purpose of increasing the mechanical strength of the solar cell module 2 and for preventing the distortion and warpage due to temperature change.
- a steel plate, a plastic plate, an FRP (glass fiber reinforced plastic) plate or the like can be preferably used.
- the backsheet 22 may have a multilayer structure composed of two or more layers.
- the multilayer structure include a structure in which one or more layers of the same component are laminated on both sides of the central layer so as to be symmetrical with respect to the central layer.
- PET / alumina vapor deposition PET / PET, PVF (brand name: Tedlar) / PET / PVF, PET / AL foil / PET etc. are mentioned, for example.
- the power generating element 24 is not particularly limited as long as it can generate power using the photovoltaic effect of the semiconductor.
- silicon single crystal, polycrystalline, amorphous
- compound semiconductor (3- Group 5, 2-6, etc.)
- polycrystalline silicon is preferred from the viewpoint of balance between power generation performance and cost.
- the sealing material 26 is not particularly limited as long as it is a member that can seal the power generating element 24.
- a resin sealing sheet containing a resin such as ethylene-vinyl acetate copolymer (EVA) is used. Can be mentioned. By heat-melting such a resin sealing sheet, the resin sealing sheet can be in close contact with the power generation element 24 or the like to be sealed and sealed. By using such a sealing material, creep of the power generation element can be prevented, and excellent adhesiveness to the protective member 20 and the backsheet 22 can be exhibited.
- EVA ethylene-vinyl acetate copolymer
- the manufacturing method of the solar cell in the present embodiment is not particularly limited, and a known method can be adopted.
- the protective member 20 / the sealing material 26 / the power generation element 24 / the sealing material 26 / the back sheet 22 are stacked in this order, and are vacuum-laminated using a vacuum laminator at 150 ° C. for 15 minutes.
- the thickness of each member of the solar cell module 2 is not particularly limited, the thickness of the protective member 20 is preferably 3 mm or more from the viewpoint of weather resistance and impact resistance, and the thickness of the back sheet 22 is from the viewpoint of insulation.
- the thickness of the power generation element 24 is preferably 140 ⁇ m to 250 ⁇ m from the viewpoint of the balance between power generation performance and cost, and the thickness of the sealing material 26 is 250 ⁇ m or more from the viewpoint of cushioning and sealing properties. preferable.
- FIG. 3 is a schematic perspective view of an example of the reflector device according to the present embodiment. It can be set as the reflector apparatus 3 provided with the light reflection mirror 32, the laminated body 30 of this Embodiment formed in the reflective surface side of the said light reflection mirror, and the support body 34 which supports the said reflection mirror 32.
- FIG. . A reflector device in which the laminated body 30 of the present embodiment is used as a protective member of the light reflecting mirror 32 (hereinafter sometimes simply referred to as “protective member”) can be provided.
- the structure of the reflector apparatus 3 is not specifically limited, It can deform
- ⁇ Solar thermal power generation system> it can be set as a solar thermal power generation system provided with the said reflector apparatus and the apparatus which converts the sunlight condensed by this reflector apparatus into an electrical energy.
- the configuration of the solar thermal power generation system is not particularly limited, and can be appropriately modified into a suitable configuration.
- the sample was diluted by adding a solvent so that the solid content in the sample was 0.1 to 20% by mass, and measured using a wet particle size analyzer (Microtrack UPA-9230 manufactured by Nikkiso).
- the haze value of the sample was measured according to JIS K7105 using the turbidimeter (Nippon Denshoku Industries make, NDH2000) (initial haze value).
- the light transmittance was measured according to JIS K7105.
- ESPEC's SH-661 is set at 40 ° C and 90% RH, the sample is stored for 16 hours, and then a drop of deionized water is placed on the coating surface for 1 minute at 23 ° C. After being allowed to stand, the contact angle was measured using a contact angle measuring device (Kyowa Interface Science, CA-X150 contact angle meter).
- ESPEC's SH-661 is set at 90 ° C and 90% RH, and the sample is allowed to stand for 24 hours. After standing for 1 minute, the contact angle was measured using a contact angle measuring device (Kyowa Interface Science, CA-X150 type contact angle meter).
- the pencil hardness of the sample was measured using a pencil hardness meter (manufactured by Tester Sangyo Co., Ltd.).
- the absolute reflectance of the sample was measured using a reflection spectral film thickness meter (manufactured by Otsuka Electronics Co., Ltd., FE3000).
- the surface resistance value of the sample was measured using a turbidimeter (manufactured by Nippon Denshoku Industries Co., Ltd., NDH2000).
- the pencil hardness of the sample was measured using a pencil hardness meter (manufactured by Tester Sangyo Co., Ltd.).
- the reflectance of the base material and the laminate was measured using an ultraviolet-visible near-infrared spectrophotometer (trade name “V-670” manufactured by JASCO Corporation) and a large integrating sphere meter. In the measurement, a value having the highest reflectance in the wavelength range of 350 nm to 500 nm was used as an evaluation value.
- a base material for measuring the reflectance of the laminated body a mirror obtained by depositing Al on 3 mm-thick blue plate glass was used. The coating composition was applied to the blue plate glass surface, and the reflectance of light incident from the coating surface was taken as a measured value.
- the coating film surface was observed 250,000 times using an electron microscope, and the maximum diameter and the maximum width of the pore diameter on the surface were determined. Furthermore, the circumscribed circle equivalent diameter was determined. The volume of the coating film was determined from the area of a square having a side of 1000 nm and the film thickness, and the porosity was calculated from the result.
- C / Si Carbon amount (C / Si) analysis of coating film surface
- the coating film formed on the base material was divided into small pieces of about 3 mm square and used as measurement samples. Measurement is performed using XPS (PHI Quantera SXM), excitation source: monoAlk ⁇ , 15 kV ⁇ 6.7 mA, analysis size: 1.5 mm ⁇ 100 ⁇ m, uptake region (survey scan; 0 to 1, 100 eV, Narrow scan; Si, 2p , C1s (K, 2p), O1s, Na1s, Ca2p, PassEnergy (survey scan; 200 eV, Narrow scan; 112 eV) The results obtained are based on the relative element concentration (atomic) of each element with Si element being 1. %) Was normalized and the C / Si ratio was calculated.
- the solution was simultaneously dropped over about 2 hours. Further, stirring was continued for about 2 hours in a state where the temperature in the reaction vessel was 80 ° C., then cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content was adjusted to 10.0% by mass with ion-exchanged water.
- the aqueous phase component was 18% by mass.
- the heat curing is continued for about 8 hours in a state where the temperature in the reaction vessel is 80 ° C., it is cooled to room temperature, filtered through a 100-mesh wire mesh, and the solid content is adjusted to 10.0% by mass with ion-exchanged water.
- an aqueous dispersion of polymer emulsion particles (HB-9) having a number average particle diameter of 90 nm was obtained.
- the aqueous phase component was 5% by mass.
- Examples 1 to 35; Tables 1 to 4 Made by Nissan Chemical Co., Ltd., trade name “Snowtex” (component (A)) dispersed in water (solid content 10% by mass), polymer emulsion particles (HB) obtained in Production Examples and tetraethoxysilane
- a coating composition was obtained by blending (C) shown in Table 1.
- the particle size of “Snowtex” listed in the table is a catalog value.
- the obtained coating composition was dip-coated on 5 cm ⁇ 5 cm glass, and then dried at 70 ° C. for 10 minutes to obtain a laminate having a coating film.
- the evaluation results are shown in Tables 1 to 4.
- the composite of each example was at least excellent in hydrophilicity and transparency. Furthermore, it was confirmed that the composites of Examples 47 and 48 were excellent in appearance after the solvent resistance test at a practical level.
- Example 54 Colloidal silica (manufactured by Nissan Chemical Industries, trade name “Snowtex O”, (A) dispersed in water, solid content 10 mass%, number average particle size 10 nm) and the polymer obtained in the production example Emulsion particles (HB-1), (HB-2) and tetraethoxysilane (C) were blended in the ratios shown in Table 10 to obtain a coating composition.
- colloidal silica manufactured by Nissan Chemical Industries, trade name “Snowtex O”
- the obtained coating composition was dip-coated on a 5 cm ⁇ 5 cm substrate (made of polycarbonate resin, thickness: 3 mm), and then dried at 70 ° C. for 10 minutes to obtain a coating film. Further, using a LM50 type vacuum laminator (NPC), the coating film was subjected to heat treatment and pressure treatment under the condition 1 (degassing at 150 ° C. for 5 minutes and then vacuum lamination for 10 minutes, pressure 100 kPa), A functional complex was obtained. Table 10 shows the evaluation results.
- Examples 55 and 56 A coating composition was obtained in the same manner as in Example 54 except that the composition was changed as shown in Table 10.
- the obtained coating composition was dip-coated on a 5 cm ⁇ 5 cm substrate (made of polycarbonate resin, thickness: 3 mm), and then dried at 70 ° C. for 10 minutes to obtain a coating film. Furthermore, the condition 1 was changed to the condition 2 (heating in air at 150 ° C. for 30 minutes), and the coating film was subjected to heat treatment to obtain a functional composite.
- Table 10 shows the evaluation results.
- Example 5 Only the polycarbonate resin as the substrate was used. Evaluation was performed in the same manner as in Example 1 except that the composition was changed as shown in Table 10. Table 10 shows the evaluation results.
- Example 57 Colloidal silica (manufactured by Nissan Chemical Industries, Ltd., trade name “Snowtex-OS” (component (A))) was diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 8 nm).
- the polymer emulsion particle aqueous dispersion synthesized in the production example is blended, and the component (C) tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-04”) is blended so as to have the composition shown in Table 11.
- the obtained coating composition was dip-coated on the glass-side surface of the substrate reflecting mirror (the back surface (lower surface) of the plate glass was subjected to an aluminum plating treatment) so as to have a predetermined thickness after drying. Next, the dip-coated one was dried at 70 ° C. for 30 minutes to obtain a laminate.
- a laminate produced in the same manner as described above was used as the measurement object except that the base material was changed from a reflecting mirror to white plate glass (thickness 2 mm, 6 ⁇ 6 cm square).
- Example 58 A laminate was produced in the same manner as in Example 57 except that the coating composition blended in the same manner as in Example 57 was used and the thickness of the coating film was changed as shown in Table 11. Furthermore, the coating composition was dip coated on the coating film of the laminate and dried at 70 ° C. for 30 minutes to obtain a laminate having a plurality of coating films.
- Example 59 Using the coating composition blended in the same manner as in Example 57 except that the composition shown in Table 11 was changed, lamination was performed in the same manner as in Example 57 except that the thickness of the coating film was changed as shown in Table 11. The body was made.
- Example 60 A laminate was prepared in the same manner as in Example 59 except that the coating composition blended in the same manner as in Example 59 was used and the thickness of the coating film was changed as shown in Table 11. Next, the surface of the coating film was rubbed 100 times with a paper file (# 1000) at a load of 22 g / cm 2 . Then, the coating composition was dip-coated on the coating film whose surface was rubbed, and dried at 70 ° C. for 30 minutes to obtain a laminate including a plurality of coating films.
- Table 11 shows the evaluation results of Examples and Comparative Examples.
- the laminate of each example was excellent in at least hydrophilicity, reflectance, transparency, and appearance.
- Example 61 (Laminated body, examination of transmittance; Tables 12 and 13) (Example 61)
- Product name “Snow Tech OS” (component (A)) manufactured by Nissan Chemical Industries, Ltd. was diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 8 nm), and synthesized in Production Example 1.
- a polymer emulsion (HB1) was blended, and a coating composition was obtained by blending as shown in Table 12 with trade name “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd. as tetraethoxysilane (C).
- the obtained coating composition was spin-coated on white plate glass (thickness 2 mm, 6 ⁇ 6 cm square) so as to have a film thickness of 250 nm, and then dried at 70 ° C. for 30 minutes to obtain a laminate.
- Example 62 After making a laminated body using the coating composition mix
- Example 63 A laminate was obtained in the same procedure as in Example 61 except that the coating liquid was adjusted according to the formulation shown in Table 12.
- Example 64 Lamination was repeated in the same procedure as in Example 61 to obtain a laminate in which 10 layers of the coating composition were laminated.
- Example 65 After the coating composition was laminated once by the same procedure as in Example 61, the coating surface was rubbed 10 times with steel wool (# 7448) at a load of 22 g / cm 2 . Thereafter, the coating composition was again laminated once to obtain a laminate.
- Example 66 A laminate was obtained in the same manner as in Example 61 except that the base material was changed to a polycarbonate resin “Iupilon” (thickness 3 mm, 5 ⁇ 5 cm square) manufactured by Mitsubishi Engineering Plastics.
- Comparative Example 10 The same coating was further repeated on the laminate obtained in Comparative Example 9, but a two-layer laminate could not be obtained due to the repellency of the coating solution.
- Tables 12 and 13 show the evaluation results of Examples and Comparative Examples.
- a photocatalyst (trade name “TSK-5”, manufactured by Ishihara Sangyo Co., Ltd., number average particle diameter 10 nm, silica-coated titanium oxide hydrosol) (component (A3)) and water of the polymer emulsion particles synthesized in the production example
- the dispersion was blended with the composition shown in Table 14 to obtain a coating composition, which was spin-coated on white plate glass (thickness 2 mm, 6 ⁇ 6 cm square) so as to have a film thickness of 250 nm. And then dried at 70 ° C. for 30 minutes to obtain a laminate comprising a white plate glass as a base material and a coating film provided thereon.
- Example 70 and 71 Further, as component (C), tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-04”) was blended and coated in the same manner as in Example 67 except that the composition shown in Table 14 was blended. A composition was obtained. A laminate was obtained in the same manner as in Example 67 except that the coating composition was used.
- component (C) tetraethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., trade name “KBE-04”) was blended and coated in the same manner as in Example 67 except that the composition shown in Table 14 was blended. A composition was obtained. A laminate was obtained in the same manner as in Example 67 except that the coating composition was used.
- Example 72 A coating composition was obtained in the same manner as in Example 67 except that the composition shown in Table 14 was used. A laminate was obtained in the same manner as in Example 67 except that the coating composition was used.
- Table 14 shows the results of Examples and Comparative Examples.
- the laminate of each example was excellent in at least initial hydrophilicity, transparency and refractive index, and also excellent in hydrophilicity after the weather resistance test and after the heating test. It was.
- Example 73 The product name “Snow Tech OS” (component (A)) manufactured by Nissan Chemical Industries, Ltd. was diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 8 nm), and the weight synthesized in the production example. The combined emulsion was blended, and a coating composition was obtained with the blending shown in Table 15. The obtained coating composition was spin-coated on white plate glass (thickness 2 mm, 6 ⁇ 6 cm square) to a film thickness of 250 nm, and then dried at 70 ° C. for 30 minutes to obtain a functional coating film.
- Example 74 A functional coating film was obtained in the same manner as in Example 74 except that the coating composition was obtained with the formulation shown in Table 15.
- Example 75 A functional coating film was obtained in the same manner as in Example 74 except that the coating composition was obtained with the formulation shown in Table 15.
- Example 76 The product name “Snow Tech OS” (component (A)) manufactured by Nissan Chemical Industries, Ltd. was diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 8 nm), and the weight synthesized in the production example The combined emulsion was blended, and a coating composition was obtained by blending the product name “KBE-04” manufactured by Shin-Etsu Chemical Co., Ltd. as tetraethoxysilane (C) with the formulation shown in Table 15. The obtained coating composition was spin-coated on white plate glass (thickness 2 mm, 6 ⁇ 6 cm square) to a film thickness of 250 nm, and then dried at 70 ° C. for 30 minutes to obtain a functional coating film.
- the product name “Snow Tech OS” (component (A)) manufactured by Nissan Chemical Industries, Ltd. was diluted with water to prepare a dispersion having a solid content of 10% by mass (number average particle size 8 nm), and the weight synthesized
- Example 77 A functional coating film was obtained in the same manner as in Example 74 except that the coating composition was obtained with the formulation shown in Table 15.
- Example 78 A functional coating film was obtained in the same manner as in Example 74 except that the coating composition was obtained with the formulation shown in Table 15.
- the obtained filtrate (H-2) was dip-coated on 5 cm ⁇ 5 cm blue plate glass and then dried at 90 ° C. for 24 hours to obtain a film-like test plate (I-2).
- a drop of deionized water was placed on the film surface of the obtained test plate (I-2) and left at 20 ° C. for 10 seconds. The initial contact angle was measured and found to be 56 °.
- the obtained filtrate (H-3) was dip-coated on 5 cm ⁇ 5 cm blue plate glass and then dried at 90 ° C. for 24 hours to obtain a film-like test plate (I-3).
- a drop of deionized water was placed on the film surface of the obtained test plate (I-3) and left at 20 ° C. for 10 seconds. The initial contact angle was measured and found to be 58 °.
- the obtained filtrate (H-5) was dip-coated on 5 cm ⁇ 5 cm blue plate glass, and then dried at 90 ° C. for 24 hours to obtain a film-like test plate (I-5).
- a drop of deionized water was placed on the film surface of the obtained test plate (I-5), allowed to stand at 20 ° C. for 10 seconds, and then the initial contact angle was measured to be 57 °.
- the obtained filtrate (H-7) was dip-coated on 5 cm ⁇ 5 cm blue plate glass, and then dried at 90 ° C. for 24 hours to obtain a film-like test plate (I-7).
- a drop of deionized water was placed on the film surface of the obtained test plate (I-7), allowed to stand at 20 ° C. for 10 seconds, and then the initial contact angle was measured to be 57 °.
- the obtained filtrate (H-8) was dip-coated on 5 cm ⁇ 5 cm blue plate glass, and then dried at 90 ° C. for 24 hours to obtain a film-like test plate (I-8).
- a drop of deionized water was placed on the film surface of the obtained test plate (I-8), allowed to stand at 20 ° C. for 10 seconds, and then the initial contact angle was measured to be 56 °.
- test plate (I-8) A drop of deionized water was placed on the film surface of the obtained test plate (I-8), allowed to stand at 20 ° C. for 10 seconds, and then the initial contact angle was measured to be 58 °.
- Example 79 To 100 g of the polymer emulsion particles (TB-1) aqueous dispersion synthesized in Production Example 12, water-dispersed colloidal silica having a number average particle size of 12 nm (trade name “Snowtex O”, manufactured by Nissan Chemical Industries, Ltd., solid content: 20% by mass ) 100 g was mixed and stirred to obtain a water-based organic / inorganic composite composition (E-1).
- the water-based organic / inorganic composite composition (E-1) is bar-coated on a 5 cm ⁇ 5 cm soda glass so that the film thickness becomes 1 ⁇ m, and then dried at 70 ° C. for 30 minutes, whereby an organic / inorganic composite film is formed.
- a test plate (G-1) having (F-1) was obtained.
- the test plate (G-1) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 80 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particle (TB-2) aqueous dispersion synthesized in Production Example 13 was used instead of the polymer emulsion particle (TB-1). A test plate (G-2) having F-2) was obtained. The test plate (G-2) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 81 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particle (TB-3) aqueous dispersion synthesized in Production Example 14 was used instead of the polymer emulsion particle (TB-1). A test plate (G-3) having F-3) was obtained.
- the test plate (G-3) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 82 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particles (TB-4) synthesized in Production Example 15 were used instead of the polymer emulsion particles (TB-1). A test plate (G-4) having F-4) was obtained.
- the test plate (G-4) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 83 An organic-inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particle (TB-5) aqueous dispersion synthesized in Production Example 16 was used instead of the polymer emulsion particle (TB-1). A test plate (G-5) having F-5) was obtained. The test plate (G-5) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 84 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particle (TB-6) aqueous dispersion synthesized in Production Example 17 was used instead of the polymer emulsion particle (TB-1). A test plate (G-6) having F-6) was obtained. The test plate (G-6) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 85 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particles (TB-7) synthesized in Production Example 18 were used instead of the polymer emulsion particles (TB-1). A test plate (G-7) having F-7) was obtained. The test plate (G-7) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 12 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particle (TB-8) aqueous dispersion synthesized in Production Example 19 was used instead of the polymer emulsion particle (TB-1). A test plate (G-8) having F-8) was obtained. The test plate (G-8) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Example 13 An organic / inorganic composite film (in the same manner as in Example 79) except that the polymer emulsion particles (TB-9) aqueous dispersion synthesized in Production Example 20 was used instead of the polymer emulsion particles (TB-1). A test plate (G-9) having F-9) was obtained. The test plate (G-9) having the organic / inorganic composite film thus obtained had an initial contact angle with water of 7.2 °.
- Table 16 shows the results of Examples and Comparative Examples.
- the coating film of each example can maintain surface hydrophilicity even at least under high temperature and high humidity.
- the coating film and coating composition according to the present invention are excellent in antifouling property, transparency, hydrophilicity and durability (impact resistance), and can maintain surface hydrophilicity even under high temperature and high humidity. It can be used as a member of various energy production devices such as modules and solar thermal power generation systems, etc., and it is a protective member for solar cells with good sunlight transmission and condensing properties, a member of a light reflector for solar thermal power generation, etc. Can be suitably used.
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Abstract
Description
〔1〕
(A)数平均粒子径が1nm~400nmの金属酸化物と、
(B)重合体粒子と、を含み、
下記式(I)で表される、前記(B)成分中の水相成分の含有率が、20質量%以下である、コーティング組成物。
水相成分の含有率(%)=((B)成分を分画分子量50,000でろ過したろ液の乾燥質量)×(100-全固形分質量)/(前記ろ液の質量-前記ろ液の乾燥質量)×100/全固形分質量 ・・・(I)
〔2〕
前記(B)成分は、
(b1)成分:加水分解性珪素化合物と、
(b2)成分:ビニル単量体と、
(b3)成分:乳化剤と、
(b4)成分:水と、
を含む重合原液中で、前記(b1)成分と前記(b2)成分とを重合して得られる重合体エマルジョン粒子(B1)である〔1〕に記載のコーティング組成物。
〔3〕
前記水相成分の含有率が、15質量%以下である、〔1〕又は〔2〕に記載のコーティング組成物。
〔4〕
前記(B)成分の数平均粒子径が10nm~800nmである、〔1〕~〔3〕のいずれか一項に記載のコーティング組成物。
〔5〕
前記(b2)成分が、水酸基、カルボキシル基、アミド基、アミノ基、及びエーテル基からなる群から選ばれる少なくとも1種の官能基を有するビニル単量体である、〔2〕~〔4〕のいずれか一項に記載のコーティング組成物。
〔6〕
前記(B)成分に対する前記(b2)成分の質量比((b2)/(B))が、0.01/1~1/1である、〔2〕~〔5〕のいずれか一項に記載のコーティング組成物。
〔7〕
前記(A)成分に対する前記(b2)成分の質量比((b2)/(A))が、0.01/1~1/1である、〔2〕~〔6〕のいずれか一項に記載のコーティング組成物。
〔8〕
前記(B)成分が、コア層と、前記コア層を被覆する1層又は2層以上のシェル層と、を備えたコア/シェル構造を有する、〔1〕~〔7〕のいずれか一項に記載のコーティング組成物。
〔9〕
前記コア層において、前記(b1)成分に対する前記(b2)成分の質量比((b2)/(b1))が、0.01/1~1/1であり、
前記シェル層の最外層において、前記(b1)成分に対する前記(b2)成分の質量比((b2)/(b1))が、0.01/1~5/1である、〔8〕に記載のコーティング組成物。
〔10〕
前記(B)成分が、前記コア層を形成するシード粒子の存在下で前記重合原液を重合して得られる重合体エマルジョン粒子であり、
前記シード粒子が、前記(b1)成分、前記(b2)成分、及び(b5)成分:前記(b2)成分と共重合可能な他のビニル単量体、からなる群から選択される少なくとも1種以上を重合して得られる、〔2〕~〔9〕のいずれか一項に記載のコーティング組成物。
〔11〕
前記(b2)成分が、2級アミド基、3級アミド基、あるいはその両方を有するビニル単量体である、〔2〕~〔10〕のいずれか一項に記載のコーティング組成物。
〔12〕
前記(B)成分に対する前記(A)成分の質量比((A)/(B))が、110/100~480/100である、〔1〕~〔11〕のいずれか一項に記載のコーティング組成物。
〔13〕
(C)成分:下記式(1)、(2)、及び(3)で表される化合物からなる群より選ばれる1種以上の加水分解性珪素化合物を、更に含む、〔1〕~〔12〕のいずれか一項に記載のコーティング組成物。
R1 nSiX4-n (1)
(式(1)中、R1は、水素原子、あるいは、ハロゲン基、ヒドロキシ基、メルカプト基、アミノ基、(メタ)アクリロイル基又はエポキシ基を有していてもよい、炭素数1~10のアルキル基、アルケニル基、アルキニル基若しくはアリール基を表す。Xは、加水分解性基を表し、nは0~3の整数である。)
X3Si-R2 n-SiX3 (2)
(式(2)中、Xは加水分解性基を表し、R2は炭素数1~6のアルキレン基又はフェニレン基を表す。nは0又は1である。)
R3-(O-Si(OR3)2)n-OR3 (3)
(式(3)中、R3は炭素数1~6のアルキル基を表す。nは2~8の整数である。)
〔14〕
前記(A)成分に対する前記(C)成分の質量比((C)/(A))が、1/100~150/100である、〔13〕に記載のコーティング組成物。
〔15〕
前記(B)成分の数平均粒子径が10nm~100nmである、〔1〕~〔14〕のいずれか一項に記載のコーティング組成物。
〔16〕
前記(A)成分が、
(A1)成分:数平均粒子径が1nm~400nmのシリカと、
(A2)成分:数平均粒子径が1nm~2000nmの赤外線吸収剤と、を含み
前記(B)成分の含有量に対する前記(A1)成分と前記(A2)成分との総含有量の質量比((A1+A2)/(B))が、60/100~1000/100であり、
前記(B)成分と前記(A1)成分との前記総含有量に対する前記(A2)成分の含有量の質量比((A2)/(A1+B))が、0.05/100~40/100である、〔1〕~〔15〕のいずれか一項に記載のコーティング組成物。
〔17〕
前記(A)成分が、
(A1)成分:数平均粒子径が1nm~400nmのシリカと、
(A3)成分:数平均粒子径が1nm~2000nmの光触媒と、を含み
前記(B)成分の含有量に対する前記(A1)成分と前記(A3)成分との総含有量の質量比((A1+A3)/(B))が、60/100~480/100であり、
前記(A1)成分と前記(A3)成分との前記総含有量に対する前記(A1)成分の含有量の質量比((A1)/(A1+A3))が、85/100~99/100である、〔1〕~〔16〕のいずれか一項に記載のコーティング組成物。
〔18〕
反射防止用である〔1〕~〔17〕のいずれか一項に記載のコーティング組成物。
〔19〕
耐溶剤用である〔1〕~〔17〕のいずれか一項に記載のコーティング組成物。
〔20〕
帯電防止用である〔1〕~〔17〕のいずれか一項に記載のコーティング組成物。
〔21〕
耐熱用である〔1〕~〔17〕のいずれか一項に記載のコーティング組成物。
〔22〕
ハードコート用である〔1〕~〔17〕のいずれか一項に記載のコーティング組成物。
〔23〕
〔1〕~〔22〕のいずれか一項に記載のコーティング組成物から得られる塗膜。
〔24〕
(A)数平均粒子径が1nm~400nmの金属酸化物と、
前記(A)成分に囲まれた重合体粒子(B)と、
を含む塗膜であって、
限外濾過法によって前記(B)成分から抽出された分画分子量50,000以下の成分(B2)をフィルムにした場合のフィルム表面の水接触角が30°以下である塗膜。
〔25〕
(A)数平均粒子径が1nm~400nmの金属酸化物と、
前記(A)成分に囲まれた重合体粒子(B)と、
を含む塗膜であって、
限外濾過法によって前記(B)成分から抽出された分画分子量50,000以下の成分(B2)をフィルムにした場合のフィルム表面の水接触角が30°を超え、その含有量が、5質量%以下である塗膜。
〔26〕
前記(B)成分がエマルジョン粒子である、〔24〕又は〔25〕に記載の塗膜。
〔27〕
20℃における表面水接触角が30°以下である、〔23〕~〔26〕のいずれか一項に記載の塗膜。
〔28〕
温度90℃、湿度90%の条件下で24時間静置する高温高湿試験後の塗膜表面の水接触角が20°以下である〔23〕~〔27〕のいずれか一項に記載の塗膜。
〔29〕
基材と、
前記基材の少なくとも一方の表面に形成された、〔1〕~〔22〕のいずれか一項に記載のコーティング組成物を塗布して得られる塗膜、又は〔23〕~〔28〕のいずれか一項に記載の塗膜と、
を備える積層体。
〔30〕
前記積層体の光線透過率が前記基材の光線透過率よりも高い、〔29〕に記載の積層体。
〔31〕
前記塗膜の屈折率が前記基材の屈折率よりも0.1以上低い、〔29〕又は〔30〕に記載の積層体。
〔32〕
前記塗膜は、2以上の層を有する塗膜である、〔29〕~〔31〕のいずれか一項に記載の積層体。
〔33〕
前記基材と反対側に位置する最表層の屈折率が前記最表層に隣接する層の屈折率よりも0.1以上低い、〔29〕~〔32〕のいずれか一項に記載の積層体。
〔34〕
前記塗膜を構成する各層の厚さ(dn)が10nm~800nmであり、
前記塗膜の総厚さ(Σdn)が100nm~4000nmである、〔32〕又は〔33〕に記載の積層体。
〔35〕
前記基材の光線透過率が30%~99%である、〔29〕~〔34〕のいずれか一項に記載の積層体。
〔36〕
前記基材における前記塗膜側の表面の反射率(Rb)に対する、前記塗膜の前記基材とは反対側表面の反射率(Rc)の割合((Rc)/(Rb))が、98%以上である、〔29〕~〔35〕のいずれか一項に記載の積層体。
〔37〕
前記塗膜と前記基材との屈折率の差が0.2以下である、〔29〕~〔36〕のいずれか一項に記載の積層体。
〔38〕
前記塗膜の屈折率が1.30~1.48である、〔29〕~〔37〕のいずれか一項に記載の積層体。
〔39〕
前記基材における前記塗膜側の表面の反射率(Rb)が80%以上である、〔36〕~〔38〕のいずれか一項に記載の積層体。
〔40〕
前記基材は、ガラス、アクリル樹脂、ポリカーボネート樹脂、環状オレフィン樹脂、ポリエチレンテレフタレート樹脂、及びエチレン-フルオロエチレン共重合体からなる群から選択される少なくとも1種を含む、〔29〕~〔39〕のいずれか一項に記載の積層体。
〔41〕
基材の少なくとも一方の表面に、〔1〕~〔22〕のいずれか一項に記載のコーティング組成物を塗布し、塗膜を形成する工程と、
前記塗膜に対して、70℃以上の加熱処理、あるいは0.1kPa以上の加圧処理の少なくとも一方を施す工程と、
を有する積層体の製造方法。
〔42〕
エネルギー変換装置用部材である、〔29〕~〔40〕のいずれか一項に記載の積層体。
〔43〕
太陽電池モジュールの保護部材である、〔42〕に記載の積層体。
〔44〕
〔42〕に記載の積層体と、
前記積層体と対向して配置されるバックシートと、
前記積層体と前記バックシートの間に配置される発電素子と、
を備える太陽電池モジュール。
〔45〕
光反射鏡の保護部材である、〔42〕に記載の積層体。
〔46〕
光反射鏡と、
前記光反射光の反射面を保護する〔45〕に記載の積層体と、
前記反射鏡を支持する支持体と、
を備えるリフレクター装置。
〔47〕
〔46〕に記載のリフレクター装置と、
前記リフレクター装置により集光される太陽光を電気エネルギーに変換する装置と、
を備える太陽熱発電システム。
本実施の形態のコーティング組成物は、
(A)数平均粒子径が1nm~400nmの金属酸化物粒子と、
(B)重合体粒子と、を含み、
下記式(I)で表される、前記(B)成分中の水相成分の含有率が、20質量%以下である。
水相成分の含有率(%)=((B)成分を分画分子量50,000でろ過したろ液の乾燥質量)×(100-全固形分質量)/(前記ろ液の質量-前記ろ液の乾燥質量)×100/全固形分質量 ・・・(I)
水相成分の含有率(%)=((B)成分を分画分子量50,000でろ過したろ液の乾燥質量)×(100-全固形分質量)/(前記ろ液の質量-前記ろ液の乾燥質量)×100/全固形分質量 ・・・(I)
SiWxRy (4)
ここで、式中、Wは炭素数1~20のアルコキシ基、水酸基、炭素数1~20のアセトキシ基、ハロゲン原子、水素原子、炭素数1~20のオキシム基、エノキシ基、アミノキシ基及びアミド基からなる群より選ばれる少なくとも1種の基を表す。Rは、直鎖状又は分岐状の炭素数が1~30個のアルキル基、炭素数5~20のシクロアルキル基、及び置換されていないか又は炭素数1~20のアルキル基若しくは炭素数1~20のアルコキシ基若しくはハロゲン原子で置換されている炭素数6~20のアリール基からなる群より選ばれる少なくとも1種の炭化水素基を表す。xは1以上4以下の整数であり、yは0以上3以下の整数である。また、x+y=4である。
(R’2SiO)m (5)
ここで、式中、R’は、水素原子、直鎖状又は分岐状の炭素数が1~30個のアルキル基、炭素数5~20のシクロアルキル基、及び置換されていないか又は炭素数1~20のアルキル基若しくは炭素数1~20のアルコキシ基若しくはハロゲン原子で置換されている炭素数6~20のアリール基からなる群より選ばれる少なくとも1種を示す。mは整数であり、2≦m≦20である。
中でも、反応性等の点からオクタメチルシクロテトラシロキサン等の環状ジメチルシロキサンオリゴマーが好ましい。
全固形分質量(質量%)=乾燥質量/(B)成分の質量×100・・・(II)
R1 nSiX4-n (1)
ここで、式(1)中、R1は水素原子、あるいは、ハロゲン基、ヒドロキシ基、メルカプト基、アミノ基、(メタ)アクリロイル基又はエポキシ基を有していてもよい、炭素数1~10のアルキル基、アルケニル基、アルキニル基若しくはアリール基を表す。Xは、加水分解性基を表し、nは0~3の整数である。加水分解性基は加水分解により水酸基が生じる基であれば特に限定されず、例えばハロゲン原子、アルコキシ基、アシルオキシ基、アミノ基、フェノキシ基、オキシム基等が挙げられる。
X3Si-R2 n-SiX3 (2)
ここで、式(2)中、Xは加水分解性基を表し、R2は炭素数1~6のアルキレン基又はフェニレン基を表す。nは0又は1である。
R3-(O-Si(OR3)2)n-OR3 (3)
ここで、式(3)中、R3は炭素数1~6のアルキル基を表す。nは2~8の整数である。
本実施の形態のコーティング組成物から得られる塗膜は、防汚性、透明性、親水性、耐久性(耐衝撃性)に優れ、さらには、高温下、高湿下、あるいは高温高湿下であっても表面親水性を維持できる塗膜とできるため、種々の用途に好適に用いることができる。そして、上述したように、これらの特性に加えて、他の特性も必要に応じて付与することができるため、種々の用途に好適に用いることができる。例えば反射防止用、耐溶剤用、帯電防止用、耐熱用、ハードコート用のコーティング組成物として好適に用いることができる。
本実施の形態のコーティング組成物は、その硬化時間が過度に長くなることがなく、使用できる基材の種類の制限も緩和することができる。さらに、得られる塗膜についても、耐光性、耐摩擦性、耐久性に優れるという利点も付与できるため、反射防止用コーティング組成物として好適に用いることもできる。液晶晶表示パネル、冷陰極線管パネル及びプラズマディスプレー等の各種表示パネル、屋外に表示される看板等のディスプレイ、並びに電光掲示板等に外光の映りを防止するとともに、画質を向上させるための反射防止膜として好適に用いることができる。
(1)
(A)成分として、数平均粒子径が1nm~400nmの金属酸化物と、
(B)成分として、数平均粒子径が10nm~800nmの重合体エマルジョン粒子と、
を含み、
(B)成分が、上記(b1)~(b4)の各成分を含む重合原液を重合して得られる重合体エマルジョン粒子であり、
(B)成分に対する(A)成分の質量比((A)/(B))が、50/100~450/100である、反射防止用コーティング組成物であることが好ましい。
特に、(A)成分としては、上記した(A1)シリカ、(A3)光触媒、及び(A4)導電性金属酸化物からなる群から選ばれる少なくとも1種以上を用いることがより好ましい。これらの各成分を用いる利点は上記の通りであるが、これに加えて、(A3)光触媒を用いる場合、光照射により光触媒活性や親水性を発現することができ、塗膜表面に汚染有機物質の優れた分解活性や耐汚染性を一層顕著に発現することができる。
(2)
上記(1)において、(B)成分に対する(b2)成分の質量比(b2)/(B)が、0.1/1~0.5/1であるであることが好ましい。
(3)
上記(1)又は(2)において、(b2)成分と、(A)成分との質量比(b2)/(A)が、0.1/1~1/1であることが好ましい。
(4)
上記(1)~(3)のいずれかにおいて、(B)成分が、コア層と、コア層を被覆する1層又は2層以上のシェル層とを備えたコア/シェル構造を有することが好ましい。
(5)
上記(4)のコア層において、(b2)成分と(b1)成分との質量比(b2)/(b1)が0.01/1~1/1であり、シェル層の最外層において、(b2)成分と(b1)成分との質量比(b2)/(b1)が0.1/1~5/1であることが好ましい。
(6)
上記(4)又は(5)において、(B)成分が、コア層を形成するシード粒子の存在下で重合原液を重合して得られ、シード粒子が、(b1)成分、(b2)成分、及び(b2)成分と共重合可能なビニル単量体よりなる群から選択される少なくとも1種以上を重合して得られるものが好ましい。
(7)
上記(1)~(6)のいずれかにおいて、(b2)成分が2級アミド基、3級アミド基、あるいはその両方を有するビニル単量体であることが好ましい。
(8)
上記(1)~(7)のいずれかにおいて、(B)成分の粒子径が120~450nmであることが好ましい。
(9)
上記(1)~(8)のいずれかにおいて、上記した(C)成分を更に含むことが好ましい。(10)
上記反射防止用コーティング組成物から形成された反射防止複合体とすることができる。
(11)
上記反射防止用コーティング組成物を含んでなる反射防止複合体とすることができる。
(12)
上記反射防止複合体を含んでなるディスプレイとすることができる。
(13)
上記反射防止複合体を含んでなる外装表示用部材とすることができる。
本実施の形態のコーティング組成物は、上記したように(A)成分と(B)成分とが相互作用する傾向があるため、得られる塗膜の防汚性、透明性、親水性だけでなく、耐候性等に優れるという利点も付与できるため、耐溶剤用コーティング組成物として好適に用いることもできる。工業生産される物品は、一般に、製造工程や製品の組み立て、取付け工程でアルコール等の溶剤で洗浄されることがあるため、耐溶剤性が求められる。例えば光学レンズ等の光学部品の場合、表面の汚れをイソプロピルアルコール等で拭き取ることが行われているが、その際に耐溶剤性がないと、表面が溶解してしまい、透明性等の光学特性が低下してしまう。そのため、このような物品に耐溶剤性を付与するためのコーティング組成物として好適に用いることができる。
(A)
(A)成分として、数平均粒子径が1nm~400nmの金属酸化物と、
(B)成分として、数平均粒子径が10nm~800nmの重合体エマルジョン粒子と、
を含み、
(B)成分が、上記(b1)~(b4)の各成分を含む重合原液を重合して得られる重合体エマルジョン粒子であり、
(B)成分に対する(A)成分の質量比((A)/(B))が、50/100~300/100である、耐溶剤用コーティング組成物であることが好ましい。
(2)
上記(1)において、(B)成分に対する(b2)成分の質量比((b2)/(B))が、0.1/1~0.5/1であることが好ましい。
(3)
上記(1)又は(2)において、(A)成分に対する(b2)成分の質量比((b2)/(A))が、0.1/1~1/1であることが好ましい。
(4)
上記(1)~(3)のいずれかにおいて、(B)成分が、コア層と、コア層を被覆する1層又は2層以上のシェル層とを備えたコア/シェル構造を有することが好ましい。
(5)
上記(4)のコア層において、(b1)成分に対する(b2)成分の質量比((b2)/(b1))が0.01/1~1/1であり、シェル層の最外層において、(b1)成分に対する(b2)成分の質量比((b2)/(b1))が0.1/1~5/1であることが好ましい。
(6)
上記(4)又は(5)のコア層において、(B)成分が、コア層を形成するシード粒子の存在下で重合原液を重合して得られ、シード粒子が、(b1)成分、(b2)成分、及び(b2)成分と共重合可能なビニル単量体よりなる群から選択される少なくとも1種以上を重合して得られるものが好ましい。
(7)
(1)~(6)のいずれかにおいて、(b2)成分が2級アミド基、3級アミド基、あるいはその両方を有するビニル単量体であることが好ましい。
(8)
(1)~(7)のいずれかにおいて、(B)成分の数平均粒子径が20~250nmであることが好ましい。
(9)
(1)~(8)のいずれかにおいて、(C)成分を更に含むことが好ましい。
(10)
上記耐溶剤用コーティング組成物から形成された耐溶剤複合体とすることができる。
(11)
上記耐溶剤用コーティング組成物を含んでなる耐溶剤複合体とすることができる。
(12)
上記耐溶剤複合体を含んでなるディスプレイとすることができる。
(13)
上記耐溶剤複合体を含んでなる外装表示用部材とすることができる。
(14)
上記の耐溶剤複合体を含んでなる窓用透明プラスチックとすることができる。
(15)
上記耐溶剤複合体を含んでなる太陽光発電用透明保護材とすることができる。
本実施の形態のコーティング組成物では、(A)成分として導電性金属酸化物を用いることができるため、帯電防止能を塗膜に付与することもできる。これにより、帯電防止用コーティング組成物として用いることもできる。帯電防止用コーティング組成物及びそれを用いた各種部材の好ましい態様の一例としては、以下のものが挙げられる。特に、(A)成分としては、上記した(A1)シリカ、(A3)光触媒、及び(A4)導電性金属酸化物からなる群から選ばれる少なくとも1種以上を用いることがより好ましい。これらの各成分を用いる利点は上記の通りであるが、以下の条件をさらに満たすことで、防汚性、透明性、親水性等だけでなく、帯電防止性能も塗膜に付与することができる。
(A)成分として、数平均粒子径が1nm~400nmの金属酸化物と、
(B)成分として、数平均粒子径が10nm~800nmの重合体エマルジョン粒子と、
を含み、
(B)成分が、上記(b1)~(b4)の各成分を含む重合原液を重合して得られる重合体エマルジョン粒子であり、
(B)成分に対する(A)成分の質量比((A)/(B))が、150/100~450/100である、帯電防止用コーティング組成物であることが好ましい。
(2)
上記(1)において、(B)成分に対する(b2)成分の質量比((b2)/(B))が、0.1/1~0.5/1であることが好ましい。
(3)
上記(1)又は(2)において、(A)成分に対する(b2)成分の質量比((b2)/(A))が、0.1/1~1/1であることが好ましい。
(4)
上記(1)~(3)のいずれかにおいて、(B)成分が、コア層と、コア層を被覆する1層又は2層以上のシェル層とを備えたコア/シェル構造を有することが好ましい。
(5)
上記(4)のコア層において、(b2)成分と(b1)成分との質量比(b2)/(b1)が0.01/1~1/1であり、シェル層の最外層において、(b2)成分と(b1)成分との質量比(b2)/(b1)が0.1/1~5/1であることが好ましい。
(6)
(4)又は(5)の帯電防止用コーティング組成物のコア層において、(B)成分が、コア層を形成するシード粒子の存在下で重合原液を重合して得られ、シード粒子が、(b1)成分、(b2)成分、及び(b2)成分と共重合可能なビニル単量体よりなる群から選択される少なくとも1種以上を重合して得られるものであることが好ましい。
(7)
(1)~(6)のいずれかにおいて、(b2)成分が2級アミド基、3級アミド基、あるいはその両方を有するビニル単量体であることが好ましい。
(8)
(1)~(7)のいずれかにおいて、(B)成分の数平均粒子径が50~350nmであることが好ましい。
89)
(1)~(8)のいずれかにおいて、上記(C)成分を更に含む帯電防止用コーティング組成物であって、
(B)成分に対する(A)成分の質量比((A)/(B))が、150/100~350/100であり、
(C)成分に対する(A)成分の質量比((C)/(A))が、0.5/100~110/100であることが好ましい。
(10)
上記の帯電防止用コーティング組成物から形成された帯電防止複合体とすることができる。
(11)
上記の帯電防止用コーティング組成物を含んでなる帯電防止複合体とすることができる。
(12)
上記の帯電防止複合体を含んでなるディスプレイとすることができる。
(13)
上記の帯電防止複合体を含んでなる外装表示用部材とすることができる。
(14)
上記の帯電防止複合体を含んでなる窓用透明プラスチックとすることができる。
(15)
上記の帯電防止複合体を含んでなる太陽光発電用透明保護材とすることができる。
本実施の形態のコーティング組成物では、(A)成分として(A2)赤外線吸収剤を用いることができるため、耐熱性能・遮熱性能を塗膜に付与することもできる。これにより、遮熱用コーティング組成物として用いることもできる。特に、(A)成分としては、上記した(A1)シリカ、(A2)赤外線吸収剤、(A3)光触媒、及び(A4)導電性金属酸化物からなる群から選ばれる少なくとも1種以上を用いることがより好ましい。これらの各成分を用いる利点は上記の通りであるが、以下の条件をさらに満たすことで、透明性、親水性、防汚性等だけでなく、耐熱・遮熱性能も塗膜に付与することができる。
(1)
(A1)成分として、数平均粒子径が1nm~400nmのシリカと、
(A2)成分として、数平均粒子径が1nm~2000nmの赤外線吸収剤と、
(B)成分として、数平均粒子径が10nm~800nmの重合体エマルジョン粒子と、を含む耐熱用コーティング組成物。
(2)
上記(1)において、前記(A2)成分が、錫をドープした酸化インジウム、アンチモンをドープした酸化錫、酸化セリウム、酸化亜鉛、及びシリカで被覆された当該剤からなる群から選ばれる少なくとも1種であることが好ましい。
(3)
上記(1)又は(2)において、前記(B)成分が、上記(b1)成分~(b4)成分を含む重合原液中で、前記(b1)成分及び前記(b2)成分を重合して得られる重合体エマルジョン粒子であることが好ましい。
(4)
上記(1)~(3)のいずれかにおいて、(B)成分の含有量に対する前記(A1)成分と前記(A2)成分との総含有量((A1+A2)/(B))の質量比が60/100~1000/100であり、
前記(B)成分と前記(A1)成分の合計含有量に対する前記(A2)成分の含有量の質量比((A2)/(B+A1))が、0.05/100~40/100であることが好ましい。
(5)
上記(1)~(4)において、前記(B)成分の含有量に対する前記(b2)成分の含有量の質量比((b2)/(B))が、0.1/1~0.5/1であることが好ましい。
(6)
上記(1)~(5)において、前記(A1)成分の含有量に対する前記(b2)成分の含有量の質量比((b2)/(A1))が、0.1/1~1/1であることが好ましい。
(7)
上記(1)~(6)において、前記(B)成分が、コア層と、当該コア層を被覆する1層又は2層以上のシェル層と、を備えるコア/シェル構造を有することが好ましい。
(8)
上記(7)のコア層において、前記(b1)成分の含有量に対する前記(b2)成分の含有量の質量比((b2)/(b1))が、0.01/1~1/1であり、
前記シェル層の最外層において、前記(b1)成分の含有量に対する前記(b2)成分の含有量の質量比((b2)/(b1))が、0.1/1~5/1であることが好ましい。
(9)
上記(7)又は(8)において、前記(B)成分が、前記コア層を形成するシード粒子を含む前記重合原液中で、前記(b1)成分及び前記(b2)成分を重合して得られる重合体エマルジョン粒子であり、
前記シード粒子が、前記(b1)成分、前記(b2)成分及び(b5)成分:前記前記(b2)成分と共重合可能な他のビニル単量体からなる群より選ばれる少なくとも1種以上の成分を重合して得られる粒子であることが好ましい。
(10)
上記(3)~(9)において、前記(b2)成分が、2級アミド基、3級アミド基、あるいはその両方を有するビニル単量体であることが好ましい。
(11)
上記(1)~(10)において、(C)成分を更に含み、
前記(A1)成分の含有量に対する前記(C)成分の含有量の質量比((C)/(A1))が、1/100~100/100であることが好ましい。
(12)
上記(1)~(11)において、前記(B)成分の数平均粒子径が10~100nmであることが好ましい。
(13)
上記(1)~(12)において、前記(A1)成分が、数平均粒子径が1nm~400nmのコロイダルシリカであることが好ましい。
(14)
上記(1)~(13)において、前記(A2)成分が、波長1000nm~2500nmの波長域で0.1%以上の吸収があることが好ましい。
(15)
基材と、前記基材上に上記の耐熱用コーティング組成物を塗布し、乾燥させて形成された塗膜と、を備える太陽電池用部材とすることができる。これらの太陽電池用部材は、太陽電池の保護部材として用いることができる。
本実施の形態のコーティング組成物は、その硬化時間が過度に長くなることがなく、使用できる基材の種類の制限も緩和することができる。さらに、得られる塗膜についても、耐光性、耐摩擦性、耐久性に優れるという利点も付与できるため、ハードコート用コーティング組成物として好適に用いることもできる。ハードコート用コーティング組成物及びそれを用いた各種部材の好ましい態様の一例としては、以下のものが挙げられる。以下の条件をさらに満たすことで、防汚性、透明性、親水性等だけでなく、ハードコート性能も塗膜に付与することができる。
(A)成分として、粒子径が1nm~400nmの金属酸化物と、
(B)成分として、粒子径が10nm~800nmの重合体エマルジョン粒子と、
を含み、
(B)成分が、上記の(b1)~(b4)の各成分を含む重合原液を重合して得られる重合体エマルジョン粒子であり、
(B)成分に対する(A)成分の質量比((A)/(B))が、50/100~350/100である、ハードコート用コーティング組成物であることが好ましい。
(2)
上記(1)において、(B)成分に対する(b2)成分の質量比((b2)/(B))が、0.1/1~0.5/1であることが好ましい。
(3)
上記(1)又は(2)において、(A)成分に対する(b2)成分の質量比((b2)/(A))が、0.1/1~1/1であることが好ましい。
(4)
上記(1)~(3)のいずれかにおいて、(B)成分が、コア層と、当該コア層を被覆する1層又は2層以上のシェル層とを備えたコア/シェル構造を有することが好ましい。
(5)
上記(4)のコア層において、(b1)成分に対する(b2)成分の質量比((b2)/(b1))が0.01/1~1/1であり、シェル層の最外層において、(b1)成分に対する(b2)成分の質量比(b2)/(b1)が0.1/1~5/1であることが好ましい。
(6)
上記(4)又は(5)において、(B)成分が、コア層を形成するシード粒子の存在下で重合原液を重合して得られ、シード粒子が、(b1)成分、(b2)成分、及び(b2)成分と共重合可能なビニル単量体よりなる群から選択される少なくとも1種以上を重合して得られるものが好ましい。
(7)
上記(1)~(6)のいずれかにおいて、(b2)成分が2級アミド基、3級アミド基、あるいはその両方を有するビニル単量体であることが好ましい。
(8)
(1)~(7)のいずれかにおいて、(B)成分の数平均粒子径が50~250nmであることが好ましい。
(9)
上記(1)~(8)のいずれかにおいて、上記の(C)成分を更に含み、
(B)成分に対する(A)成分の質量比((A)/(B))が、50/100~350/100であり、
(C)成分に対する(A)成分の質量比((C)/(A))が、5/100~90/100であることが好ましい。
(10)
上記のハードコート用コーティング組成物から形成されたハードコート複合体とすることができる。
(11)
上記のハードコート用コーティング組成物を含んでなるハードコート複合体とすることができる。
(12)
上記のハードコート複合体を含んでなるディスプレイとすることができる。
(13)
上記のハードコート複合体を含んでなる外装表示用部材とすることができる。
(14)
上記のハードコート複合体を含んでなる乗り物用窓とすることができる。
(15)
上記のハードコート複合体を含んでなる太陽光発電用透明保護材とすることができる。
(B)成分から抽出された分画分子量50,000以下の成分(B2)を、乾燥フィルムにしたときの20℃における水との表面接触角が30°より大きければよく、(A)成分、(B)成分、及び(B2)成分の組成等は特に限定されない。例えば上述した(A)成分や(B)成分等を採用してもよい。ここで、表面接触角とは、乾燥フィルムと、その表面に存在する水滴の接線とのなす角度をいい、液滴法によって測定できる。
本実施の形態の塗膜及びコーティング組成物から積層体を得ることができる。図1は、本実施の形態の積層体の一例の概略断面図である。本実施の形態の積層体1は、基材10と、前記基材10の少なくとも一方の表面に形成された、上記のコーティング組成物を塗布して得られる塗膜12と、を備える。
本実施の形態の積層体は、エネルギー変換装置用部材として好適に用いることができる。エネルギー変換装置としては、例えば太陽光を利用した発電装置等が挙げられる。エネルギー用部材としては、例えば太陽光を利用した発電に使用できる部材をいい、より具体的には、太陽電池モジュールに用いられる部材、太陽熱発電システムに用いられる部材等が挙げられる。より具体的には、太陽電池モジュールの表面の保護部材であるカバーガラスや裏面の保護部材であるバックシート、封止材、アルミ枠等の型枠、集光型太陽電池のフレネルレンズ、太陽熱発電に用いられる光反射鏡等として用いることができる。
本実施の形態の積層体を太陽電池モジュールの保護部材(以下、単に保護部材という場合がある。)とした太陽電池モジュールとすることができる。図2は、本実施の形態の太陽電池の一態様の簡略断面図である。本実施の形態の太陽電池モジュール2は、保護部材20と、前記保護部材20と対向して配置されるバックシート22と、前記保護部材20と前記バックシート22の間に配置される発電素子24と、を備える。さらに、発電素子24は、封止材26によって封止されている。太陽電池モジュール2において太陽光Lは、保護部材20側から入射して発電素子24に到達する。
図3は、本実施の形態のリフレクター装置の一例の概略斜視図である。光反射鏡32と、前記光反射鏡の反射面側に形成された本実施の形態の積層体30と、前記反射鏡32を支持する支持体34と、を備えるリフレクター装置3とすることができる。本実施の形態の積層体30を光反射鏡32の保護部材(以下、単に「保護部材」という場合がある。)としたリフレクター装置することができる。リフレクター装置3の構成は、特に限定されず、適宜好適な構成に変形することができる。
本実施の形態では、前記リフレクター装置と、このリフレクター装置により集光される太陽光を電気エネルギーに変換する装置と、を備える太陽熱発電システムとすることができる。太陽熱発電システムの構成は、特に限定されず、適宜好適な構成に変形することができる。
試料中の固形分含有量が0.1~20質量%となるよう溶媒を加えて希釈し、湿式粒度分析計(日機装製マイクロトラックUPA-9230)を用いて測定した。
試料の表面(コーティング組成物の塗工面)に脱イオン水の水滴を乗せ、23℃で1分間放置した後、接触角測定装置(協和界面科学製、CA-X150型接触角計)を用いて測定した。
濁度計(日本電色工業製、NDH2000)を用い、JIS K7105に準じて、試料のヘイズ値を測定した(初期ヘイズ値)。なお、光線透過率は、JIS K7105に準じて測定した。
試料(コーティング組成物の塗工面)の外観をマイクロスコープ(キーエンス社製;倍率100倍)で観察した。その結果を以下のように評価した。
○:微小クラックがほとんどない、
△:微小クラックが多い、
×:成膜できない
試料を70℃で10日間保存した後、コーティング面に脱イオン水の水滴を乗せ、23℃で1分間放置した後、接触角測定装置(協和界面科学製、CA-X150型接触角計)を用いて測定した。
ESPEC社製、SH-661を40℃、90%RHに設定し、試料を16時間保存した後、コーティング面に脱イオン水の水滴を乗せ、23℃で1分間放置した後、接触角測定装置(協和界面科学製、CA-X150型接触角計)を用いて測定した。
ESPEC社製、SH-661を90℃、90%RHに設定し、試料を24時間静置した後、コーティング面に脱イオン水の水滴を乗せ、23℃で1分間放置した後、接触角測定装置(協和界面科学製、CA-X150型接触角計)を用いて測定した。
試料の鉛筆硬度は鉛筆硬度計(テスター産業社製)を用いて測定した。
試料の表面を綿棒で500gの荷重をかけて10往復擦り目視により変化を観察した。
○:ほとんど変化無し、
△:若干傷あり、
×:傷が多い
試料の絶対反射率は、反射分光膜厚計(大塚電子社製、FE3000)を用いて測定した。
試料の表面抵抗値は、濁度計(日本電色工業製、NDH2000)を用いて測定した。
耐溶剤用複合体を作成した後、イソプロピルアルコールに浸しておいた綿棒に500gの荷重をかけて耐溶剤用複合体のコーティング組成物塗工面を10往復擦り、塗膜の状態をマイクロスコープ(キーエンス社製;倍率100倍)で観察した。その結果を以下のように評価した。
○:微小クラックがほとんどない、
△:微小クラックあり、
×:クラックが多発した。
耐熱用複合体を作成した後、150℃の熱板に10分間押し当て、その後、濁度計(日本電色工業製、NDH2000)を用いヘイズ値を測定した。結果を以下のように評価した。
○:ヘイズ≦2、
△:2<ヘイズ≦10、
×:10<ヘイズ。
機能性複合体(比較例については塗膜)を作製した後、アセトンを浸した綿棒でその表面を10往復擦って、その後の表面の外観を目視判定した。
◎:ほとんど変化ない、
○:わずかに変化有り、
△:多少白化、
×:著しい白化
試料(比較例については塗膜)の鉛筆硬度は鉛筆硬度計(テスター産業社製)を用いて測定した。
紫外可視近赤外分光光度計(日本分光製、商品名「V-670」)と大型積分球計とを用いて、基材及び積層体の反射率を測定した。測定は、波長350nm~500nmの範囲で反射率が最も高い値を評価値とした。積層体の反射率を測定する際の基材は、3mm厚の青板ガラスにAl蒸着した鏡を使用した。青板ガラス面にコーティング組成物を塗布し、その塗膜面から入射した光の反射率を測定値とした。
膜厚計(大塚電子製、商品名「FE-3000」)を用い、積層された塗膜の膜厚並びにその塗膜及び基材の屈折率(波長:633nm)を測定した。
基材上に積層された塗膜に対して、キセノンウエザメータ(スガ試験製、サイクル条件:キセノンランプ照度60W/m2、BPT63℃、50%RH、102分間、降雨、30℃、95%RH、18分間)で2500時間耐候性試験を実施した。次いで、塗膜の表面に脱イオン水の水滴を載せ、23℃で1分間放置した後、接触角測定装置(協和界面科学製、CA-X150型接触角計)を用いて、その水滴の接触角を測定した。
電子顕微鏡を用いて塗膜表面を25万倍で観察し、その表面の空孔径の最大直径、最大幅を求めた。さらに、外接円相当径を求めた。塗膜体積は1辺1000nmの正方形の面積と膜厚から求め、その結果から空隙率を算出した。
基材上に形成された塗膜を約3mm四方の小片に分割して測定用試料とした。測定はXPS(PHI Quantera SXM)を用いて、励起源:monoAlkα、15kV×6.7mA、分析サイズ:1.5mm×100μm、取り込み領域(survey scan;0~1、100eV、Narrow scan;Si,2p、C1s(K,2p)、O1s、Na1s,Ca2p,PassEnergy(survey scan;200eV、Narrow scan;112eV)の条件で実施した。得られた結果はSi元素を1として各元素の相対元素濃度(atomic%)を規格化して求め、C/Siの比率を算出した。
(重合体エマルジョン粒子(HB-1)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル150g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド165g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径70nmの重合体エマルジョン粒子(HB-1)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-2)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸4.6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル86g、フェニルトリメトキシシラン133g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド137g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径100nmの重合体エマルジョン粒子(HB-2)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-3)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸2.6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル86g、フェニルトリメトキシシラン133g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド137g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径180nmの重合体エマルジョン粒子(HB-3)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-4)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸4gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル86g、フェニルトリメトキシシラン133g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド137g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径130nmの重合体エマルジョン粒子(HB-4)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-5)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸10gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル86g、フェニルトリメトキシシラン133g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド137g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径40nmの重合体エマルジョン粒子(HB-5)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-6)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸20gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル86g、フェニルトリメトキシシラン133g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド137g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径20nmの重合体エマルジョン粒子(HB-6)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-7)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。
次にアクリル酸ブチル150g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とN-イソプロピルアクリルアミド165g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径70nmの重合体エマルジョン粒子(HB-7)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-8)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にアクリル酸ブチル150g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド150g、(メタ)アクリル酸エチレングリコール15g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で約2時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径70nmの重合体エマルジョン粒子(HB-7)水分散体を得た。水相成分は18質量%であった。
(重合体エマルジョン粒子(HB-9)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にメタクリル酸メチル150g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド165g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で熱養生を約8時間続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径90nmの重合体エマルジョン粒子(HB-9)水分散体を得た。水相成分は5質量%であった。
(重合体エマルジョン粒子(HB-10)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にメタクリル酸シクロヘキシル75g、メタクリル酸メチル75g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド165g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で熱養生として約8時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径70nmの重合体エマルジョン粒子(HB-10)水分散体を得た。水相成分は5質量%であった。
(重合体エマルジョン粒子(HB-11)水分散体の合成)
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸6gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次にメタクリル酸シクロヘキシル75g、メタクリル酸メチル75g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド165g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに反応容器中の温度が80℃の状態で熱養生として約4時間撹拌を続行した後、室温まで冷却し、100メッシュの金網で濾過した後、イオン交換水で固形分を10.0質量%に調整し、数平均粒子径70nmの重合体エマルジョン粒子(HB-11)水分散体を得た。水相成分は9質量%であった。
日産化学工業社製、商品名「スノーテックス」((A)成分)を水中に分散させたもの(固形分10質量%)と製造例で得られた重合体エマルジョン粒子(HB)とテトラエトキシシラン(C)を表1に示す配合にてコーティング組成物を得た。表に記載の「スノーテックス」の粒子径はカタログ値を記載した。
5cm×5cmのガラス上に、得られたコーティング組成物をディップコートした後、70℃、10分間乾燥して塗膜を有する積層体を得た。これらの評価結果を表1~4に示す。
日産化学工業社製、商品名「スノーテックスO」((A)成分)を水中に分散させたもの(固形分10質量%、数平均粒子径10nm)と、製造例で得られた重合体エマルジョン粒子(HB)と、テトラエトキシシラン(C)と、を表5に示すように配合して、帯電防止用コーティング組成物を得た。次に、5cm×5cmのガラス上に、得られたコーティング組成物をディップコートした後、70℃、10分間乾燥して帯電防止用複合体を得た。これらの評価結果を表5に示す。
日産化学工業社製、商品名「スノーテックスO」((A)成分)を水中に分散させたもの(固形分10質量%、数平均粒子径10nm)と、製造例で得られた重合体エマルジョン粒子(HB)と、テトラエトキシシラン(C)とを表6に示すように配合にして、反射防止用コーティング組成物を得た。次に、5cm×5cmのガラス上に、得られたコーティング組成物をディップコートした後、70℃、10分間乾燥して反射防止用複合体を得た。これらの評価結果を表6に記載した。
日産化学工業社製、商品名「スノーテックスO」((A)成分)を水中に分散させたもの(固形分10質量%、数平均粒子径10nm)と、製造例で得られた重合体エマルジョン粒子(HB)と、テトラエトキシシラン(C)と、を表7に示すように配合して、ハードコート用コーティング組成物を得た。次に、5cm×5cmのポリカーボネート:PC(厚さ3mm)上に、得られたコーティング組成物をディップコートした後、70℃、10分間乾燥してハードコート用複合体を得た。これらの評価結果を表7に記載した。
日産化学工業社製、商品名「スノーテックスO」((A)成分)を水中に分散させたもの(固形分10質量%、数平均粒子径10nm)と、製造例で得られた重合体エマルジョン粒子(HB)と、テトラエトキシシラン(C)と、を表8に示すように配合して、耐溶剤用コーティング組成物を得た。次に、5cm×5cmのポリカーボネート上に、得られたコーティング組成物をディップコートした後、70℃、10分間乾燥して耐溶剤用複合体を得た。これらの評価結果を表8に記載した。
日産化学工業社製、商品名「スノーテックスO」((A)成分)を水中に分散させたもの(固形分10質量%、数平均粒子径10nm)と、製造例で得られた重合体エマルジョン粒子(HB)と、テトラエトキシシラン(C)と、を表9に示すように配合して、耐熱用コーティング組成物を得た。次に、5cm×5cmのガラス上に、得られたコーティング組成物をディップコートした後、70℃、10分間乾燥して耐熱用複合体を得た。これらの評価結果を表9記載した。
(実施例54)
コロイダルシリカ(日産化学工業社製、商品名「スノーテックスO」、(A)を水中に分散させたもの、固形分10質量%、数平均粒子径10nm)と、製造例で得られた重合体エマルジョン粒子(HB-1)、(HB-2)とテトラエトキシシラン(C)とを表10に示す比率で配合してコーティング組成物を得た。
組成を表10に示すように変更した以外は実施例54と同様にしてコーティング組成物を得た。5cm×5cmの基材(ポリカーボネート樹脂製、厚さ:3mm)上に、得られたコーティング組成物をディップコートした後、70℃で10分間乾燥して塗膜を得た。さらに、条件1を条件2(大気中、150℃にて30分間加熱)に代えて、塗膜に加熱処理を施し、機能性複合体を得た。評価結果を表10に示す。
基材であるポリカーボネート樹脂のみを用いた。組成を表10に示すように変更した以外は実施例1と同様にして評価した。評価結果を表10に示す。
(実施例57)
コロイダルシリカ(日産化学工業社製、商品名「スノーテックス-OS」((A)成分)を水で希釈して、固形分10質量%の分散液(数平均粒子径8nm)に調整した。そこに、製造例で合成した重合体エマルジョン粒子水分散体を配合し、(C)成分のテトラエトキシシラン(信越化学社製、商品名「KBE-04」)を表11に示す組成となるよう配合し、全体の固形分が4質量%になるように純水で調整して、コーティング組成物を得た。
得られたコーティング組成物を、乾燥後に所定の厚さになるように基材の反射鏡(板ガラスの裏面(下面)にアルミニウムメッキ処理を施したもの)におけるガラス側の表面上にディップコートした。次いで、ディップコートした後のものを、70℃で30分間乾燥して積層体を得た。
なお、ヘイズ値の測定に際して、基材を反射鏡から白板ガラス(厚さ2mm、6×6cm角)に変更した以外は上記と同様にして作製した積層体を測定対象とした。
実施例57と同様にして配合したコーティング組成物を用いて、塗膜の厚さを表11に示すように替えた以外は実施例57と同様にして積層体を作製した。さらにその積層体の塗膜上にコーティング組成物をディップコートし、70℃で30分間乾燥して、複数層の塗膜を備える積層体を得た。
表11に示す組成に替えた以外は実施例57と同様にして配合したコーティング組成物を用いて、塗膜の厚さを表11に示すように替えた以外は実施例57と同様にして積層体を作製した。
実施例59と同様にして配合したコーティング組成物を用いて、塗膜の厚さを表11に示すように替えた以外は実施例59と同様にして積層体を作製した。次いで、塗膜表面を紙ヤスリ(#1000)により荷重22g/cm2で100回擦った。その後、表面を擦った塗膜上にコーティング組成物をディップコートし、70℃で30分間乾燥して、複数層の塗膜を備える積層体を得た。
基材である反射鏡のみを用いた。
(実施例61)
日産化学工業社製、商品名「スノーテックOS」((A)成分)を水で希釈して固形分10質量%の分散液(数平均粒子径8nm)に調整し、製造例1で合成した重合体エマルジョン(HB1)を配合し、テトラエトキシシラン(C)として信越化学社製、商品名「KBE-04」を表12に示す配合にてコーティング組成物を得た。
得られたコーティング組成物を膜厚250nmになるように白板ガラス(厚み2mm、6×6cm角)の上に、スピンコートした後、70℃、30分間乾燥させて積層体を得た。
表12に記載の組成になるように実施例61と同様に配合したコーティング組成物を用いて積層体を作成した後、同じ手順でコーティング組成物を積層し、多層の積層体を得た。
表12に示す配合にて塗液を調整した以外は、実施例61と同様の手順で積層体を得た。
実施例61と同様の手順で積層を繰り返し、コーティング組成物が10層積層された積層体を得た。
実施例61と同様の手順でコーティング組成物を1回積層した後に、塗膜表面をスチールウール(#7448)で荷重22g/cm2で10回擦過した。その後、再度コーティング組成物を1回積層して積層体を得た。
基材を三菱エンジニアリングプラスチック社製、ポリカーボネート樹脂「ユーピロン」(厚み3mm、5×5cm角)に変更した以外は実施例61と同様に積層体を得た。
基材の白板ガラスのみの評価結果を表13に示す。
基材のポリカーボネート樹脂のみの評価結果を表13に示す。
日産化学工業社製、商品名「スノーテックOS」((A)成分)を水で希釈して固形分10質量%の分散液(数平均粒子径8nm)に調整し、製造例で合成した重合体エマルジョンを表13に示す割合で配合し、さらにメチルトリメトキシシラン(C)として信越化学社製、商品名「KBM-13」を30部配合してコーティング組成物を得た。
得られたコーティング組成物を膜厚250nmになるように白板ガラス(厚み2mm、6×6cm角)の上に、スピンコートした後、70℃、30分間乾燥させて積層体を得た。
比較例9で得た積層体にさらに同様のコーティングを繰り返したが、コーティング液のハジキにより2層の積層体を得ることが出来なかった。
(実施例67~69)
コロイダルシリカ(日産化学工業社製、商品名「スノーテックス-OS」((A)成分)を水で希釈して、固形分10質量%の分散液(粒子の数平均粒子径8nm)に調整した。そこに、光触媒(石原産業社製、商品名「TSK-5」、数平均粒子径10nm、シリカ被覆酸化チタンヒドロゾル)((A3)成分)と製造例で合成した重合体エマルジョン粒子の水分散体とを表14に示す組成で配合し、コーティング組成物を得た。得られたコーティング組成物を膜厚250nmになるように白板ガラス(厚み2mm、6×6cm角)上にスピンコートにて塗布した後、70℃で30分間乾燥させて、基材である白板ガラスと、その上に設けられた塗膜とを備える積層体を得た。
更に(C)成分として、テトラエトキシシラン(信越化学社製、商品名「KBE-04」)を配合し、表14に示す組成になるように配合した以外は実施例67と同様にして、コーティング組成物を得た。そのコーティング組成物を用いた以外は実施例67と同様にして、積層体を得た。
表14記載の組成になるように配合した以外は実施例67と同様にして、コーティング組成物を得た。そのコーティング組成物を用いた以外は実施例67と同様にして、積層体を得た。
(実施例73)
日産化学工業社製、商品名「スノーテックOS」((A)成分)を水で希釈して固形分10質量%の分散液(数平均粒子径8nm)に調整し、製造例で合成した重合体エマルジョンを配合し、表15に示す配合にてコーティング組成物を得た。
得られたコーティング組成物を膜厚250nmになるように白板ガラス(厚み2mm、6×6cm角)の上に、スピンコートした後、70℃、30分間乾燥させて機能性塗膜を得た。
表15に示す配合にてコーティング組成物を得た以外は実施例74と同様にして機能性塗膜を得た。
表15に示す配合にてコーティング組成物を得た以外は実施例74と同様にして機能性塗膜を得た。
日産化学工業社製、商品名「スノーテックOS」((A)成分)を水で希釈して固形分10質量%の分散液(数平均粒子径8nm)に調整し、製造例で合成した重合体エマルジョンを配合し、テトラエトキシシラン(C)として信越化学社製、商品名「KBE-04」を表15に示す配合にてコーティング組成物を得た。
得られたコーティング組成物を膜厚250nmになるように白板ガラス(厚み2mm、6×6cm角)の上に、スピンコートした後、70℃、30分間乾燥させて機能性塗膜を得た。
表15に示す配合にてコーティング組成物を得た以外は実施例74と同様にして機能性塗膜を得た。
表15に示す配合にてコーティング組成物を得た以外は実施例74と同様にして機能性塗膜を得た。
基材のガラスのみを用いて評価した。
重合体エマルジョン粒子(TB-1)水分散体の合成
還流冷却器、滴下槽、温度計及び撹拌装置を有する反応器に、イオン交換水1600g、ドデシルベンゼンスルホン酸4gを投入した後、撹拌下で温度を80℃に加温した。これに、ジメチルジメトキシシラン185g、フェニルトリメトキシシラン117gの混合液を反応容器中の温度を80℃に保った状態で約2時間かけて滴下し、その後、反応容器中の温度が80℃の状態で約1時間撹拌を続行した。次に、アクリル酸ブチル150g、テトラエトキシシラン30g、フェニルトリメトキシシラン145g、3-メタクリロキシプロピルトリメトキシシラン1.3gの混合液とジエチルアクリルアミド165g、アクリル酸3g、反応性乳化剤(商品名「アデカリアソープSR-1025」、旭電化社製、固形分25質量%水溶液)13g、過硫酸アンモニウムの2質量%水溶液40g、イオン交換水1900gの混合液を、反応容器中の温度を80℃に保った状態で約2時間かけて同時に滴下した。さらに熱養生として、反応容器中の温度が80℃の状態で約15時間撹拌を続行した。その後室温まで冷却し、100メッシュの金網で濾過し、固形分14.03質量%、水相成分2.76質量%、数平均粒子径131nmの重合体エマルジョン粒子(TB-1)水分散体を得た。
重合体エマルジョン粒子(TB-1)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-1)を得た。得られたろ液(H-1)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-1)を得た。得られた試験板(I-1)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、57°であった。
重合体エマルジョン粒子(TB-2)水分散体の合成
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を8時間とし、固形分14.05質量%、水相成分4.57質量%、数平均粒子径132nmの重合体エマルジョン粒子(TB-2)水分散体を得た。
重合体エマルジョン粒子(TB-2)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-2)を得た。得られたろ液(H-2)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-2)を得た。得られた試験板(I-2)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、56°であった。
重合体エマルジョン粒子(TB-3)水分散体の合成
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を4時間とし、固形分14.08質量%、水相成分8.91質量%、数平均粒子径131nmの重合体エマルジョン粒子(TB-3)水分散体を得た。
重合体エマルジョン粒子(TB-3)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-3)を得た。得られたろ液(H-3)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-3)を得た。得られた試験板(I-3)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、58°であった。
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を3.5時間とし、固形分14.02質量%、水相成分11.46質量%、数平均粒子径131nmの重合体エマルジョン粒子(TB-4)水分散体を得た。
重合体エマルジョン粒子(B-4)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-4)を得た。得られたろ液(H-4)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-4)を得た。得られた試験板(I-4)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、57°であった。
重合体エマルジョン粒子(TB-5)水分散体の合成
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を3時間とし、固形分14.05質量%、水相成分14.12質量%、数平均粒子径130nmの重合体エマルジョン粒子(TB-5)水分散体を得た。
重合体エマルジョン粒子(TB-5)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-5)を得た。得られたろ液(H-5)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-5)を得た。得られた試験板(I-5)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、57°であった。
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を2.5時間とし、固形分14.07質量%、水相成分16.34質量%、数平均粒子径130nmの重合体エマルジョン粒子(TB-6)水分散体を得た。
重合体エマルジョン粒子(B-6)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-6)を得た。得られたろ液(H-6)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-6)を得た。得られた試験板(I-6)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、58°であった。
重合体エマルジョン粒子(TB-7)水分散体の合成
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を2時間とし、固形分14.06質量%、水相成分18.19質量%、数平均粒子径129nmの重合体エマルジョン粒子(TB-7)水分散体を得た。
重合体エマルジョン粒子(TB-7)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-7)を得た。得られたろ液(H-7)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-7)を得た。得られた試験板(I-7)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、57°であった。
重合体エマルジョン粒子(TB-8)水分散体の合成
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生時間を1時間とし、固形分14.09質量%、水相成分21.93質量%、数平均粒子径130nmの重合体エマルジョン粒子(TB-8)水分散体を得た。
重合体エマルジョン粒子(TB-8)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-8)を得た。得られたろ液(H-8)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-8)を得た。得られた試験板(I-8)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、56°であった。
重合体エマルジョン粒子(TB-9)水分散体の合成
合成例1と同様の方法で重合を行い、製造例12に記載の熱養生を行わず、固形分14.11質量%、水相成分28.66質量%、数平均粒子径128nmの重合体エマルジョン粒子(TB-9)水分散体を得た。
重合体エマルジョン粒子(TB-8)水分散体を、限外ろ過装置を用いてろ過し、水相成分を含有するろ液(H-8)を得た。得られたろ液(H-8)を5cm×5cmの青板ガラス上にディップコートした後、90℃で24時間乾燥させることにより、フィルム状の試験板(I-8)を得た。得られた試験板(I-8)のフィルム表面に脱イオン水の滴を乗せ、20℃で10秒間放置した後、初期接触角を測定したところ、58°であった。
製造例12で合成した重合体エマルジョン粒子(TB-1)水分散体100gに数平均粒子径12nmの水分散コロイダルシリカ(商品名「スノーテックスO」、日産化学工業社製、固形分20質量%)100gを混合、攪拌し水系有機・無機複合組成物(E-1)を得た。
5cm×5cmの青板ガラスに上記水系有機・無機複合組成物(E-1)を膜厚が1μmとなるようにバーコートした後、70℃で30分間乾燥することにより、有機・無機複合体皮膜(F-1)を有する試験板(G-1)を得た。得られた有機・無機複合体皮膜を有する試験板(G-1)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例13で合成した重合体エマルジョン粒子(TB-2)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-2)を有する試験板(G-2)を得た。得られた有機・無機複合体皮膜を有する試験板(G-2)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例14で合成した重合体エマルジョン粒子(TB-3)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-3)を有する試験板(G-3)を得た。得られた有機・無機複合体皮膜を有する試験板(G-3)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例15で合成した重合体エマルジョン粒子(TB-4)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-4)を有する試験板(G-4)を得た。得られた有機・無機複合体皮膜を有する試験板(G-4)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例16で合成した重合体エマルジョン粒子(TB-5)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-5)を有する試験板(G-5)を得た。得られた有機・無機複合体皮膜を有する試験板(G-5)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例17で合成した重合体エマルジョン粒子(TB-6)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-6)を有する試験板(G-6)を得た。得られた有機・無機複合体皮膜を有する試験板(G-6)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例18で合成した重合体エマルジョン粒子(TB-7)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-7)を有する試験板(G-7)を得た。得られた有機・無機複合体皮膜を有する試験板(G-7)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例19で合成した重合体エマルジョン粒子(TB-8)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-8)を有する試験板(G-8)を得た。得られた有機・無機複合体皮膜を有する試験板(G-8)の水との初期接触角は7.2゜であった。
重合体エマルジョン粒子(TB-1)に替えて製造例20で合成した重合体エマルジョン粒子(TB-9)水分散体を用いた以外は実施例79と同様の方法で有機・無機複合体皮膜(F-9)を有する試験板(G-9)を得た。得られた有機・無機複合体皮膜を有する試験板(G-9)の水との初期接触角は7.2゜であった。
10…基材
12…塗膜
2…太陽電池モジュール
20…保護部材
22…バックシート
24…発電素子
26…封止材
202…基盤
204…塗膜
3…リフレクター装置
30…積層体(保護部材)
32…光反射鏡
34…支持体
Claims (47)
- (A)数平均粒子径が1nm~400nmの金属酸化物粒子と、
(B)重合体粒子と、を含み、
下記式(I)で表される、前記(B)成分中の水相成分の含有率が、20質量%以下である、コーティング組成物。
水相成分の含有率(%)=((B)成分を分画分子量50,000でろ過したろ液の乾燥質量)×(100-全固形分質量)/(前記ろ液の質量-前記ろ液の乾燥質量)×100/全固形分質量 ・・・(I) - 前記(B)成分は、
(b1)成分:加水分解性珪素化合物と、
(b2)成分:ビニル単量体と、
(b3)成分:乳化剤と、
(b4)成分:水と、
を含む重合原液中で、前記(b1)成分と前記(b2)成分とを重合して得られる重合体エマルジョン粒子(B1)である請求項1に記載のコーティング組成物。 - 前記水相成分の含有率が、15質量%以下である、請求項1又は2に記載のコーティング組成物。
- 前記(B)成分の数平均粒子径が10nm~800nmである、請求項1~3のいずれか一項に記載のコーティング組成物。
- 前記(b2)成分が、水酸基、カルボキシル基、アミド基、アミノ基、及びエーテル基からなる群から選ばれる少なくとも1種の官能基を有するビニル単量体である、請求項2~4のいずれか一項に記載のコーティング組成物。
- 前記(B)成分に対する前記(b2)成分の質量比((b2)/(B))が、0.01/1~1/1である、請求項2~5のいずれか一項に記載のコーティング組成物。
- 前記(A)成分に対する前記(b2)成分の質量比((b2)/(A))が、0.01/1~1/1である請求項2~6のいずれか一項に記載のコーティング組成物。
- 前記(B)成分が、コア層と、前記コア層を被覆する1層又は2層以上のシェル層と、を備えたコア/シェル構造を有する請求項1~7のいずれか一項に記載のコーティング組成物。
- 前記コア層において、前記(b1)成分に対する前記(b2)成分の質量比((b2)/(b1))が、0.01/1~1/1であり、
前記シェル層の最外層において、前記(b1)成分に対する前記(b2)成分の質量比((b2)/(b1))が、0.01/1~5/1である、請求項2~8のいずれか一項に記載のコーティング組成物。 - 前記(B)成分が、前記コア層を形成するシード粒子の存在下で前記重合原液を重合して得られる重合体エマルジョン粒子であり、
前記シード粒子が、前記(b1)成分、前記(b2)成分、及び(b5)成分:前記(b2)成分と共重合可能な他のビニル単量体、からなる群から選択される少なくとも1種以上を重合して得られる、請求項2~9のいずれか一項に記載のコーティング組成物。 - 前記(b2)成分が、2級アミド基、3級アミド基あるいはその両方を有するビニル単量体である、請求項2~10のいずれか一項に記載のコーティング組成物。
- 前記(B)成分に対する前記(A)成分の質量比(A/B)が、110/100~480/100である、請求項1~11のいずれか一項に記載のコーティング組成物。
- (C)成分:下記式(1)、(2)、及び(3)で表される化合物からなる群より選ばれる1種以上の加水分解性珪素化合物を、更に含む、請求項1~12のいずれか一項に記載のコーティング組成物。
R1 nSiX4-n (1)
(式(1)中、R1は、水素原子、あるいは、ハロゲン基、ヒドロキシ基、メルカプト基、アミノ基、(メタ)アクリロイル基又はエポキシ基を有していてもよい、炭素数1~10のアルキル基、アルケニル基、アルキニル基若しくはアリール基を表す。Xは、加水分解性基を表し、nは0~3の整数である。)
X3Si-R2 n-SiX3 (2)
(式(2)中、Xは加水分解性基を表し、R2は炭素数1~6のアルキレン基又はフェニレン基を表す。nは0又は1である。)
R3-(O-Si(OR3)2)n-OR3 (3)
(式(3)中、R3は炭素数1~6のアルキル基を表す。nは2~8の整数である。) - 前記(A)成分に対する前記(C)成分の質量比((C)/(A))が、1/100~100/100である、請求項13に記載のコーティング組成物。
- 前記(B)成分の数平均粒子径が10nm~100nmである、請求項1~14のいずれか一項に記載のコーティング組成物。
- 前記(A)成分が、
(A1)成分:数平均粒子径が1nm~400nmのシリカと、
(A2)成分:数平均粒子径が1nm~2000nmの赤外線吸収剤と、を含み
前記(B)成分の含有量に対する前記(A1)成分と前記(A2)成分との総含有量の質量比((A1+A2)/(B))が、60/100~1000/100であり、
前記(B)成分と前記(A1)成分との前記総含有量に対する前記(A2)成分の含有量の質量比((A2)/(A1+B))が、0.05/100~40/100である、請求項1~15のいずれか一項に記載のコーティング組成物。 - 前記(A)成分が、
(A1)成分:数平均粒子径が1nm~400nmのシリカと、
(A3)成分:数平均粒子径が1nm~2000nmの光触媒と、を含み
前記(B)成分の含有量に対する前記(A1)成分と前記(A3)成分との総含有量の質量比((A1+A3)/(B))が、60/100~480/100であり、
前記(A1)成分と前記(A3)成分との前記総含有量に対する前記(A1)成分の含有量の質量比((A1)/(A1+A3))が、85/100~99/100である、請求項1~16のいずれか一項に記載のコーティング組成物。 - 反射防止用である請求項1~17のいずれか一項に記載のコーティング組成物。
- 耐溶剤用である請求項1~17のいずれか一項に記載のコーティング組成物。
- 帯電防止用である請求項1~17のいずれか一項に記載のコーティング組成物。
- 耐熱用である請求項1~17のいずれか一項に記載のコーティング組成物。
- ハードコート用である請求項1~17のいずれか一項に記載のコーティング組成物。
- 請求項1~22のいずれか一項に記載のコーティング組成物から得られる塗膜。
- 金属酸化物粒子(A)と、
前記(A)成分に囲まれた重合体粒子(B)と、
を含む塗膜であって、
限外濾過法によって前記(B)成分から抽出された分画分子量50,000以下の成分(B2)をフィルムにした場合のフィルム表面の水接触角が30°以下である塗膜。 - (A)数平均粒子径が1nm~400nmの金属酸化物と、
前記(A)成分に囲まれた重合体粒子(B)と、
を含む塗膜であって、
限外濾過法によって前記(B)成分から抽出された分画分子量50,000以下の成分(B2)をフィルムにした場合のフィルム表面の水接触角が30°を超え、その含有量が、5質量%以下である塗膜。 - 前記(B)成分がエマルジョン粒子である、請求項24又は25に記載の塗膜。
- 20℃における表面水接触角が30°以下である、請求項23~26のいずれか一項に記載の塗膜。
- 温度90℃、湿度90%の条件下で24時間静置する高温高湿試験後の塗膜表面の水接触角が20°以下である請求項23~27のいずれか一項に記載の塗膜。
- 基材と、
前記基材の少なくとも一方の表面に形成された、請求項1~22のいずれか一項に記載のコーティング組成物を塗布して得られる塗膜、又は請求項23~28のいずれか一項に記載の塗膜と、
を備える積層体。 - 前記積層体の光線透過率が前記基材の光線透過率よりも高い、請求項29に記載の積層体。
- 前記塗膜の屈折率が前記基材の屈折率よりも0.1以上低い、請求項29又は30に記載の積層体。
- 前記塗膜は、2以上の層を有する塗膜である、請求項29~31のいずれか一項に記載の積層体。
- 前記基材と反対側に位置する最表層の屈折率が前記最表層に隣接する層の屈折率よりも0.1以上低い、請求項29~32のいずれか一項に記載の積層体。
- 前記塗膜を構成する各層の厚さ(dn)が10nm~800nmであり、
前記塗膜の総厚さ(Σdn)が100nm~4000nmである、請求項32又は33に記載の積層体。 - 前記基材の光線透過率が30%~99%である、請求項29~34のいずれか一項に記載の積層体。
- 前記基材における前記塗膜側の表面の反射率(Rb)に対する、前記塗膜の前記基材とは反対側表面の反射率(Rc)の割合((Rc)/(Rb))が、98%以上である、請求項29~35のいずれか一項に記載の積層体。
- 前記塗膜と前記基材との屈折率の差が0.2以下である、請求項29~36のいずれか一項に記載の積層体。
- 前記塗膜の屈折率が1.3~1.48である、請求項29~37のいずれか一項に記載の積層体。
- 前記基材における前記塗膜側の表面の反射率(Rb)が80%以上である、請求項36~38のいずれか一項に記載の積層体。
- 前記基材は、ガラス、アクリル樹脂、ポリカーボネート樹脂、環状オレフィン樹脂、ポリエチレンテレフタレート樹脂、エチレン-フルオロエチレン共重合体からなる群から選択される少なくとも1種を含む、請求項29~39のいずれか一項に記載の積層体。
- 基材の少なくとも一方の表面に、請求項1~22のいずれか一項に記載のコーティング組成物を塗布し、塗膜を形成する工程と、
前記塗膜に対して、70℃以上の加熱処理、あるいは0.1kPa以上の加圧処理の少なくとも一方を施す工程と、
を有する積層体の製造方法。 - エネルギー変換装置用部材である、請求項29~40のいずれか一項に記載の積層体。
- 太陽電池モジュールの保護部材である、請求項42に記載の積層体。
- 請求項42に記載の積層体と、
前記積層体と対向して配置されるバックシートと、
前記積層体と前記バックシートの間に配置される発電素子と、
を備える太陽電池モジュール。 - 光反射鏡の保護部材である、請求項42に記載の積層体。
- 光反射鏡と、
前記光反射光の反射面を保護する請求項45に記載の積層体と、
前記反射鏡を支持する支持体と、
を備えるリフレクター装置。 - 請求項46に記載のリフレクター装置と、
前記リフレクター装置により集光される太陽光を電気エネルギーに変換する装置と、
を備える太陽熱発電システム。
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TW201431979A (zh) | 2014-08-16 |
US20150068603A1 (en) | 2015-03-12 |
US9833811B2 (en) | 2017-12-05 |
KR20110091559A (ko) | 2011-08-11 |
US20120285528A1 (en) | 2012-11-15 |
CN102341467A (zh) | 2012-02-01 |
US8916266B2 (en) | 2014-12-23 |
ES2547416T3 (es) | 2015-10-06 |
JPWO2010104146A1 (ja) | 2012-09-13 |
JP5669722B2 (ja) | 2015-02-12 |
EP2407521B1 (en) | 2015-07-29 |
EP2407521A1 (en) | 2012-01-18 |
US20150079292A1 (en) | 2015-03-19 |
KR101263125B1 (ko) | 2013-05-15 |
TW201038685A (en) | 2010-11-01 |
EP2407521A4 (en) | 2012-07-11 |
TWI506104B (zh) | 2015-11-01 |
TWI553065B (zh) | 2016-10-11 |
BRPI1009429B1 (pt) | 2019-06-18 |
US9630208B2 (en) | 2017-04-25 |
BRPI1009429A2 (pt) | 2017-05-16 |
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