WO2013080913A1 - Matière de revêtement, film de revêtement, feuille arrière de module de cellule solaire et module de cellule solaire - Google Patents

Matière de revêtement, film de revêtement, feuille arrière de module de cellule solaire et module de cellule solaire Download PDF

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Publication number
WO2013080913A1
WO2013080913A1 PCT/JP2012/080453 JP2012080453W WO2013080913A1 WO 2013080913 A1 WO2013080913 A1 WO 2013080913A1 JP 2012080453 W JP2012080453 W JP 2012080453W WO 2013080913 A1 WO2013080913 A1 WO 2013080913A1
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Prior art keywords
coating film
group
paint
coating
sheet
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PCT/JP2012/080453
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English (en)
Japanese (ja)
Inventor
秀人 中川
健司 午坊
秀典 尾崎
和哉 浅野
重仁 匂坂
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ダイキン工業株式会社
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Publication of WO2013080913A1 publication Critical patent/WO2013080913A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6275—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6279—Polymers of halogen containing compounds having carbon-to-carbon double bonds; halogenated polymers of compounds having carbon-to-carbon double bonds containing fluorine atoms
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
    • C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
    • C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • H01L31/049—Protective back sheets
    • 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
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a paint, a coating film, a back sheet of a solar cell module, and a solar cell module. More specifically, the present invention relates to a coating material suitable for coating a back sheet of a solar cell module, a coating film obtained from the coating material, and a back sheet and a solar cell module of the solar cell module having the coating film.
  • a solar cell module is usually composed of a surface layer, a sealing material layer that seals solar cells, and a back sheet.
  • a sealing material for forming the sealing material layer a copolymer of ethylene and vinyl acetate (hereinafter also referred to as EVA) is usually used.
  • the back sheet is required to have various properties such as mechanical strength, weather resistance, waterproof / moisture resistance, and electrical insulation.
  • the structure of the normal back sheet has a multilayer structure, for example, in order from the side in contact with the sealing layer of the solar battery cell, from the weather resistant layer / electrical insulating layer / waterproof / moisture proof layer / back layer located on the back side of the solar battery. It has become.
  • a polyvinyl fluoride film is used for the weather resistant layer and the back surface layer for reasons such as excellent weather resistance, waterproof / moisture resistance, and electrical insulation
  • a PET film is used for the base sheet. It has been.
  • a PET film on which a metal compound such as silica is deposited or a metal layer such as an aluminum foil is provided on the surface of the base sheet.
  • the thickness of the back sheet is usually 20 to 500 ⁇ m in order to satisfy the required characteristics and various required characteristics such as durability and light shielding properties.
  • weight reduction and thinning of the backsheet there has been a demand for weight reduction and thinning of the backsheet.
  • a two-layer backsheet in which a metal substrate (water-impermeable sheet) is coated with a PVdF-based paint in which a specific amount of tetraalkoxysilane or a partial hydrolyzate thereof is blended with PVdF having no functional group.
  • PVdF-based paint Since this PVdF-based paint does not have a functional group, PVdF alone has poor adhesion to EVA as a sealing material.
  • Patent Document 2 attempts to improve this point by blending a specific amount of tetraalkoxysilane or its partial hydrolyzate and orienting the tetraalkoxysilane or its partial hydrolyzate at the interface with EVA.
  • a back sheet for a solar cell module in which a cured coating film of a curable functional group-containing fluorine-containing polymer coating is formed on at least one surface of a water-impermeable sheet (see, for example, Patent Document 3).
  • a curable tetrafluoroethylene (TFE) copolymer Zeffle GK570
  • TFE tetrafluoroethylene
  • Patent Document 3 by using the curable functional group-containing fluorine-containing polymer coating, the thickness of the back sheet can be reduced compared to the pasting of the sheet, and the film thickness is reduced while maintaining the mechanical strength. It is described that the adhesion to the water-impermeable sheet can be improved without introducing tetraalkoxysilane or the like by introducing a functional group into the fluorine-containing polymer. Yes.
  • a back sheet for a solar cell module in which a layer is formed has been proposed (for example, see Patent Document 4).
  • Patent Document 4 such a cured coating layer is particularly excellent in flexibility and adhesion to a base material, and is a lightweight and highly productive sun that does not cause problems of cracks, cracks, whitening, and peeling. It is described that a battery module back sheet is obtained.
  • the present invention has been made in view of the above-described present situation, and is capable of forming a coating film excellent in blocking resistance, the coating film, and a solar cell module backsheet having the coating film, and
  • the object is to provide a solar cell module.
  • the present inventor has studied various kinds of coating materials that can form a coating film excellent in blocking resistance against the contact surface.
  • the coating materials containing the curable functional group-containing fluorine-containing polymer the type of the curing agent is appropriately selected. It has been found that by selecting, it is possible to obtain a coating material that gives a cured coating film with greatly improved blocking resistance against the contact surface as compared with conventional coating materials.
  • the curing agent is a polyisocyanate compound derived from isophorone diisocyanate
  • the article (sheet or the like) on which the coating film is formed is wound up or stacked, the non-painted surface or the other where the coating film contacts
  • blocking with the painted surface can be sufficiently suppressed as compared with a coating film obtained from a conventional paint.
  • seat of the solar cell module excellent in the blocking resistance with respect to a contact surface was obtained by forming this coating film on base materials, such as a water-impermeable sheet, and reached
  • the present invention is a paint comprising a curable functional group-containing fluorine-containing polymer and a polyisocyanate compound derived from isophorone diisocyanate.
  • This invention is also a coating film characterized by being obtained from the said coating material.
  • the present invention also provides a back sheet for a solar cell module comprising a water-impermeable sheet and a coating film made of the coating material formed on at least one surface of the water-impermeable sheet.
  • the present invention also includes a water-impermeable sheet, a coating film made of the coating material formed on at least one surface of the water-impermeable sheet, and a sealing material layer formed on the coating film. It is also a solar cell module characterized by this.
  • the present invention is described in detail below.
  • the coating material of the present invention contains a curable functional group-containing fluorine-containing polymer.
  • the curable functional group-containing fluorine-containing polymer include polymers in which a curable functional group is introduced into the fluorine-containing polymer.
  • the fluorine-containing polymer includes a resinous polymer having a clear melting point, an elastomeric polymer exhibiting rubber elasticity, and an intermediate thermoplastic elastomeric polymer.
  • Examples of the functional group that imparts curability to the fluorinated polymer include a hydroxyl group (excluding a hydroxyl group contained in a carboxyl group; the same applies hereinafter), a carboxyl group, a group represented by —COOCO—, a cyano group, and an amino group. , A glycidyl group, a silyl group, a silanate group, an isocyanate group, and the like. Among these, at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, a group represented by —COOCO—, a cyano group, an amino group, and a silyl group is preferable from the viewpoint of good curing reactivity.
  • At least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a silyl group is more preferred, and in particular, a hydroxyl group and a carboxyl group from the viewpoint of easy availability of the polymer and good reactivity. More preferred is at least one group selected from the group consisting of These curable functional groups are usually introduced into the fluorinated polymer by copolymerizing a fluorinated monomer and a curable functional group-containing monomer.
  • the curable functional group-containing monomer examples include a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and a silicone-based vinyl monomer. Species or two or more can be used.
  • the curable functional group-containing fluorine-containing polymer includes a polymer unit based on a fluorine-containing monomer, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, and a silicone-based vinyl monomer.
  • the curable functional group-containing fluorine-containing polymer is a polymer unit based on a fluorine-containing monomer, and at least one curable functional group selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer. More preferably, it contains polymerized units based on group-containing monomers.
  • the polymerized units based on the curable functional group-containing monomer is preferably 1 to 20 mol% with respect to the total polymerized units of the curable functional group-containing fluoropolymer.
  • a more preferred lower limit is 2 mol%, and a more preferred upper limit is 10 mol%.
  • fluorine-containing monomer that is, a monomer for forming a fluorine-containing polymer into which a curable functional group is introduced
  • a monomer for forming a fluorine-containing polymer into which a curable functional group is introduced for example, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride, and , Fluorovinyl ether can be mentioned, and one or more of these can be used.
  • At least one selected from the group consisting of tetrafluoroethylene, chlorotrifluoroethylene, and vinylidene fluoride is preferable, and at least one selected from the group consisting of tetrafluoroethylene and chlorotrifluoroethylene It is more preferable that Specific examples of the fluorinated polymer into which a curable functional group-containing monomer or a curable functional group is introduced will be described later.
  • the coating material of the present invention further contains a polyisocyanate compound derived from isophorone diisocyanate (IPDI) (hereinafter also simply referred to as polyisocyanate compound).
  • the polyisocyanate compound functions as a curing agent in the coating material of the present invention.
  • polyisocyanate compound examples include an adduct obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, an isocyanurate structure (nurate structure) composed of isophorone diisocyanate, and isophorone diisocyanate. Can be mentioned biuret.
  • adduct examples include the following general formula (1):
  • R 1 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • R 2 represents the following chemical formula (2):
  • R 1 in the general formula (1) is a hydrocarbon group based on the above trivalent or higher aliphatic polyhydric alcohol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and 3 to 6 carbon atoms. The aliphatic hydrocarbon group is more preferable.
  • the k is a number corresponding to the valence of a trihydric or higher aliphatic polyhydric alcohol. K is more preferably an integer of 3 to 10, and still more preferably an integer of 3 to 6.
  • the isocyanurate structure has the following chemical formula (3) in the molecule:
  • isocyanurate structure examples include a trimer obtained by a trimerization reaction of isophorone diisocyanate, a pentamer obtained by a pentamerization reaction, a heptamer obtained by a heptamerization reaction, and the like. Among them, the following general formula (4):
  • the isocyanurate structure is preferably a trimer of isophorone diisocyanate.
  • the biuret is represented by the following general formula (5):
  • R 2 has the general formula (1) is the same as R 2 in.
  • the polyisocyanate compound is preferably at least one selected from the group consisting of the adduct and the isocyanurate structure. That is, the polyisocyanate compound is at least selected from the group consisting of an adduct obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol, and an isocyanurate structure composed of isophorone diisocyanate. One type is preferable. Specific examples of the polyisocyanate compound will be described later.
  • the coating material of this invention contains the said sclerosing
  • curable functional group-containing fluorine-containing polymer examples include, but are not limited to, the following. In addition, these 1 type (s) or 2 or more types can be used.
  • Hydroxyl-containing monomer examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxy-2-methylpropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methyl. Hydroxyl-containing vinyl ethers such as butyl vinyl ether, 5-hydroxypentyl vinyl ether and 6-hydroxyhexyl vinyl ether; hydroxyl-containing allyl ethers such as 2-hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether and glycerol monoallyl ether . Of these, hydroxyl group-containing vinyl ethers, particularly 4-hydroxybutyl vinyl ether and 2-hydroxyethyl vinyl ether, are preferred from the viewpoint of excellent polymerization reactivity and functional group curability.
  • hydroxyl group-containing monomers examples include hydroxyalkyl esters of (meth) acrylic acid such as 2-hydroxyethyl acrylate and 2-hydroxyethyl methacrylate.
  • Carboxyl group-containing monomer examples include a general formula (6):
  • R 3 , R 4 and R 5 are the same or different and all are hydrogen atoms, alkyl groups, carboxyl groups or ester groups; n is 0 or 1), Unsaturated carboxylic acids such as saturated dicarboxylic acids, monoesters or acid anhydrides thereof; or general formula (7):
  • R 6 and R 7 are the same or different and both are saturated or unsaturated linear or cyclic alkyl groups; n is 0 or 1; m is 0 or 1) And monomers.
  • carboxyl group-containing monomer examples include, for example, acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, cinnamic acid, 3-allyloxypropionic acid, 3- (2-allyloxyethoxycarbonyl) propionic acid, and itacone.
  • examples thereof include acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, fumaric acid, fumaric acid monoester, vinyl phthalate, and vinyl pyromellitic acid.
  • crotonic acid, itaconic acid, maleic acid, maleic acid monoester, fumaric acid, fumaric acid monoester, and 3-allyloxypropionic acid which have low homopolymerization, have low homopolymerization and are difficult to form a homopolymer. This is preferable.
  • carboxyl group-containing vinyl ether monomer represented by the general formula (7) examples include 3- (2-allyloxyethoxycarbonyl) propionic acid, 3- (2-allyloxybutoxycarbonyl) propionic acid, Examples thereof include one or more of 3- (2-vinyloxyethoxycarbonyl) propionic acid, 3- (2-vinyloxybutoxycarbonyl) propionic acid and the like.
  • 3- (2-allyloxyethoxycarbonyl) propionic acid and the like are advantageous and preferable in terms of good monomer stability and polymerization reactivity.
  • Silicone vinyl monomer examples include CH 2 ⁇ CHCO 2 (CH 2 ) 3 Si (OCH 3 ) 3 , CH 2 ⁇ CHCO 2 (CH 2 ) 3 Si (OC 2 H 5 ) 3 , and CH 2 ⁇ C.
  • vinyl silanes include: vinyl ethers such as trimethoxysilylethyl vinyl ether, triethoxysilylethyl vinyl ether, trimethoxysilylbutyl vinyl ether, methyldimethoxysilylethyl
  • fluorine-containing polymer into which the curable functional group is introduced may include the following, depending on the polymer units constituting the polymer.
  • Perfluoroolefin polymer mainly composed of perfluoroolefin units Specific examples include a homopolymer of tetrafluoroethylene (TFE), a copolymer of TFE and hexafluoropropylene (HFP), perfluoro (alkyl vinyl ether) (PAVE), and the like, and further copolymerizable therewith. And copolymers with other monomers.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • PAVE perfluoro (alkyl vinyl ether)
  • Examples of the other copolymerizable monomers include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl versatate, vinyl laurate, vinyl stearate, cyclohexyl carboxyl.
  • Carboxylic acid vinyl esters such as vinyl acid vinyl, vinyl benzoate and vinyl para-t-butylbenzoate;
  • Alkyl vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, cyclohexyl vinyl ether; ethylene, propylene, n-butene, isobutene, etc.
  • Non-fluorinated olefins fluorinated monomers such as vinylidene fluoride (VdF), chlorotrifluoroethylene (CTFE), vinyl fluoride (VF), fluorovinyl ether, etc.
  • VdF vinylidene fluoride
  • CTFE chlorotrifluoroethylene
  • VF vinyl fluoride
  • fluorovinyl ether etc.
  • the present invention is not limited only to.
  • TFE-based polymers mainly composed of TFE are preferable in terms of excellent pigment dispersibility, weather resistance, copolymerization, and chemical resistance.
  • curable functional group-containing perfluoroolefin-based polymer examples include, for example, a copolymer of TFE / isobutylene / hydroxybutyl vinyl ether / other monomers, TFE / vinyl versatate / hydroxybutyl vinyl ether / other monomers.
  • a copolymer of / hydroxybutyl vinyl ether / other monomers is preferable.
  • TFE-based curable polymer composition for paint examples include Zeffle (registered trademark) GK series manufactured by Daikin Industries, Ltd.
  • CTFE polymer mainly composed of chlorotrifluoroethylene (CTFE) unit Specific examples include a copolymer of CTFE / hydroxybutyl vinyl ether / other monomers.
  • CTFE-based curable polymer compositions for paint examples include Lumiflon (registered trademark) manufactured by Asahi Glass Co., Ltd., Fluonate (registered trademark) manufactured by DIC Corporation, and Cefral Coat (registered trademark) manufactured by Central Glass Co., Ltd. And ZAFLON (registered trademark) manufactured by Toa Gosei Co., Ltd. can be exemplified.
  • VdF polymers mainly composed of vinylidene fluoride (VdF) units Specific examples include VdF / TFE / hydroxybutyl vinyl ether / a copolymer of other monomers.
  • fluoroalkyl group-containing polymer examples include Unidyne (registered trademark) manufactured by Daikin Industries, Ltd., FTONE (registered trademark), Zonyl (registered trademark) manufactured by DuPont, and the like.
  • perfluoroolefin-based polymers are preferable.
  • the curable functional group-containing fluorine-containing polymer can be produced, for example, by the method disclosed in JP-A-2004-204205.
  • the content of the curable functional group-containing fluorine-containing polymer in the coating material of the present invention is preferably 20 to 95% by mass with respect to 100% by mass of the total nonvolatile content in the coating material. More preferably, it is 40 to 95% by mass.
  • polyisocyanate compound is an adduct of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol
  • specific examples of the trihydric or higher aliphatic polyhydric alcohol include glycerol, trimethylolpropane (TMP).
  • 1,2,6-hexanetriol trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1,1,1-tris (bishydroxymethyl) propane, 2,2-bis (hydroxymethyl) Trihydric alcohols such as butanol-3; tetrahydric alcohols such as pentaerythritol and diglycerol; pentavalent alcohols such as arabit, ribitol and xylitol (pentit); hexavalent alcohols such as sorbit, mannitol, galactitol and allozulcit ) Etc. Of these, trimethylolpropane and pentaerythritol are preferable.
  • Adducts suitably used in the present invention can be obtained by addition polymerization of isophorone diisocyanate and a trihydric or higher aliphatic polyhydric alcohol as described above.
  • R 8 represents the following chemical formula (2):
  • TMP adduct of isophorone diisocyanate represented by the general formula (8)
  • Takenate (registered trademark) D140N manufactured by Mitsui Chemicals, Inc., NCO content 11%) and the like can be mentioned. .
  • the content of the polyisocyanate compound is 0.1 to 5 equivalents, preferably 0.5 to 1.5 equivalents, relative to 1 equivalent of the curable functional group in the curable functional group-containing fluoropolymer.
  • the content of the curable functional group in the curable functional group-containing fluorine-containing polymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and neutralization titration depending on the type of monomer. .
  • content of the said curable functional group containing fluorine-containing polymer and the said polyisocyanate compound is based on the mass of the non volatile matter except a solvent etc., respectively.
  • the paint of the present invention can be prepared in a conventional manner in the form of a solvent-type paint, a water-type paint, a powder-type paint, and the like.
  • a solvent-type paint is preferable from the viewpoint of easiness of film formation, curability and good drying properties.
  • an organic solvent is preferable, and esters such as ethyl acetate, butyl acetate, isopropyl acetate, isobutyl acetate, cellosolve acetate, and propylene glycol methyl ether acetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Cyclic ethers such as tetrahydrofuran and dioxane; amides such as N, N-dimethylformamide and N, N-dimethylacetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; propylene glycol methyl ether and ethyl cellosolve Glycol ethers such as diethylene glycol esters such as carbitol acetate; n-pentane, n-hexane, n-heptane
  • the concentration of the curable functional group-containing fluorine-containing polymer with respect to the total amount of the paint of 100% by mass is preferably 5 to 95% by weight, and preferably 10 to 70% by weight. More preferred.
  • additives can be further blended in the coating material of the present invention according to required characteristics.
  • the additive include a curing accelerator, a curing retarder, a pigment, a pigment dispersant, an antifoaming agent, a leveling agent, an ultraviolet absorber, a light stabilizer, a thickening agent, an adhesion improving agent, and a matting agent.
  • curing accelerator examples include organic tin compounds, acidic phosphate esters, reaction products of acidic phosphate esters and amines, saturated or unsaturated polycarboxylic acids or acid anhydrides thereof, organic titanate compounds, amine compounds, Examples include lead octylate.
  • the blending ratio of the curing accelerator is preferably about 1.0 ⁇ 10 ⁇ 6 to 1.0 ⁇ 10 ⁇ 2 parts by weight, preferably 5.0 ⁇ 10 ⁇ 5 to 100 parts by weight of the curable functional group-containing fluoropolymer. About 1.0 ⁇ 10 ⁇ 3 parts by weight is more preferable.
  • the paint of the present invention preferably further contains a pigment.
  • a pigment thereby, the cured coating film obtained becomes excellent in UV shielding property.
  • a pigment from the viewpoint of making the appearance of the solar cell module beautiful.
  • Specific examples of pigments include white pigments such as titanium oxide and calcium carbonate, black pigments such as carbon black, and composite metals such as Cu—Cr—Mn alloys; phthalocyanines, quinacridones, azos, etc. However, it is not limited to these.
  • the addition amount of the pigment is preferably 0.1 to 200 parts by weight, and more preferably 0.1 to 160 parts by weight with respect to 100 parts by weight of the curable functional group-containing fluorine-containing polymer.
  • the paint of the present invention preferably further contains an ultraviolet absorber. Since solar cells are used outdoors for a long time with strong ultraviolet rays, countermeasures against deterioration of the backsheet due to ultraviolet rays are required. If an ultraviolet absorber is added to the coating material of this invention, the function of ultraviolet absorption can be provided to the cured coating film layer.
  • an ultraviolet absorber both organic and inorganic ultraviolet absorbers can be used. Examples of the organic type include ultraviolet absorbers such as salicylic acid ester type, benzotriazole type, benzophenone type, and cyanoacrylate type, and inorganic type such as filler type inorganic ultraviolet absorbers such as zinc oxide and cerium oxide are preferable.
  • An ultraviolet absorber may be used individually by 1 type, and may be used in combination of 2 or more type.
  • the amount of the ultraviolet absorber is preferably 0.1 to 15% by mass with respect to 100% by mass of the total amount of the curable functional group-containing fluoropolymer in the paint. When the amount of the ultraviolet absorber is too small, the effect of improving the light resistance cannot be sufficiently obtained, and when the amount is too large, the effect is saturated.
  • This invention is also a coating film obtained from the said coating material.
  • the coating film can be formed by applying the coating material of the present invention to a suitable substrate and curing it according to the application.
  • the cured coating film is formed on the base material by applying the coating material of the present invention to the base material according to the form of the coating material.
  • the coating may be performed within a temperature range of normal conditions in the coating form, and curing and drying are performed at 10 to 300 ° C., usually 100 to 200 ° C. for 30 seconds to 3 days in the case of a solvent-type paint. Therefore, when the coating material of the present invention is used for coating the back sheet of the solar cell module, a material that is desired to avoid treatment at a high temperature, such as a Si-deposited PET sheet, can be used without any problem as the water-impermeable sheet. After curing and drying, curing may be performed, and curing is usually completed at 20 to 300 ° C. for 1 minute to 3 days.
  • the coating on the substrate may be performed by directly applying the coating material of the present invention to the substrate, or may be performed by applying it through a primer layer or the like.
  • the primer layer is formed by a conventional method using a conventionally known primer coating.
  • Typical examples of the primer coating include epoxy resin, urethane resin, acrylic resin, silicone resin, polyester resin, and the like.
  • the film thickness of the cured coating film is preferably 5 ⁇ m or more from the viewpoint of good concealability, weather resistance, chemical resistance, and moisture resistance. More preferably, it is 7 micrometers or more, More preferably, it is 10 micrometers or more.
  • the upper limit is preferably about 1000 ⁇ m, and more preferably 100 ⁇ m because if the thickness is too thick, the effect of reducing the weight cannot be obtained.
  • the film thickness is particularly preferably 10 to 40 ⁇ m.
  • the coating film obtained from the coating material of the present invention is also excellent in blocking resistance at the time of winding, it can be particularly suitably applied to the coating of a back sheet of a solar cell module that is generally produced through a winding process.
  • the coating film is formed on one side or both sides of a substrate such as a water-impermeable sheet.
  • the coating film obtained from the coating material of the present invention is formed on one side of the base material and the other side of the base material is a non-coating surface, the coating film is not coated with the base material in the winding process. It will come into contact with the painted surface.
  • the above-mentioned coating film is formed on one side of the substrate and the other side of the substrate is a coating made of another coating (a cured coating of a fluorine-containing polymer coating having no curable functional group described later, polyester Paint film, primer layer, etc.) and other sheets are provided
  • the paint film obtained from the paint of the present invention is a film made of other paint on the substrate in the winding process. It will come into contact with other sheets.
  • the coating film obtained from the coating material of the present invention is formed on both surfaces of the substrate, the coating film is the same type of coating film formed on the other surface of the substrate in the winding process. Will be in contact with. In any of these cases, the coating film obtained from the paint of the present invention can exhibit excellent blocking resistance against the contacting surface.
  • This invention is also a back sheet
  • the water-impermeable sheet is a layer provided so that moisture does not permeate the sealing material or solar cell, and can be used as long as water does not substantially permeate, but weight, price, flexibility From these points, PET sheets, Si-deposited PET sheets, metal thin sheets such as aluminum and stainless steel, and the like are frequently used. Of these, PET sheets are often used. The thickness is usually about 50 to 250 ⁇ m. Of these, Si vapor-deposited PET sheets are often used when moisture resistance is particularly required. The thickness is usually about 10 to 20 ⁇ m.
  • the surface treatment include corona discharge treatment, plasma discharge treatment, chemical conversion treatment, and blast treatment in the case of a metal sheet.
  • the method for forming the coating film on the water-impermeable sheet is as described above.
  • the said coating film may be formed only in the single side
  • the present invention relates to a water-impermeable sheet, a coating film made of the above-mentioned paint formed on at least one surface of the water-impermeable sheet, and a sun having a sealing material layer formed on the coating film It is also a battery module.
  • Examples of a preferable structure of the solar cell module include those shown in FIGS.
  • the solar cell 1 is sealed with a sealing material layer 2, and the sealing material layer 2 is sandwiched between a surface layer 3 and a back sheet 4.
  • the back sheet 4 further comprises a water-impermeable sheet 5 and a cured coating film 6 obtained from the paint of the present invention.
  • the cured coating film 6 is provided only on the sealing material layer 2 side.
  • the sealing material layer 2 is made of an ethylene / vinyl acetate copolymer (EVA), polyvinyl butyral (PVB), a silicone resin, an epoxy resin, an acrylic resin, or the like.
  • EVA ethylene / vinyl acetate copolymer
  • PVB polyvinyl butyral
  • silicone resin an epoxy resin
  • acrylic resin an acrylic resin
  • surface layer 3 a glass plate is usually used, but a flexible material such as a resin sheet may be used.
  • the second structure shown in FIG. 2 has a three-layer structure in which a cured coating film 6 is formed on both surfaces of a water-impermeable sheet 5.
  • This second structure combines the advantages of both the cured coating film 6 on the side of the sealing material layer 2 and the cured coating film 6 on the side opposite to the sealing material layer 2 although the film thickness of the backsheet increases. It has.
  • a fluorine-containing polymer having a cured coating film obtained from the paint of the present invention formed on one side of a water-impermeable sheet and having no curable functional group on the other side. It may be a three-layer back sheet formed by forming a cured coating film of a paint, a fluorine-containing polymer sheet, a polyester sheet, or a coating film (other sheet or coating film) of a polyester paint.
  • the third structure shown in FIG. 3 is such that a cured coating film 6 obtained from the paint of the present invention is formed on the sealing material layer 2 side of the water-impermeable sheet 5 and the other side is opposite to the sealing material layer 2.
  • the coating film 7 is formed.
  • the material constituting the coating film 7 may be a cured coating film of a fluorine-containing polymer paint having no curable functional group, a fluorine-containing polymer sheet, a polyester sheet, or a coating film of a polyester paint.
  • a conventionally known surface treatment may be performed on the coating film. Examples of the surface treatment include corona discharge treatment, plasma discharge treatment, chemical conversion treatment, and blast treatment.
  • a cured coating film of the above-mentioned fluorine-containing polymer paint having no curable functional group for example, a cured coating of a paint prepared by blending tetraalkoxysilane or a partial hydrolyzate thereof with PVdF described in JP-A-2004-214342.
  • Film, cured coating film of mixed paint of VdF / TFE / CTFE copolymer and alkoxysilane unit-containing acrylic resin cured coating film of mixed paint of VdF / TFE / HFP copolymer and hydroxyl group-containing acrylic resin, VdF / Examples thereof include a cured coating film of a paint in which an aminosilane coupling agent is blended with an HFP copolymer.
  • the film thickness is usually preferably 5 to 300 ⁇ m from the viewpoint of good concealability, weather resistance, chemical resistance and moisture resistance. More preferably, it is 10 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m. In this case also, a primer layer or the like may be interposed.
  • fluoropolymer sheet examples include a PVdF sheet, a PVF sheet, a PCTFE sheet, a TFE / HFP / ethylene copolymer sheet, a TFE / HFP copolymer (FEP) sheet, a TFE / PAVE copolymer (PFA) sheet, and ethylene.
  • fluorine-containing polymer sheets used in current backsheets such as a / TFE copolymer (ETFE) sheet and an ethylene / CTFE copolymer (ECTFE) sheet.
  • the film thickness is usually preferably 5 to 300 ⁇ m from the viewpoint of good weather resistance. More preferably, it is 10 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m.
  • the adhesion to the water-impermeable sheet 5 is an acrylic adhesive, urethane adhesive, epoxy adhesive, polyester adhesive. It can be performed by an agent or the like.
  • the film thickness is usually preferably 5 to 300 ⁇ m from the viewpoint of good weather resistance, cost, and transparency. More preferably, it is 10 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m.
  • polyester paint examples include those using a saturated polyester resin using polyvalent carboxylic acid and polyhydric alcohol, and those using an unsaturated polyester resin using maleic anhydride, fumaric acid and the like and glycols, etc.
  • a coating film can be formed by a coating method such as roll coating, curtain coating, spray coating, or die coating.
  • the film thickness is preferably 5 to 300 ⁇ m from the viewpoint of good concealability, weather resistance, chemical resistance and moisture resistance. More preferably, it is 10 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m. In this case also, a primer layer or the like may be interposed.
  • the paint of the present invention can be suitably applied to various films and sheets produced through a winding process, in addition to the above-described solar cell module applications, directly on a substrate such as metal or resin, or a wash primer. It can be applied over an undercoat such as an anti-rust paint, epoxy paint, acrylic resin paint or polyester resin paint.
  • the coating material of the present invention has the above-described configuration, it is possible to form a coating film excellent in blocking resistance during winding. Such a coating film is extremely useful as a coating for a back sheet of a solar cell module.
  • FIG. 1 is a schematic cross-sectional view of a first structure of a solar cell module.
  • FIG. 2 is a schematic cross-sectional view of a second structure of the solar cell module.
  • FIG. 3 is a schematic cross-sectional view of a third structure of the solar cell module.
  • the glass beads were filtered through a # 80 mesh sieve, and 283 parts by mass of a curable TFE copolymer (Zeffle GK570) and 85 parts by mass of butyl acetate were added to the solution to prepare a white paint.
  • a curable TFE copolymer Zeffle GK570
  • Curing agent (Takenate D140N, manufactured by Mitsui Chemicals, Adduct of IPDI and TMP, NCO content 10.8%) 7 parts by mass (curing functionality in curable TFE copolymer) Paint 1 was prepared by blending 1.0 equivalent to 1 equivalent of the base).
  • Example 1 As a water-impermeable sheet, a PET film (Lumirror S10 manufactured by Toray Industries, Inc., thickness 250 ⁇ m. Sheet A) is used, and the coating 1 prepared in Preparation Example 1 on one side of the sheet A has a dry film thickness of 10 ⁇ m. Then, it was coated with a coater so as to be dried at 120 ° C. for 2 minutes to prepare a backsheet A1 having a two-layer structure. This sample was examined for blocking resistance. The results are shown in Table 1.
  • test method and measurement method are as follows.
  • Blocking resistance test This was performed according to JIS K5600-3-5.
  • the prepared paint was applied to a 50 mm ⁇ 100 mm PET film, and dried by heating in a dryer (SPHH-400, manufactured by Espec Corp.) at 120 ° C. for 2 minutes. Thereafter, the test piece was taken out and allowed to cool to room temperature. Next, the films were sandwiched with glass so that the painted surface and the unpainted surface of the test piece overlap each other with an area of 50 mm ⁇ 50 mm.
  • a 20 kg weight was placed thereon, and maintained at 40 ° C. for 24 hours while a pressure of 0.08 MPa was applied to the contact surface between the films.
  • Evaluation is allowed to cool the two films to room temperature, pull the two films to the left and right, and visually observe the peelability of the backsheet A1 and PET and the degree of disturbance of the coating film at that time, Evaluation was made in 5 stages.
  • the evaluation criteria are as follows. 5: Leave with nature. 4: Two pieces leave with very little force. 3: Peel off when force is applied, and the surface of the coating film is slightly disturbed. 2: Peel off when force is applied, and the surface of the coating is disturbed. 1: It cannot be removed even if force is applied.
  • Example 2 As a curing agent, Desmodur Z4470 (manufactured by Sumika Bayer Urethane Co., Ltd., IPDI isocyanurate structure, NCO content 11%) 28.4 parts by mass (one equivalent of the curable functional group in the curable TFE copolymer) A coating 2 was prepared in the same manner as in Preparation Example 1 except that 1.0 equivalent was used, and a backsheet A2 having a two-layer structure was prepared in the same manner as in Example 1. This sample was examined for blocking resistance. The results are shown in Table 1.
  • Comparative Example 1 Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., isocyanurate structure of hexamethylene diisocyanate, NCO content 21.1%) as a curing agent 14.8 parts by mass (curable functional group 1 in curable TFE copolymer) Comparative paint 1 was prepared in the same manner as in Preparation Example 1 except that 1.0 equivalent to equivalent weight) was used, and a comparative backsheet A1 having a two-layer structure was prepared in the same manner as in Example 1. This sample was examined for blocking resistance. The results are shown in Table 1.

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Abstract

La présente invention porte sur : une matière de revêtement qui peut former un film de revêtement ayant une excellente résistance de blocage ; ledit film de revêtement ; une feuille arrière de module de cellule solaire qui comprend ledit film de revêtement ; et un module de cellule solaire. La présente invention est une matière de revêtement caractérisée comme contenant ce qui suit : un polymère contenant du fluor qui contient un groupe fonctionnel durcissable ; et un composé polyisocyanate issu de diisocyanate d'isophorone.
PCT/JP2012/080453 2011-12-02 2012-11-26 Matière de revêtement, film de revêtement, feuille arrière de module de cellule solaire et module de cellule solaire WO2013080913A1 (fr)

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Cited By (2)

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Publication number Priority date Publication date Assignee Title
US9252295B2 (en) 2011-11-04 2016-02-02 Daikin Industries, Ltd. Coating material, coating film, backsheet for solar cell module, and solar cell module
CN115477875A (zh) * 2022-10-10 2022-12-16 江苏中来新材科技有限公司 一种黑色辐射降温功能涂料及制作方法、背板及应用

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104553209B (zh) * 2014-12-19 2016-09-14 苏州佳亿达电器有限公司 一种太阳能光伏板保护膜

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JPH04106117A (ja) * 1990-08-28 1992-04-08 Dainippon Ink & Chem Inc 含ふっ素ビニル重合体組成物
WO1997011130A1 (fr) * 1995-09-22 1997-03-27 Daikin Industries, Ltd. Inhibiteur de deposition de polluants et composition de materiau de revetement
WO2006077751A1 (fr) * 2005-01-19 2006-07-27 Daikin Industries, Ltd. Composition de revêtement faiblement teintant et film de revêtement faiblement teintant produit à partir de celle-ci
WO2007063698A1 (fr) * 2005-11-30 2007-06-07 Daikin Industries, Ltd. Composition de revêtement pour des doublages de protection de piles solaires
WO2010035782A1 (fr) * 2008-09-26 2010-04-01 旭硝子株式会社 Composition fluoropolymère
WO2010126000A1 (fr) * 2009-04-27 2010-11-04 ダイキン工業株式会社 Module de cellule solaire et feuille arrière destinée audit module
JP2011162598A (ja) * 2010-02-05 2011-08-25 Dic Corp コーティング剤組成物
WO2011158898A1 (fr) * 2010-06-16 2011-12-22 ダイキン工業株式会社 Couche arrière exposable aux intempéries pour module de cellule solaire

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Publication number Priority date Publication date Assignee Title
JPH04106117A (ja) * 1990-08-28 1992-04-08 Dainippon Ink & Chem Inc 含ふっ素ビニル重合体組成物
WO1997011130A1 (fr) * 1995-09-22 1997-03-27 Daikin Industries, Ltd. Inhibiteur de deposition de polluants et composition de materiau de revetement
WO2006077751A1 (fr) * 2005-01-19 2006-07-27 Daikin Industries, Ltd. Composition de revêtement faiblement teintant et film de revêtement faiblement teintant produit à partir de celle-ci
WO2007063698A1 (fr) * 2005-11-30 2007-06-07 Daikin Industries, Ltd. Composition de revêtement pour des doublages de protection de piles solaires
WO2010035782A1 (fr) * 2008-09-26 2010-04-01 旭硝子株式会社 Composition fluoropolymère
WO2010126000A1 (fr) * 2009-04-27 2010-11-04 ダイキン工業株式会社 Module de cellule solaire et feuille arrière destinée audit module
JP2011162598A (ja) * 2010-02-05 2011-08-25 Dic Corp コーティング剤組成物
WO2011158898A1 (fr) * 2010-06-16 2011-12-22 ダイキン工業株式会社 Couche arrière exposable aux intempéries pour module de cellule solaire

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9252295B2 (en) 2011-11-04 2016-02-02 Daikin Industries, Ltd. Coating material, coating film, backsheet for solar cell module, and solar cell module
CN115477875A (zh) * 2022-10-10 2022-12-16 江苏中来新材科技有限公司 一种黑色辐射降温功能涂料及制作方法、背板及应用
CN115477875B (zh) * 2022-10-10 2023-10-31 江苏中来新材科技有限公司 一种黑色辐射降温功能涂料及制作方法、背板及应用

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