WO2019101065A1 - 组合物、涂料、涂膜、太阳能电池组件背板以及太阳能电池组件 - Google Patents

组合物、涂料、涂膜、太阳能电池组件背板以及太阳能电池组件 Download PDF

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WO2019101065A1
WO2019101065A1 PCT/CN2018/116412 CN2018116412W WO2019101065A1 WO 2019101065 A1 WO2019101065 A1 WO 2019101065A1 CN 2018116412 W CN2018116412 W CN 2018116412W WO 2019101065 A1 WO2019101065 A1 WO 2019101065A1
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composition
group
coating film
acid
solar cell
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English (en)
French (fr)
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刘韦韦
中川秀人
长门大
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Daikin Fluorochemicals China Co Ltd
Daikin Industries Ltd
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Daikin Fluorochemicals China Co Ltd
Daikin Industries Ltd
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Priority to CN201880075351.5A priority Critical patent/CN111511852A/zh
Priority to US16/766,313 priority patent/US11746252B2/en
Priority to CA3083003A priority patent/CA3083003A1/en
Priority to KR1020207018136A priority patent/KR102449432B1/ko
Priority to JP2020528287A priority patent/JP7023362B2/ja
Publication of WO2019101065A1 publication Critical patent/WO2019101065A1/zh
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
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    • 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
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    • 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
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    • 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
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    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
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    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a composition, a coating, a coating film, a solar cell module back sheet, and a solar cell module. More particularly, the present invention relates to a composition suitable for coating of a solar cell module back sheet, a coating film obtained from the composition, and a solar cell module back sheet and solar cell module having the coating film.
  • a solar cell module is generally composed of a surface layer, a sealing material layer that seals the solar cell unit, and a back sheet.
  • a sealing material forming the sealant layer a copolymer of ethylene and vinyl acetate (hereinafter also referred to as EVA.) is usually used.
  • Patent Document 1 describes a solar battery module back sheet obtained by forming a cured coating film of a fluoropolymer coating containing a curable functional group on at least one surface of a water-impermeable sheet.
  • Patent Document 1 Japanese Laid-Open Patent Publication No. 2007-35694
  • An object of the present invention is to provide a composition capable of forming a coating film which also has good adhesion to a substrate after a high pressure cooking test, a coating film obtained from the composition, and a solar cell module back sheet having the coating film and Solar cell module.
  • the present invention relates to a composition
  • a composition comprising a curable functional group-containing fluoropolymer and a pentamethylene diisocyanate curing agent.
  • the present invention relates to a coating film which is obtained from the above composition.
  • the invention further relates to a laminate comprising a substrate and a layer obtained from the above composition.
  • the present invention relates to a solar cell module back sheet characterized by having a water-impermeable sheet and a coating film formed on at least one side of the water-impermeable sheet, the coating film being composed of the above composition get.
  • the present invention relates to a solar cell module characterized by having a water-impermeable sheet, a coating film formed on at least one side of the water-impermeable sheet, and a film formed on the coating film.
  • a sealant layer obtained from the above composition.
  • composition of the present invention contains a fluoropolymer containing a curable functional group.
  • the fluoropolymer containing a curable functional group may be a polymer obtained by introducing a curable functional group into a fluoropolymer.
  • the curable functional group-containing fluoropolymer includes a resinous polymer having a clear melting point, an elastomeric polymer exhibiting rubber elasticity, and a thermoplastic elastomeric polymer interposed therebetween.
  • the functional group which imparts curability to the fluorinated polymer can be appropriately selected from the ease of production of the polymer or the curing system, and examples thereof include a hydroxyl group (excluding a hydroxyl group contained in a carboxyl group, the same applies hereinafter), a carboxyl group, and a -COOCO- A group represented by a group, a cyano group, an amino group, an epoxy group, a silyl group or the like.
  • At least one group selected from the group consisting of a group represented by a hydroxyl group, a carboxyl group, and -COOCO-, an amino group, a cyano group, and a silyl group is preferred from the viewpoint of good curing reactivity, and more preferably At least one group selected from the group consisting of a hydroxyl group, a carboxyl group, an amino group, and a silyl group is further preferably at least one group selected from the group consisting of a hydroxyl group, a carboxyl group, and an amino group, and particularly preferably selected from the group consisting of a hydroxyl group and At least one group of the group consisting of carboxyl groups.
  • These curable functional groups are usually introduced into the fluoropolymer by copolymerization of a monomer having a curable functional group.
  • the above-mentioned curable functional group-containing monomer may, for example, be a hydroxyl group-containing monomer, a carboxyl group-containing monomer, an amino group-containing monomer, or a silicone-based vinyl monomer, and one type or two or more types may be used.
  • the curable functional group-containing fluoropolymer preferably contains a polymerization unit based on a fluorine-containing monomer and a polymerization unit based on a curable functional group-containing monomer selected from a hydroxyl group-containing monomer and a carboxyl group-containing monomer. At least one of the group consisting of a body, an amino group-containing monomer, and a silicone-based vinyl monomer.
  • the above-mentioned curable functional group-containing fluoropolymer more preferably contains a polymer unit based on a fluorine-containing monomer, and at least one curable functional group based on a group selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer.
  • the unit of polymerization of the body preferably contains a polymer unit based on a fluorine-containing monomer, and at least one curable functional group based on a group selected from the group consisting of a hydroxyl group-containing monomer and a carboxyl group-containing monomer.
  • the fluorine-containing monomer may, for example, be tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride, vinyl fluoride or fluorovinyl ether, and one type or two or more types may 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 is more preferable.
  • the polymer unit based on the fluorine-containing monomer is preferably 15% by mole to 50% by mole based on the total of the polymerizable units of the curable functional group-containing fluoropolymer.
  • a more preferred lower limit is 20% by mole, a still more preferred lower limit is 30% by mole, and a particularly preferred lower limit is 40% by mole.
  • a more preferable upper limit is 49 mol%, and a further more preferable upper limit is 47 mol%.
  • the polymerization unit based on the curable functional group-containing monomer is preferably from 8 mol% to 30 mol% based on the total polymerized unit of the curable functional group-containing fluoropolymer.
  • a more preferred lower limit is 10% by mole, and a more preferred upper limit is 20% by mole.
  • the following monomers can be exemplified, but are not limited thereto.
  • one type or two or more types can be used.
  • the hydroxyl group-containing monomer may, for example, be 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether or 2-hydroxy-2-methylpropyl vinyl ether.
  • a hydroxyl group-containing vinyl ether such as 4-hydroxybutyl vinyl ether, 4-hydroxy-2-methylbutyl vinyl ether, 5-hydroxypentyl vinyl ether or 6-hydroxyhexyl vinyl ether;
  • a hydroxyl group-containing allyl ether such as hydroxyethyl allyl ether, 4-hydroxybutyl allyl ether or glycerol monoallyl ether.
  • a hydroxyl group-containing vinyl ether is preferable from the viewpoint of excellent polymerization reactivity and curability of a functional group, and it is more preferable to preferably form the formula (1):
  • the hydroxyl group-containing monomer represented by the formula (wherein l is 0 or 1 and m is an integer of 2 or more) is more preferably selected from the group consisting of 4-hydroxybutyl vinyl ether, 2-hydroxyethyl vinyl ether, and 2-hydroxyethyl group. At least one monomer of the group consisting of allyl ether and 4-hydroxybutyl allyl ether.
  • Examples of the other hydroxyl group-containing monomer include a hydroxyalkyl ester of (meth)acrylic acid such as 2-hydroxyethyl acrylate or 2-hydroxyethyl methacrylate.
  • carboxyl group-containing monomer for example, it is preferably selected from the formula (2):
  • R 1 R 2 C CR 3 -(CH 2 ) n -COOH
  • R 1 , R 2 and R 3 are the same or different and are a hydrogen atom, an alkyl group, a carboxyl group, an acyloxy group or an alkoxycarbonyl group.
  • n is an integer of 0 or more
  • R 4 and R 5 are the same or different and are each a saturated or unsaturated linear, branched or cyclic alkylene group.
  • n is 0 or 1
  • m is 0 or 1
  • carboxyl group-containing monomer examples include acrylic acid, methacrylic acid, vinyl acetic acid, crotonic acid, pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, decenoic acid, and decene.
  • Acid undecylenic acid, dodecenoic acid, tridecenoic acid, tetradecenoic acid, pentadecenoic acid, hexadecenoic acid, heptacosic acid, octadecenoic acid, Xydecenoic acid, eicosenoic acid, 22-docosaenoic acid, cinnamic acid, itaconic acid, itaconic acid monoester, maleic acid, maleic acid monoester, maleic anhydride, Fumar Acid, fumaric acid monoester, vinyl phthalate, vinyl pyromelliate, 3-allyloxypropionic acid, 3-(2-allyloxyethoxycarbonyl)propionic acid, 3- (2-allyloxybutoxycarbonyl)propionic acid, 3-(2-vinyloxyethoxycarbonyl)propionic acid, 3-(2-vinyloxybutoxycarbonyl)propionic acid, and the like.
  • it is preferably selected from the group consisting of acrylic acid, crotonic acid, undecylenic acid, itaconic acid, maleic acid, maleic acid monoester, and rich.
  • the silyl group-containing monomer may, for example, be a silicone-based vinyl monomer.
  • the curable functional group-containing fluoropolymer preferably contains a polymerization unit based on at least one non-fluorinated vinyl monomer selected from the group consisting of a carboxylic acid vinyl ester, an alkyl vinyl ether, and a non-fluorinated olefin.
  • the above carboxylic acid vinyl ester has an effect of improving compatibility.
  • Examples of the carboxylic acid vinyl ester include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl hexate, vinyl versatate, and vinyl laurate. , vinyl stearate, vinyl cyclohexate, vinyl benzoate, vinyl p-tert-butylbenzoate, and the like.
  • alkyl vinyl ether examples include methyl vinyl ether, ethyl vinyl ether, butyl vinyl ether, and cyclohexyl vinyl ether.
  • non-fluorinated olefin examples include ethylene, propylene, n-butene, and isobutylene.
  • the above-mentioned polymerizable unit based on the non-fluorinated vinyl monomer preferably constitutes all the polymerization units other than the polymerization unit based on the curable functional group-containing monomer and the polymerization unit based on the fluorine-containing monomer.
  • the fluoropolymer containing the curable functional group may, for example, be (1) a perfluoroolefin-based polymer mainly composed of a perfluoroolefin unit, and (2) a chlorotrifluoroethylene (CTFE) unit as a main component.
  • CTFE chlorotrifluoroethylene
  • a CTFE-based polymer (3) a VdF-based polymer mainly composed of a vinylidene fluoride (VdF) unit, (4) a fluoroalkyl-based polymer mainly composed of a fluoroalkyl unit, and (5) A vinyl acetate polymer or the like having a vinyl acetate unit as a main component.
  • the polymer (1), (2), and (5) are preferred from the viewpoint of weather resistance and moisture resistance.
  • the perfluoroolefin-based polymer mainly composed of a perfluoroolefin unit preferably contains a perfluoroolefin unit.
  • the perfluoroolefin unit is preferably 20% by mole to 49% by mole based on the total polymerization unit of the perfluoroolefin polymer.
  • a more preferred lower limit is 30% by mole, and a still more preferred lower limit is 40% by mole.
  • a more preferred upper limit is 47% by mole.
  • perfluoroolefin examples include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), and perfluoro(alkyl vinyl ether) (PAVE), among which pigment dispersibility, weather resistance, copolymerizability, and TFE is preferred in terms of excellent chemical resistance.
  • TFE tetrafluoroethylene
  • HFP hexafluoropropylene
  • PAVE perfluoro(alkyl vinyl ether)
  • the perfluoroolefin-based polymer preferably contains a unit of another monomer copolymerizable with the perfluoroolefin.
  • Examples of the other monomer copolymerizable include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl hexanoate, vinyl versatate, and laurel.
  • Vinyl vinyl esters such as vinyl acetate, vinyl stearate, vinyl cyclohexate, vinyl benzoate, vinyl p-tert-butylbenzoate; methyl vinyl ether, ethyl vinyl ether, butyl
  • An alkyl vinyl ether such as a vinyl ether or a cyclohexyl vinyl ether; a non-fluorinated olefin such as ethylene, propylene, n-butene or isobutylene; a vinylidene fluoride (VdF) or a chlorotrifluoroethylene (CTFE);
  • a fluorine-based monomer such as fluoroethylene (VF) or fluorovinyl ether is not limited to these.
  • Examples of the perfluoroolefin-based polymer mainly composed of a perfluoroolefin unit include a copolymer of TFE/isobutylene/hydroxybutyl vinyl ether/other monomer, and TFE/vinyl versatate/hydroxybutylvinyl group. Copolymer of ether/other monomer, copolymer of TFE/vinyl versatate/hydroxyethyl vinyl ether/other monomer, copolymer of TFE/VdF/hydroxybutyl vinyl ether/other monomer, etc.
  • a coating material of such a curable polymer for example, Zeffle (registered trademark) GK series manufactured by Daikin Industries Co., Ltd., and the like can be exemplified.
  • CTFE-based polymer mainly composed of chlorotrifluoroethylene (CTFE) unit
  • the CTFE-based polymer mainly composed of a CTFE unit may, for example, be a copolymer of CTFE/hydroxybutyl vinyl ether/other monomer.
  • LUMIFLON registered trademark
  • FLUONATE registered trademark
  • Cefral Coat produced by Central Glass Co., Ltd.
  • Registered trademark Zaffron (registered trademark) manufactured by Toagosei Co., Ltd., etc.
  • VdF polymer mainly based on vinylidene fluoride (VdF) unit
  • the VdF-based polymer mainly composed of a VdF unit may, for example, be a copolymer of VdF/TFE/hydroxybutyl vinyl ether/other monomer.
  • the fluoroalkyl group-containing polymer for example, UNIDYNE (registered trademark) or FTONE (registered trademark) manufactured by Daikin Industries, Ltd., and Zonyl (registered trademark) manufactured by DuPont Co., Ltd., and the like can be exemplified.
  • the vinyl acetate-based polymer mainly composed of the vinyl acetate unit may be a fluorine-containing monomer/vinyl acetate/hydroxyl group represented by the formula (1)/carboxy group represented by the formula (2). a copolymer of monomers.
  • the molar ratio of the fluorine-containing monomer/vinyl acetate/hydroxyl group represented by the formula (1) to the carboxyl group-containing monomer represented by the formula (2) is preferably 15 to 50/20 to 75/ 5 to 22/0.1 to 5, more preferably 15 to 50/23 to 75/5 to 22/0.1 to 5.
  • the total number of moles of the unit and the proportion of the fluorine-containing monomer unit are also preferably from 0.16 to 0.51.
  • the above ratio is preferably 0.22 or more, and preferably 0.50 or less.
  • the above ratio can be calculated from the fluorine content (% by mass) measured by elemental analysis and the composition analysis based on 1 H NMR spectrum.
  • the copolymer having the above ratio is a novel copolymer discovered by the present inventors.
  • the hydroxyl group-containing monomer represented by the formula (1) is preferably selected from the group consisting of hydroxyethyl vinyl ether (HEVE), hydroxybutyl vinyl ether (HBVE), 2-hydroxyethyl allyl ether, and 4-hydroxyl group. At least one monomer in the group consisting of butyl allyl ether.
  • the carboxyl group-containing monomer represented by the formula (2) preferably has a large n value from the viewpoint of improving the polymerization reactivity and improving the compatibility with an additive such as a curing agent.
  • n is preferably 2 or more, more preferably 4 or more, still more preferably 8 or more.
  • the upper limit is, for example, 20.
  • the carboxyl group-containing monomer represented by the formula (2) is preferably selected from the group consisting of pentenoic acid, hexenoic acid, heptenoic acid, octenoic acid, decenoic acid, decenoic acid, undecylenic acid, and twelve carbon.
  • At least one of the group consisting of 22-docosaenoic acid is more preferably undecylenic acid.
  • the above copolymer may also contain other monomer units.
  • the other monomer unit is preferably 0% by mole or more and 40% by mole or less, and more preferably 25% by mole or less based on the total of the structural units constituting the above copolymer.
  • Examples of the other monomer include non-aromatic vinyl esters other than vinyl acetate.
  • Examples of the non-aromatic vinyl ester include vinyl versatate, vinyl laurate, vinyl stearate, and vinyl cyclohexylcarboxylate.
  • the vinyl acetate polymer preferably has a number average molecular weight of 3,000 to 100,000.
  • the number average molecular weight is more preferably 5,000 or more, further preferably 8,000 or more, more preferably 50,000 or less, still more preferably 35,000 or less.
  • the above number average molecular weight can be measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluent.
  • the glass transition temperature (second run) obtained by the differential scanning calorimeter (DSC) of the vinyl acetate polymer is preferably 10 to 70 ° C, and more preferably 15 to 60 ° C. .
  • the acid value of the vinyl acetate polymer is preferably 0.6 mgKOH/g to 28.8 mgKOH/g, and more preferably 2 mgKOH/g to 12 mgKOH/g.
  • the above acid value was measured in accordance with JIS K 5601.
  • the vinyl acetate polymer preferably has a hydroxyl value of from 29 mgKOH/g to 120 mgKOH/g, more preferably 100 mgKOH/g or less.
  • the above hydroxyl value can be calculated from the actual amount of the hydroxyl group monomer and the solid content concentration at the time of polymerization.
  • the curable functional group-containing fluoropolymer can be produced by a method disclosed in, for example, JP-A-2004-204205 and JP-A-2013-177536.
  • a novel copolymer having a ratio of a fluorine-containing monomer unit to a vinyl acetate unit of from 0.16 to 0.51 can be produced by a solution polymerization method, an emulsion polymerization method, a suspension polymerization method or a bulk polymerization method, and is preferably obtained by a solution polymerization method.
  • a monomer, an organic solvent, and a polymerization initiator can be used.
  • the polymerization temperature is usually from 0 ° C to 150 ° C, preferably from 5 ° C to 95 ° C.
  • the polymerization pressure is usually from 0.1 MPaG to 10 MPaG (1 kgf/cm 2 G to 100 kgf/cm 2 G).
  • organic solvent examples include esters such as methyl acetate, ethyl acetate, propyl acetate, n-butyl acetate, and t-butyl acetate; ketones such as acetone, methyl ethyl ketone, and cyclohexanone; and hexane; , aliphatic hydrocarbons such as cyclohexane, octane, decane, decane, undecane, dodecane, mineral essential oils; aromatic hydrocarbons such as benzene, toluene, xylene, naphthalene, solvent naphtha; Alcohols such as ethanol, tert-butanol, isopropanol, and ethylene glycol monoalkyl ether; cyclic ethers such as tetrahydrofuran, tetrahydropyran, and dioxane; dimethyl sulfoxide; etc.; or a mixture thereof Wait
  • persulfate such as ammonium persulfate or potassium persulfate
  • a reducing agent such as sodium hydrogen sulfite, sodium metabisulfite, cobalt naphthenate or dimethylaniline
  • Redox initiators formed from oxidizing agents (such as ammonium peroxide, potassium peroxide, etc.) and reducing agents (such as sodium sulfite, etc.) and transition metal salts (such as iron sulfate, etc.); acetyl peroxide, benzoyl peroxide, etc.
  • Oxidized diacyl groups dialkyloxycarbonyl peroxides such as isopropoxycarbonyl peroxide and t-butoxycarbonyl peroxide; peroxy ketones such as methyl ethyl ketone peroxide and cyclohexanone peroxide Hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide or cumene hydroperoxide; dialkyl peroxides such as di-tert-butyl peroxide and dicumyl peroxide; tert-butyl Alkyl peroxyesters such as peroxyacetate, t-butyl peroxypivalate; 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethyl Pentylene nitrile), 2,2'-azobis(2-methylvaleronitrile), 2,2'-azobis(2-cyclopropylpropionitrile), 2,2'-azo diiso Dimethyl, 2,2'-azobis [
  • composition of the present invention contains a pentamethylene diisocyanate curing agent.
  • the pentamethylene diisocyanate curing agent is preferably selected from the group consisting of a blocked isocyanate compound based on pentamethylene diisocyanate (PDI) and a derivative derived from pentamethylene diisocyanate (PDI). At least one of the group consisting of isocyanate compounds.
  • the above aqueous dispersion can have a sufficient shelf life (use time).
  • PDI penta methylene diisocyanate
  • the blocked isocyanate is preferably one obtained by reacting a polyisocyanate compound derived from pentamethylene diisocyanate (hereinafter also referred to as polyisocyanate compound (II)) with a blocking agent.
  • a polyisocyanate compound derived from pentamethylene diisocyanate hereinafter also referred to as polyisocyanate compound (II)
  • the polyisocyanate compound (II) may, for example, be an adduct obtained by addition polymerization of pentamethylene diisocyanate and a trivalent or higher aliphatic polyol, or an isoform formed of pentamethylene diisocyanate.
  • adduct for example, it is preferred to have a structure represented by the following formula (6):
  • R 4 represents an aliphatic hydrocarbon group having 3 to 20 carbon atoms.
  • k is an integer of 3 to 20).
  • R 4 in the above formula (6) is a hydrocarbon group based on the above-described trivalent or higher aliphatic polyol, more preferably an aliphatic hydrocarbon group having 3 to 10 carbon atoms, and still more preferably an aliphatic group having 3 to 6 carbon atoms. Hydrocarbyl group.
  • the above k is a number corresponding to the number of elements of the aliphatic polyol having 3 or more members.
  • the above k is more preferably an integer of from 3 to 10, still more preferably an integer of from 3 to 6.
  • the isocyanurate structure has one or two or more isocyanurate rings represented by the following formula (2) in the molecule.
  • Examples of the isocyanurate structure include a trimer obtained by a trimerization reaction of the above isocyanate, a pentamer obtained by a pentamerization reaction, and a pentamethylene glycol obtained by a hemerization reaction. Polymer and so on.
  • trimer represented by the following formula (7) is preferred.
  • the biuret is a compound having a structure represented by the following formula (8):
  • This compound can be obtained by trimerating pentamethylene diisocyanate under conditions different from those in the case of obtaining the above isocyanurate structure.
  • a compound having an active hydrogen is preferably used.
  • the compound having active hydrogen described above for example, at least one selected from the group consisting of alcohols, terpenes, lactams, active methylene compounds, and pyrazole compounds is preferably used.
  • the blocked isocyanate is obtained by reacting a polyisocyanate compound derived from pentamethylene diisocyanate with a blocking agent, and the blocking agent is preferably selected from the group consisting of alcohols, terpenes, and lactams. At least one of the group consisting of an active methylene compound and a pyrazole compound.
  • the tribasic or higher aliphatic polyol is specifically That is, glycerin, trimethylolpropane (TMP), 1,2,6-hexanetriol, trimethylolethane, 2,4-dihydroxy-3-hydroxymethylpentane, 1 a trihydric alcohol such as 1,1-tris(dihydroxymethyl)propane or 2,2-bis(hydroxymethyl)butanol-3; a tetrahydric alcohol such as pentaerythritol or diglycerin; arabitol, ribitol, and wood
  • TMP trimethylolpropane
  • 1,2,6-hexanetriol trimethylolethane
  • 2,4-dihydroxy-3-hydroxymethylpentane 1,1-tris(dihydroxymethyl)propane or 2,2-bis(hydroxymethyl)butanol-3
  • a tetrahydric alcohol such as pentaerythritol or diglycerin
  • the adduct is obtained by addition polymerization of pentamethylene diisocyanate and the above trivalent or higher aliphatic polyol.
  • the active hydrogen-reactive compound to be reacted with the above polyisocyanate compound (II) include alcohols such as methanol, ethanol, n-propanol, isopropanol, and methoxypropanol; - anthracene such as butanone oxime, cyclohexanone oxime; lactams such as ⁇ -caprolactam; active methylene compounds such as methyl acetoacetate and ethyl malonate; 3-methylpyrazole, 3,5-di
  • One type or two or more types of the pyrazole compound such as methylpyrazole or 3,5-diethylpyrazole can be used.
  • active methylene compounds and anthraquinones are preferred, and active methylene compounds are more preferred.
  • polyisocyanate compound a polyisocyanate compound derived from pentamethylene diisocyanate (PDI) (hereinafter also referred to as a polyisocyanate compound (III)) can also be used.
  • PDI pentamethylene diisocyanate
  • III polyisocyanate compound
  • polyisocyanate compound (III) examples include D370N, D376N, and D3725N manufactured by Mitsui Chemicals, Inc., and the like.
  • composition of the present invention may further contain other components as long as it contains the curable functional group-containing fluoropolymer and the pentamethylene diisocyanate curing agent. These other components may be used alone or in combination of two or more.
  • the content of the curable functional group-containing fluoropolymer is preferably 20% by mass to 95% by mass based on 100% by mass of the total of the nonvolatile components in the composition.
  • the content of the pentamethylene diisocyanate curing agent is from 0.1 equivalent to 5 equivalents, preferably from 0.5 equivalents to 1.5 equivalents, per equivalent of the curable functional group in the curable functional group-containing fluoropolymer.
  • the ratio of the pentamethylene diisocyanate curing agent to the curable functional group-containing fluoropolymer is a ratio of the number of functional groups in the fluoropolymer containing the curable functional group.
  • the number of functional groups in the pentamethylene diisocyanate curing agent is from 0.1 equivalent to 5 equivalents, preferably from 0.5 equivalents to 1.5 equivalents, more preferably from 0.7 equivalents to 1.2 equivalents.
  • the content of the curable functional group in the curable functional group-containing fluoropolymer can be calculated by appropriately combining NMR, FT-IR, elemental analysis, fluorescent X-ray analysis, and neutralization titration according to the type of the monomer.
  • the content of the curable functional group-containing fluoropolymer and the pentamethylene diisocyanate curing agent is based on the mass of the nonvolatile component after removing the solvent or the like.
  • composition of the present invention contains the curable functional group-containing fluoropolymer and the pentamethylene diisocyanate-based curing agent, it is possible to form a coating film having good adhesion to the substrate even after the autoclave test. Further, the coating film also has good adhesion to a sealing material layer such as EVA.
  • composition of the present invention preferably further contains a polyol compound from the viewpoint of good adhesion to the substrate.
  • the above polyol compound preferably has a hydroxyl value of from 10 to 300.
  • the obtained coating film is firmly adhered to the water-impermeable sheet and the sealing material layer formed of EVA.
  • the polyol compound preferably has a number average molecular weight of 300 to 4,000.
  • the above number average molecular weight is determined by gel permeation chromatography.
  • the polyol compound is preferably selected from the group consisting of a cyclohexane-containing polyol, a polyester polyol, a polycarbonate polyol, and a polyether from the viewpoint of good adhesion to a substrate or a sealing material layer such as EVA.
  • a polyol and a polybutadiene polyol At least one of the group consisting of a polyol and a polybutadiene polyol. More preferably, it is at least one selected from the group consisting of a cyclohexane-containing polyol, a polyester polyol, a polyether polyol, and a polybutadiene polyol.
  • the polyol compound is 0.1% by mass or more and less than 100% by mass based on the fluoropolymer.
  • the polyol compound is preferably 1% by mass or more, more preferably 5% by mass or more, particularly preferably 20% by mass or more, and particularly preferably 50% by mass or less, and more preferably 40% by mass or less, based on the fluoropolymer.
  • the content of the above polyol compound is too large, the weather resistance of the coating film may be deteriorated. If the content is too small, the adhesion between the coating film and the water-impermeable sheet and the sealing material layer formed of EVA may be deteriorated.
  • a commercially available product can also be used as the above polyol compound.
  • composition of the present invention preferably further contains a melamine resin from the viewpoint of good adhesion to a substrate or a sealing material layer such as EVA.
  • melamine resin preferred are compounds obtained by mixing methanol, ethanol, isopropanol, butanol, isobutanol or the like as a lower alcohol with methylol melamine obtained by condensing melamine and formaldehyde. The reaction is carried out and etherification is carried out to obtain the compound.
  • the methylol melamine derivative may, for example, be monomethylol melamine, dimethylol melamine, trimethylol melamine, tetramethylol melamine, pentamethylol melamine or hexamethylol melamine.
  • the classification of the melamine resin it can be classified into a completely alkyl group, a methylol group, an imino group, a hydroxymethyl group/imino group depending on the ratio of alkoxylation, and they can be used in the present invention.
  • a benzene ring-containing melamine resin is more preferable.
  • the melamine resin is preferably 0.1% by mass to 10% by mass based on the fluoropolymer. It is more preferably 0.1% by mass to 5% by mass, and still more preferably 0.1% by mass to 3% by mass. If the content of the melamine resin is too large, the weather resistance may be deteriorated; if the content is too small, the adhesion of the coating film may be deteriorated.
  • additives may be further compounded in the composition of the present invention according to the desired characteristics.
  • the additive include a curing accelerator, a pigment, a pigment dispersant, an antifoaming agent, a leveling agent, an ultraviolet absorber, a light stabilizer, a thickener, an adhesion improver, and a matting agent.
  • the curing accelerator examples include an organotin compound, an acid phosphate, a reaction product of an acid phosphate and an amine, a saturated or unsaturated polycarboxylic acid or an anhydride thereof, an organic titanate compound, an amine compound, and lead octoate. Wait.
  • a usual acid catalyst can be used.
  • an acid catalyst blocked with an amine such as dimethyloxazolidine or 2-amino-2-methyl-1-propanol, unblocked dodecylbenzenesulfonic acid, p-toluenesulfonic acid or diterpene may be mentioned. Naphthalenesulfonic acid and the like.
  • the acid catalyst is preferably selected from the group consisting of dodecylbenzenesulfonic acid, dodecylbenzenesulfonic acid blocked with an amine, p-toluenesulfonic acid, acid phenyl phosphate, dinonylnaphthalenesulfonic acid blocked with an amine, and acidity. At least one of the group consisting of phenyl phosphate.
  • the curing accelerator is preferably 0.01% by mass to 10% by mass based on the fluoropolymer. It is more preferably 0.01% by mass to 5% by mass, and still more preferably 0.1% by mass to 3% by mass. If the content of the curing accelerator is too large, the usable time may be deteriorated; if the content is too small, the adhesion between the coating film and the water-impermeable sheet may be deteriorated.
  • One type of the curing accelerator may be used, or two or more types may be used in combination.
  • the composition of the present invention preferably further contains a pigment.
  • a pigment preferably further contains a pigment.
  • the pigment examples include inorganic pigments such as titanium dioxide, calcium carbonate, carbon black as a black pigment, and a composite metal such as a Cu-Cr-Mn alloy; phthalocyanine and quinacridone. Or organic pigments such as azo, etc., but are not limited to these.
  • the amount of the pigment added is preferably from 0.1 part by mass to 200 parts by mass, more preferably from 0.1 part by mass to 160 parts by mass, per 100 parts by mass of the fluoropolymer containing the curable functional group.
  • the composition of the present invention preferably further contains an ultraviolet absorber. Since solar cells can be used outdoors for a long period of time in which ultraviolet rays are strong, countermeasures against deterioration of the back sheet due to ultraviolet rays are required. When an ultraviolet absorber is added to the composition of the present invention, an ultraviolet absorbing function can be imparted to the cured coating film layer.
  • any of an organic or inorganic ultraviolet absorber can be used.
  • the organic compound system include an ultraviolet absorber such as a salicylate type, a benzotriazole type, a benzophenone type, or a cyanoacrylate type; and among inorganic types, zinc oxide and cerium oxide are preferable.
  • a filler-type inorganic ultraviolet absorber or the like are preferable.
  • the ultraviolet absorber may be used singly or in combination of two or more.
  • the amount of the ultraviolet absorber is preferably from 0.1% by mass to 15% by mass based on 100% by mass of the total of the curable functional group-containing fluoropolymer in the coating material.
  • the amount of the ultraviolet absorber is too small, the effect of improving the light resistance cannot be sufficiently obtained; and even if it is too large, the effect is saturated.
  • composition of the present invention is one of the preferred modes for the coating.
  • composition of the present invention can be produced in the form of a solvent-based paint, an aqueous paint, a powder paint or the like according to a conventional method.
  • a form of a solvent-based paint is preferred from the viewpoints of easiness of film formation, curability, and excellent dryness.
  • the solvent in the solvent-based coating material is preferably an organic solvent, and examples thereof include 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, cyclohexanone; cyclic ethers such as tetrahydrofuran and dioxane; N,N-dimethylformamide, N,N-dimethyl Amide such as acetamide; aromatic hydrocarbons such as xylene, toluene and solvent naphtha; glycol ethers such as propylene glycol methyl ether and ethyl cellosolve; and diethylene glycol esters such as carbitol acetate; An aliphatic hydrocarbon such as n-pentane, n
  • esters are more preferred, and butyl acetate is further preferred.
  • the concentration of the curable functional group-containing fluoropolymer is preferably from 5% by mass to 95% by mass, and more preferably 10%, based on 100% by mass of the total amount of the coating material. Mass% to 70% by mass.
  • the present invention also relates to a coating film obtained from the above composition.
  • the coating film can be formed by applying the composition of the present invention to a suitable substrate and curing it according to the use.
  • the formation of the cured coating film on the substrate can be carried out by applying the composition of the present invention to the substrate according to the form of the coating.
  • the coating may be carried out in a temperature range of a normal condition in a coating form, and in the case of a solvent-based coating, it is carried out at 10 ° C to 300 ° C, usually at 100 ° C to 200 ° C for 30 seconds. 3 days. Therefore, in the case where the composition of the present invention is used for coating of a solar cell module back sheet, as a water-impermeable sheet, even a material such as a Si-evaporated PET sheet which is to be treated under high temperature can be used without problems. Use. Curing can be carried out after curing and drying, and curing is usually carried out at 20 ° C to 300 ° C for 1 minute to 3 days.
  • Coating on the substrate can be carried out by directly coating the composition of the present invention on a substrate.
  • the film thickness of the cured coating film is preferably 1 ⁇ m or more from the viewpoints of good concealability, weather resistance, chemical resistance, and moisture resistance. It is more preferably 3 ⁇ m or more, and still more preferably 5 ⁇ m or more.
  • the reason why the weight reduction effect is not obtained when the thickness is too large is preferably about 100 ⁇ m, and more preferably about 100 ⁇ m.
  • the film thickness is particularly preferably 3 ⁇ m to 40 ⁇ m.
  • the coating film obtained from the composition of the present invention also has good adhesion to the substrate after the autoclave test, and is excellent in adhesion to ordinary EVA as a sealing material for a solar cell module, and not only when it is wound, but also during winding. It is also excellent in blocking resistance, and thus can be suitably used for coating of a solar cell module back sheet which is usually produced by a winding process.
  • the above-mentioned coating film is formed on one surface or both surfaces of a substrate such as a water-impermeable sheet.
  • the coating film obtained from the composition of the present invention is formed on one surface of the substrate and the other surface of the substrate is a non-coated surface, the coating film is not coated with the substrate in the winding process. contact.
  • the coating film is formed on one surface of the substrate, and a coating film obtained from another coating material is provided on the other surface of the substrate (a cured coating film of a fluoropolymer coating material having no curable functional group to be described later, In the case of a coating film, an undercoat layer or the like of a polyester coating, or other sheets, the coating film obtained from the composition of the present invention and the coating film or other sheet obtained from other coating materials on the substrate in the winding process contact. Further, when the coating film obtained from the composition of the present invention is formed on both surfaces of the substrate, the coating film is brought into contact with the same type of coating film formed on the other surface of the substrate in the winding step.
  • the coating film obtained from the composition of the present invention can exhibit excellent blocking resistance with respect to the contact surface in either case.
  • the present invention also relates to a back sheet of a solar cell module having a water-impermeable sheet and a coating film formed on at least one side of the water-impermeable sheet, the coating film being obtained from the above composition.
  • the water-impermeable sheet is a layer that is provided so that moisture does not permeate into the sealing material or the solar cell, and can be used as long as it is a material that does not substantially permeate water, and examples thereof include polycarbonate.
  • Resin acrylic resin, methacrylic resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), polystyrene, polyolefin resin (polyethylene, polypropylene, etc.), polyhalogenated vinyl resin (polymerized) Vinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, etc., polyester resin (polyethylene terephthalate, polybutylene terephthalate, etc.), polyamide resin (Nylon 6, nylon 66, MXD nylon (m-xylylenediamine-adipic acid copolymer), etc.), a polymer of a substituted olefin (polyvinyl
  • a PET sheet, a Si vapor-deposited PET sheet, a metal foil such as aluminum or stainless steel, or the like is often used.
  • PET sheets are often used.
  • the thickness is usually about 50 ⁇ m to 250 ⁇ m.
  • a Si vapor-deposited PET sheet is often used.
  • the thickness is usually about 10 ⁇ m to 20 ⁇ m.
  • a conventionally known surface treatment can be performed on the water-impermeable sheet.
  • the surface treatment for example, a corona discharge treatment, a plasma discharge treatment, a chemical treatment, a sandblasting treatment in the case of a metal sheet, or the like can be exemplified.
  • the method of forming the above coating film on the above water-impermeable sheet is as described above.
  • the coating film may be formed only on one surface of the water-impermeable sheet, or may be formed on both surfaces.
  • the solar cell module including the backing plate is less likely to generate voids at the interface between the sealing material and the backing plate, and the solar cell can be more reliably protected.
  • the present invention also relates to a solar cell module having a water-impermeable sheet, a coating film formed on at least one side of the water-impermeable sheet, and a sealing material layer formed on the coating film, the coating The film was obtained from the above composition.
  • Preferred structures of the above solar cell module include the structures shown in Figs. 1 to 3, for example.
  • the solar cell unit 1 is sealed by the sealant layer 2, and the sealant layer 2 is sandwiched between the surface layer 3 and the backing plate 4.
  • the back sheet 4 is further composed of a water-impermeable sheet 5 and a cured coating film 6, which is obtained from the composition of the present invention.
  • the cured coating film 6 is provided only on the side of the sealing material layer 2.
  • the sealing material layer 2 is composed 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 or the like.
  • a glass plate is usually used for the surface layer 3 described above, but a flexible material such as a resin sheet may also be used.
  • the second structure shown in FIG. 2 is a three-layer structure in which the cured coating film 6 is formed on both surfaces of the water-impermeable sheet 5.
  • the film thickness of the back sheet is increased, but the adhesion between the cured coating film 6 on the side of the sealing material layer 2 and the cured coating film 6 on the opposite side to the sealing material layer 2 are also provided.
  • the advantages of both weather resistance are also provided.
  • a back sheet of the three-layer structure As the back sheet of the three-layer structure, a back sheet of a three-layer structure formed by forming a cured coating film obtained from the composition of the present invention on one surface of the water-impermeable sheet and forming no on the other surface may be used.
  • the third structure shown in FIG. 3 is such that the cured coating film 6 obtained from the composition of the present invention is formed on the side of the sealing material layer 2 of the water-impermeable sheet 5, and the other coating film 7 is formed on the side opposite to the sealing material layer 2. structure.
  • the material constituting the coating film 7 may be a cured coating film of a fluoropolymer coating material having no curable functional group, and may be a fluoropolymer sheet, and may be a polyester sheet or a coating film of a polyester coating material.
  • the coating film may be subjected to a conventionally known surface treatment.
  • a corona discharge treatment, a plasma discharge treatment, a chemical treatment, a sandblasting treatment, or the like can be exemplified.
  • the cured coating film of the fluoropolymer coating material having no curable functional group is, for example, a mixture of tetraalkoxysilane or a partially hydrolyzed product thereof in PVdF as described in JP-A-2004-214342.
  • Cured coating film, cured coating film of VdF/TFE/CTFE copolymer and acrylic resin containing alkoxysilane unit, mixed coating of VdF/TFE/HFP copolymer and hydroxyl group-containing acrylic resin A cured coating film, a cured coating film of a coating material obtained by mixing an aminosilane coupling agent with a VdF/HFP copolymer, and the like.
  • the film thickness is usually preferably 5 ⁇ m to 300 ⁇ m from the viewpoints of good concealability, weather resistance, chemical resistance, and moisture resistance. It is more preferably 10 ⁇ m to 100 ⁇ m, still more preferably 10 ⁇ m to 50 ⁇ m. In this case, an undercoat layer or the like can also be inserted.
  • the formation of the undercoat layer is carried out by a conventional method using a conventionally known coating material for a primer.
  • a coating material for a primer for example, an epoxy resin, a urethane resin, an acrylic resin, a silicone resin, a polyester resin, etc. are mentioned as a representative example.
  • the fluoropolymer sheet examples include a PVdF sheet or a PVF sheet, a PCTFE sheet, a TFE/HFP/ethylene copolymer sheet, a TFE/HFP copolymer (FEP) sheet, and a TFE/PAVE copolymer.
  • PFA PTFE/TFE copolymer
  • ETFE PTFE/CTFE copolymer
  • ECTFE ethylene/CTFE copolymer
  • the film thickness is usually preferably from 5 ⁇ m to 300 ⁇ m. It is more preferably 10 ⁇ m to 100 ⁇ m, still more preferably 10 ⁇ m to 50 ⁇ m.
  • the polyester sheet a sheet used in a conventional back sheet can be used as it is, and the adhesion to the water-impermeable sheet 5 can be made of an acrylic adhesive, a urethane-based adhesive, or an epoxy. It is carried out by a bonding agent, a polyester-based bonding agent, or the like. From the viewpoint of good weather resistance, cost, and transparency, the film thickness is usually preferably 5 ⁇ m to 300 ⁇ m. It is more preferably 10 ⁇ m to 100 ⁇ m, still more preferably 10 ⁇ m to 50 ⁇ m.
  • polyester coating material examples include a coating material using a saturated polyester resin obtained by using a polyvalent carboxylic acid or a polyhydric alcohol, and an unsaturated resin obtained by using maleic anhydride, fumaric acid or the like and a glycol.
  • a coating film of a polyester resin or the like can be formed into a coating film by a coating method such as roll coating, curtain coating, spray coating, or die coating.
  • the film thickness is preferably from 5 ⁇ m to 300 ⁇ m from the viewpoints of good concealability, weather resistance, chemical resistance, and moisture resistance. It is more preferably 10 ⁇ m to 100 ⁇ m, still more preferably 10 ⁇ m to 50 ⁇ m. In this case, an undercoat layer or the like can also be inserted.
  • composition of the present invention can be used as a coating material for outdoor use such as building materials and interior materials, building materials, exterior materials, automobiles, aircrafts, ships, and electric vehicles, in addition to the above-described solar cell module applications. It is applied to metal, concrete, plastic, etc., or overlaid on primers such as etch coatings, rust-preventive coatings, epoxy coatings, acrylic coatings, and polyester resin coatings. In particular, it can be suitably used for a coating layer which is in close contact with the EVA layer, or various films or sheet materials which are produced by the winding process.
  • the present invention also relates to a laminate comprising a substrate and a layer obtained from the above composition.
  • the layer obtained from the above composition may be formed by coating the above composition on a substrate, or may be formed by laminating the above composition into a film and then laminating the film on a substrate, or may be the composition described above. Cured cured film.
  • the layer obtained from the above composition may be formed only on one side of the above-mentioned substrate or on both sides.
  • the shape, thickness, and the like of the base material may be appropriately adjusted depending on the use of the laminate.
  • the substrate is preferably composed of metal, concrete or plastic.
  • the base material and the layer obtained from the above composition may be directly bonded or may be bonded via another layer such as a primer layer, and the layer obtained from the above composition may be excellent in adhesion to the substrate. Direct bonding. When the base material is directly bonded to the layer obtained from the above composition, the thickness of the laminate can be reduced.
  • the thickness of the layer obtained from the above composition is preferably 1 ⁇ m or more from the viewpoints of good concealability, weather resistance, chemical resistance, and moisture resistance. It is more preferably 3 ⁇ m or more, and still more preferably 5 ⁇ m or more.
  • the reason why the weight reduction effect is not obtained when the thickness is too large is preferably about 100 ⁇ m, and more preferably about 100 ⁇ m.
  • the thickness of the layer obtained from the above composition is particularly preferably from 3 to 40 ⁇ m.
  • plastic material of the base material composed of the above plastics examples include a polycarbonate resin, an acrylic resin, a methacrylic resin, an acrylonitrile-butadiene-styrene copolymer (ABS resin), and polystyrene.
  • Polyolefin resin polyethylene, polypropylene, etc.
  • polyhalogenated vinyl resin polyvinyl chloride, polyvinylidene chloride, polyvinyl fluoride, polyvinylidene fluoride, etc.
  • polyester resin polyethylene terephthalate
  • a polycarbonate resin an acrylic resin, polyvinyl chloride, polyethylene terephthalate, or
  • a conventionally known surface treatment can be performed on the substrate.
  • a corona discharge treatment, a plasma discharge treatment, a chemical treatment, a sandblasting treatment in the case of a metal sheet, or the like can be exemplified.
  • the above laminated body can be used for building materials, interior materials, exterior materials, automobiles, aircraft, ships (decks, decks, bottoms, etc.), electric trains, storage tanks, bridges, and the like. In particular, it is useful as a component inside and outside the vehicle.
  • composition of the present invention contains the above-described configuration, it is possible to form a coating film which has good adhesion to the substrate even after the high-pressure cooking test. Such a coating film is extremely useful as a coating film for a solar cell module back sheet.
  • FIG. 1 is a schematic cross-sectional view showing a first structure of a solar cell module.
  • FIG. 2 is a schematic cross-sectional view showing a second structure of a solar cell module.
  • Fig. 3 is a schematic cross-sectional view showing a third structure of the solar cell module.
  • Fluororesin Curable TFE copolymer solution, trade name Zeffle GK570, manufactured by Daikin Industries Co., Ltd.
  • Glycol a cyclohexane-containing diol, trade name Sovermol 908 (compound having the following structure), manufactured by BASF Corporation
  • Glycol polyester diol, CMA-3190, manufactured by Jiangsu Huada Company
  • Curing accelerator (acid catalyst): CYCAT 600, 70% by mass isopropanol solution of dodecylbenzenesulfonic acid available from Cytec, Inc.)
  • PDI curing agent D3725N, manufactured by Mitsui Chemicals, Inc.
  • XDI curing agent Takenate D120N, manufactured by Mitsui Chemicals, Inc.
  • HDI curing agent manufactured by Sumidur N3300 and Sumika Bayer Urethane
  • a curable TFE-based copolymer solution (Zeffle GK570 manufactured by Daikin Industries, Ltd., solid content: 65 mass%, hydroxyl value: 60 mgKOH/g, solvent: butyl acetate), and titanium dioxide as a white pigment 263.0 parts by mass of R960) manufactured by DuPont Co., Ltd. and 167.0 parts by mass of butyl acetate were pre-mixed, and then 632 parts by mass of glass beads having a diameter of 1.2 mm were placed, and dispersed at 1,500 rpm for 1 hour using a pigment disperser.
  • a curable TFE-based copolymer solution (Zeffle GK570 manufactured by Daikin Industries, Ltd., solid content: 65 mass%, hydroxyl value: 60 mgKOH/g, solvent: butyl acetate), and titanium dioxide as a white pigment 263.0 parts by mass of R960) manufactured by DuPont Co., Ltd. and 167.0 parts by mass of butyl acetate were pre-mix
  • the glass beads were filtered through a #80 mesh sieve, and 283.0 parts by mass of a curable TFE-based copolymer solution (Zeffle GK570) and 85.0 parts by mass of butyl acetate were added to the solution to prepare a white paint.
  • a curable TFE-based copolymer solution Zeffle GK570
  • the coating material 1 was prepared by the fact that the NCO content was 22.8%, and 66.2 parts by mass (1 equivalent of the curable functional group in the curable TFE-based copolymer, equivalent to 1.0 equivalent).
  • a PET film (DS10 manufactured by Tosoh Corp., thickness: 250 ⁇ m, sheet A) was used as the water-impermeable sheet, and one side of the sheet A was subjected to corona treatment at 2000 W, and dried to a thickness of 10 ⁇ m by a coater.
  • the coating material 1 prepared in Preparation Example 1 was applied and dried at 150 ° C for 2 minutes to prepare a back sheet A1 having a two-layer structure.
  • the coating film surface of the back sheet A1 was subjected to corona treatment at 2000 W, and cured at 50 ° C for 48 hours, and then an EVA resin sheet (F806P manufactured by Foster, thickness: 500 ⁇ m) was placed on the surface of the coating film. Further, tempered glass (manufactured by Wuxi Haida, 3.2 mm thick) was placed on the EVA resin sheet, and pressure-bonded at 142 ° C to prepare a sample A1 having a three-layer structure (the method shown in Fig. 1). Adhesion (between EVA and backsheet) was examined for this glass/EVA/backsheet bonded sample A1. The results are listed in Table 1.
  • test method and measurement method are as follows.
  • the EVA/backsheet bonding sample A1 obtained in Example 1 was measured by the peeling test after 48 hours in the initial state and PCT (high pressure cooking test, 121 ° C, humidity 100% RH, 2 atmospheres). The adhesion between the layers.
  • the EVA/back plate portion of the measurement sample was cut to a width of 1 cm ⁇ 15 cm, and a 180-degree peeling test was performed using Tensilon (manufactured by ORIENTEC), and the adhesion strength between the EVA/back sheet was measured in units of N/cm.
  • the coating film after the initial state and the PCT 48 hours was visually evaluated in the same manner as the peel strength.
  • the coating film after the initial state and the PCT 48 hours was visually evaluated in the same manner as the peel strength.
  • the measurement was performed using a micrometer (manufactured by Mitutoyo Co., Ltd.) in accordance with JIS C-2151.
  • a coating material was prepared in the same manner as in Preparation Example 1 except that the components of the coating material were changed as described in Table 1 or Table 2.
  • a bonded sample of a back sheet and a glass/EVA/back sheet having a two-layer structure was produced in the same manner as in Example 1.

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Abstract

提供能够形成即使在高压蒸煮测试后也与基材具有良好密合性的涂膜的组合物、由该组合物得到的涂膜(6)、以及具有该涂膜的太阳能电池组件背板(4)和太阳能电池组件。该组合物含有含固化性官能团的含氟聚合物以及五亚甲基二异氰酸酯系固化剂。

Description

组合物、涂料、涂膜、太阳能电池组件背板以及太阳能电池组件 【技术领域】
本发明涉及组合物、涂料、涂膜、太阳能电池组件背板以及太阳能电池组件。更详细地说，本发明涉及适于太阳能电池组件背板的涂布的组合物、由该组合物得到的涂膜、以及具有该涂膜的太阳能电池组件背板和太阳能电池组件。
【背景技术】
太阳能电池组件通常由表面层、密封太阳能电池单元的密封材层以及背板构成。作为形成密封材层的密封材，通常使用乙烯与乙酸乙烯酯的共聚物(下文中也称为EVA。)。
例如，在专利文献1中记载了一种太阳能电池组件背板，其是在不透水性片材的至少一个面上形成含固化性官能团的含氟聚合物涂料的固化涂膜而成的。
【现有技术文献】
【专利文献】
专利文献1：日本特开2007-35694号公报
【发明内容】
【发明所要解决的课题】
本发明的目的在于提供能够形成在高压蒸煮测试后也与基材具有良好密合性的涂膜的组合物、由该组合物得到的涂膜、以及具有该涂膜的太阳能电池组件背板和太阳能电池组件。
【解决课题的手段】
本发明涉及一种组合物，其特征在于，其含有含固化性官能团的含氟聚合物以及五亚甲基二异氰酸酯系固化剂。
此外，本发明还涉及一种涂膜，其特征在于，其是由上述组合物得到的。
本发明还涉及一种层积体，其特征在于，其包含基材以及由上述组合物得到的层。
此外，本发明还涉及一种太阳能电池组件背板，其特征在于，其具有不透水性片材以及形成在上述不透水性片材的至少一个面上的涂膜，该涂膜由上述组合物得到。
此外，本发明还涉及一种太阳能电池组件，其特征在于，其具有不透水性片材、形成在上述不透水性片材的至少一个面上的涂膜、以及形成在上述涂膜之上的密封材层，该涂膜由上述组合物得到。
以下详细说明本发明。
本发明的组合物含有含固化性官能团的含氟聚合物。
作为上述含固化性官能团的含氟聚合物，可以举出在含氟聚合物中导入固化性官能团而成的聚合物。需要说明的是，含固化性官能团的含氟聚合物中包括具有明确熔点的树脂性聚合物、显示出橡胶弹性的弹性体性聚合物、介于两者之间的热塑性弹性体性聚合物。
对含氟聚合物赋予固化性的官能团可结合聚合物的制造容易性或固化体系进行适当选择，可以举出例如羟基(其中不包括羧基所含有的羟基。以下同样)、羧基、-COOCO-所表示的基团、氰基、氨基、环氧基、甲硅烷基等。其中，从固化反应性良好的方面考虑，优选为选自由羟基、羧基、-COOCO-所表示的基团、氨基、氰基以及甲硅烷基组成的组中的至少一种基团，更优选为选自由羟基、羧基、氨基以及甲硅烷基组成的组中的至少一种基团，进一步优选为选自由羟基、羧基和氨基组成的组中的至少一种基团，特别优选为选自由羟基以及羧基组成的组中的至少一种基团。这些固化性官能团通常通过含有固化性官能团的单体的共聚而被导入到含氟聚合物中。
作为上述含固化性官能团单体，可以举出例如含羟基单体、含羧基单体、含氨基单体以及硅酮系乙烯基单体，可以使用它们中的1种或2种以上。
上述含固化性官能团的含氟聚合物优选含有基于含氟单体的聚合单元以及基于含固化性官能团单体的聚合单元，该含固化性官能团单体为选自由含羟基单体、含羧基单体、含氨基单体以及硅酮系乙烯基单体组成的组中的至少一种。此外，上述含固化性官能团的含氟聚合物更优选含有基于含氟单体的聚合单元、以及基于选自由含羟基单体和含羧基单体组成的组中的至少一种含固化性官能团单体的聚合单元。
作为上述含氟单体，可以举出例如四氟乙烯、三氟氯乙烯、偏二氟乙烯、氟乙烯以及氟乙烯基醚，可以使用它们中的1种或2种以上。
其中优选为选自由四氟乙烯、三氟氯乙烯以及偏二氟乙烯组成的组中的至少一 种，更优选为选自由四氟乙烯和三氟氯乙烯组成的组中的至少一种。
上述基于含氟单体的聚合单元相对于上述含固化性官能团的含氟聚合物的全部聚合单元优选为15摩尔％～50摩尔％。更优选的下限为20摩尔％、进一步优选的下限为30摩尔％、特别优选的下限为40摩尔％。更优选的上限为49摩尔％、进一步优选的上限为47摩尔％。
上述基于含固化性官能团单体的聚合单元相对于含固化性官能团的含氟聚合物的全部聚合单元优选为8摩尔％～30摩尔％。更优选的下限为10摩尔％、更优选的上限为20摩尔％。
作为上述含固化性官能团单体，例如可示例出下述单体，但并不仅限于这些。需要说明的是，可以使用它们中的1种或2种以上。
(1-1)含羟基单体：
作为含羟基单体，可以举出例如2-羟基乙基乙烯基醚、3-羟基丙基乙烯基醚、2-羟基丙基乙烯基醚、2-羟基-2-甲基丙基乙烯基醚、4-羟基丁基乙烯基醚、4-羟基-2-甲基丁基乙烯基醚、5-羟基戊基乙烯基醚、6-羟基己基乙烯基醚等含羟基的乙烯基醚类；2-羟基乙基烯丙基醚、4-羟基丁基烯丙基醚、甘油单烯丙基醚等含羟基的烯丙基醚类等。它们之中，从聚合反应性、官能团的固化性优异的方面考虑，优选含羟基乙烯基醚类，更优选优选由式(1)：
CH 2＝CH-(CH 2) l-O-(CH 2) m-OH
(式中，l为0或1、m为2以上的整数)表示的含羟基单体，进一步优选选自由4-羟基丁基乙烯基醚、2-羟基乙基乙烯基醚、2-羟基乙基烯丙基醚和4-羟基丁基烯丙基醚组成的组中的至少一种单体。
作为其他含羟基单体，还可以举出例如丙烯酸-2-羟基乙酯、甲基丙烯酸-2-羟基乙酯等(甲基)丙烯酸的羟基烷基酯等。
(1-2)含羧基单体：
作为含羧基单体，例如优选为选自由式(2)：
R 1R 2C＝CR 3-(CH 2) n-COOH
(式中，R 1、R 2和R 3相同或不同，为氢原子、烷基、羧基、酰氧基或烷氧羰基。n为0以上的整数)所表示的含羧基单体、它们的酯和酸酐以及式(3)：
CH 2＝CH(CH 2) nO(R 4OCO) mR 5COOH
(式中，R 4和R 5相同或不同，均为饱和或不饱和的直链、支化或环状的亚烷基。n为0或1，m为0或1)所表示的含羧基乙烯基醚单体组成的组中的至少一种单体。
作为上述含羧基单体的具体例，可以举出例如丙烯酸、甲基丙烯酸、乙烯基乙酸、丁烯酸、戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、十一碳烯酸、十二碳烯酸、十三碳烯酸、十四碳烯酸、十五碳烯酸、十六碳烯酸、十七碳烯酸、十八碳烯酸、十九碳烯酸、二十碳烯酸、22-二十三碳烯酸、肉桂酸、衣康酸、衣康酸单酯、马来酸、马来酸单酯、马来酸酐、富马酸、富马酸单酯、邻苯二甲酸乙烯酯、苯均四酸乙烯酯、3-烯丙氧基丙酸、3-(2-烯丙氧基乙氧基羰基)丙酸、3-(2-烯丙氧基丁氧基羰基)丙酸、3-(2-乙烯氧基乙氧基羰基)丙酸、3-(2-乙烯氧基丁氧基羰基)丙酸等。它们之中，出于均聚性低、难以得到均聚物的理由，优选为选自由丙烯酸、丁烯酸、十一碳烯酸、衣康酸、马来酸、马来酸单酯、富马酸、富马酸单酯、3-烯丙氧基丙酸以及3-(2-烯丙氧基乙氧基羰基)丙酸组成的组中的至少一种酸。
(1-3)含氨基单体：
作为含氨基单体，可以举出例如CH 2＝CH-O-(CH 2) x-NH 2(x＝0～10)所表示的氨基乙烯基醚类；CH 2＝CH-O-CO(CH 2) x-NH 2(x＝1～10)所表示的烯丙基胺类；以及氨基甲基苯乙烯、乙烯基胺、丙烯酰胺、乙烯基乙酰胺、乙烯基甲酰胺等。
(1-4)含甲硅烷基单体：
作为含甲硅烷基单体，可以举出例如硅酮系乙烯基单体。作为硅酮系乙烯基单体，可示例出例如：CH 2＝CHCO 2(CH 2) 3Si(OCH 3) 3、CH 2＝CHCO 2(CH 2) 3Si(OC 2H 5) 3、CH 2＝C(CH 3)CO 2(CH 2) 3Si(OCH 3) 3、CH 2＝C(CH 3)CO 2(CH 2) 3Si(OC 2H 5) 3、CH 2＝CHCO 2(CH 2) 3SiCH 3(OC 2H 5) 2、CH 2＝C(CH 3)CO 2(CH 2) 3SiC 2H 5(OCH 3) 2、CH 2＝C(CH 3)CO 2(CH 2) 3Si(CH 3) 2(OC 2H 5)、CH 2＝C(CH 3)CO 2(CH 2) 3Si(CH 3) 2OH、CH 2＝CH(CH 2) 3Si(OCOCH 3) 3、CH 2＝C(CH 3)CO 2(CH 2) 3SiC 2H 5(OCOCH 3) 2、CH 2＝C(CH 3)CO 2(CH 2) 3SiCH 3(N(CH 3)COCH 3) 2、CH 2＝CHCO 2(CH 2) 3SiCH 3[ON(CH 3)C 2H 5] 2、CH 2＝C(CH 3)CO 2(CH 2) 3SiC 6H 5[ON(CH 3)C 2H 5] 2等(甲基)丙烯酸酯类；CH 2＝CHSi[ON＝C(CH 3)(C 2H 5)] 3、CH 2＝CHSi(OCH 3) 3、CH 2＝CHSi(OC 2H 5) 3、CH 2＝CHSiCH 3(OCH 3) 2、CH 2＝CHSi(OCOCH 3) 3、CH 2＝CHSi(CH 3) 2(OC 2H 5)、CH 2＝CHSi(CH 3) 2SiCH 3(OCH 3) 2、CH 2＝CHSiC 2H 5(OCOCH 3) 2、 CH 2＝CHSiCH 3[ON(CH 3)C 2H 5] 2、乙烯基三氯硅烷或它们的部分水解物等乙烯基硅烷类；三甲氧基甲硅烷基乙基乙烯基醚、三乙氧基甲硅烷基乙基乙烯基醚、三甲氧基甲硅烷基丁基乙烯基醚、甲基二甲氧基甲硅烷基乙基乙烯基醚、三甲氧基甲硅烷基丙基乙烯基醚、三乙氧基甲硅烷基丙基乙烯基醚等乙烯基醚类；等等。
上述含固化性官能团的含氟聚合物优选含有基于选自由羧酸乙烯基酯、烷基乙烯基醚和非氟化烯烃组成的组中的至少一种非含氟乙烯基单体的聚合单元。
上述羧酸乙烯基酯具有改善相容性的作用。作为羧酸乙烯基酯，可以举出乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、异丁酸乙烯酯、新戊酸乙烯酯、已酸乙烯酯、叔碳酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、环己基甲酸乙烯酯、苯甲酸乙烯酯、对叔丁基苯甲酸乙烯酯等。
作为上述烷基乙烯基醚，可以举出甲基乙烯基醚、乙基乙烯基醚、丁基乙烯基醚、环己基乙烯基醚等。
作为上述非氟化烯烃，可以举出乙烯、丙烯、正丁烯、异丁烯等。
上述基于非含氟乙烯基单体的聚合单元优选构成除基于含固化性官能团单体的聚合单元以及基于含氟单体的聚合单元以外的全部聚合单元。
作为上述含固化性官能团的含氟聚合物，可以举出例如：(1)以全氟烯烃单元为主体的全氟烯烃系聚合物、(2)以三氟氯乙烯(CTFE)单元为主体的CTFE系聚合物、(3)以偏二氟乙烯(VdF)单元为主体的VdF系聚合物、(4)以氟代烷基单元为主体的含氟代烷基的聚合物、(5)以乙酸乙烯酯单元为主体的乙酸乙烯酯系聚合物等。
作为上述含固化性官能团的含氟聚合物，上述(1)～(5)中，从耐候性和防湿性的方面出发，优选(1)、(2)和(5)的聚合物。
(1)以全氟烯烃单元为主体的全氟烯烃系聚合物
以全氟烯烃单元为主体的全氟烯烃系聚合物优选含有全氟烯烃单元。上述全氟烯烃单元相对于全氟烯烃系聚合物的全部聚合单元优选为20摩尔％～49摩尔％。更优选的下限为30摩尔％、进一步优选的下限为40摩尔％。更优选的上限为47摩尔％。
作为上述全氟烯烃，可以举出四氟乙烯(TFE)、六氟丙烯(HFP)、全氟(烷基乙烯基醚)(PAVE)等，其中，从颜料分散性、耐候性、共聚性和耐化学药品性优异的方面考虑，优选TFE。
上述全氟烯烃系聚合物优选含有能够与全氟烯烃共聚的其他单体的单元。
作为上述能够共聚的其他单体，可以举出例如乙酸乙烯酯、丙酸乙烯酯、丁酸乙烯酯、异丁酸乙烯酯、新戊酸乙烯酯、已酸乙烯酯、叔碳酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、环己基甲酸乙烯酯、苯甲酸乙烯酯、对叔丁基苯甲酸乙烯酯等羧酸乙烯基酯类；甲基乙烯基醚、乙基乙烯基醚、丁基乙烯基醚、环己基乙烯基醚等烷基乙烯基醚类；乙烯、丙烯、正丁烯、异丁烯等非氟系烯烃类；偏二氟乙烯(VdF)、三氟氯乙烯(CTFE)、氟乙烯(VF)、氟乙烯基醚等氟系单体等，但并不仅限于这些物质。
作为以全氟烯烃单元为主体的全氟烯烃系聚合物，可以举出例如TFE/异丁烯/羟基丁基乙烯基醚/其他单体的共聚物、TFE/叔碳酸乙烯酯/羟基丁基乙烯基醚/其他单体的共聚物、TFE/叔碳酸乙烯酯/羟基乙基乙烯基醚/其他单体的共聚物、TFE/VdF/羟基丁基乙烯基醚/其他单体的共聚物等，特别优选为选自由TFE/异丁烯/羟基丁基乙烯基醚/其他单体的共聚物以及TFE/叔碳酸乙烯酯/羟基丁基乙烯基醚/其他单体的共聚物组成的组中的至少一种共聚物。作为这样的固化性聚合物的涂料，可示例出例如大金工业株式会社制造的Zeffle(注册商标)GK系列等。
(2)以三氟氯乙烯(CTFE)单元为主体的CTFE系聚合物
作为以CTFE单元为主体的CTFE系聚合物，可以举出例如CTFE/羟基丁基乙烯基醚/其他单体的共聚物等。作为CTFE系聚合物的固化性聚合物涂料，可示例出例如旭硝子株式会社制造的LUMIFLON(注册商标)、大日本油墨制造株式会社制造的FLUONATE(注册商标)、Central Glass株式会社制造的Cefral Coat(注册商标)、东亚合成株式会社制造的Zaffron(注册商标)等。
(3)以偏二氟乙烯(VdF)单元为主体的VdF系聚合物
作为以VdF单元为主体的VdF系聚合物，可以举出例如VdF/TFE/羟基丁基乙烯基醚/其他单体的共聚物等。
(4)以氟代烷基单元为主体的含氟代烷基的聚合物
作为以氟代烷基单元为主体的含氟代烷基的聚合物，可以举出例如CF 3CF 2(CF 2CF 2) nCH 2CH 2OCOCH＝CH 2(n＝3与4的混合物)/甲基丙烯酸-2-羟乙酯/丙烯酸硬脂基酯共聚物等。作为含氟代烷基的聚合物，可示例出例如大金工业株式会社制造的UNIDYNE(注册商标)或FTONE(注册商标)、杜邦公司制造的Zonyl(注册商标)等。
(5)以乙酸乙烯酯单元为主体的乙酸乙烯酯系聚合物
作为上述以乙酸乙烯酯单元为主体的乙酸乙烯酯系聚合物，可以举出含氟单体/乙酸乙烯酯/式(1)所表示的含羟基单体/式(2)所表示的含羧基单体的共聚物。上述共聚物中，含氟单体/乙酸乙烯酯/式(1)所表示的含羟基单体/式(2)所表示的含羧基单体的摩尔比优选为15～50/20～75/5～22/0.1～5、更优选为15～50/23～75/5～22/0.1～5。
关于在上述共聚物中的含氟单体单元与乙酸乙烯酯单元的比例，从耐候性、耐溶剂性、耐污染性和涂膜硬度的方面出发，相对于含氟单体单元和乙酸乙烯酯单元的合计摩尔数，含氟单体单元的比例还优选为0.16～0.51。上述比例优选为0.22以上、优选为0.50以下。上述比例可以根据由元素分析测定的含氟量(质量％)和基于 1HNMR光谱的组成分析而计算出。具有上述比例的共聚物是本发明人所发现的新型共聚物。
作为式(1)所表示的含羟基单体，优选为选自由羟基乙基乙烯基醚(HEVE)、羟基丁基乙烯基醚(HBVE)、2-羟基乙基烯丙基醚和4-羟基丁基烯丙基醚组成的组中的至少一种单体。
作为式(2)所表示的含羧基单体，从提高聚合反应性、并且提高与固化剂等添加剂的相容性的方面考虑，优选n值大。作为n，优选为2以上、更优选为4以上、进一步优选为8以上。上限例如为20。作为式(2)所表示的含羧基单体，优选为选自由戊烯酸、己烯酸、庚烯酸、辛烯酸、壬烯酸、癸烯酸、十一碳烯酸、十二碳烯酸、十三碳烯酸、十四碳烯酸、十五碳烯酸、十六碳烯酸、十七碳烯酸、十八碳烯酸、十九碳烯酸、二十碳烯酸和22-二十三碳烯酸组成的组中的至少一种，更优选为十一碳烯酸。
上述共聚物也可以含有其他单体单元。其他单体单元相对于构成上述共聚物的全部结构单元优选为0摩尔％以上40摩尔％以下、更优选为25摩尔％以下。作为其他单体，可以举出乙酸乙烯酯以外的非芳香族系乙烯基酯等。作为非芳香族系乙烯基酯，可以举出叔碳酸乙烯酯、月桂酸乙烯酯、硬脂酸乙烯酯、环己基甲酸乙烯酯等。
上述乙酸乙烯酯系聚合物优选数均分子量为3000～100000。上述数均分子量更优选为5000以上、进一步优选为8000以上，更优选为50000以下、进一步优选为35000以下。上述数均分子量可以通过使用四氢呋喃作为洗脱液的凝胶渗透色谱法(GPC)来测定。
上述乙酸乙烯酯系聚合物利用差示扫描量热计(DSC)求出的玻璃化转变温度(第2次循环(second run))优选为10℃～70℃、更优选为15℃～60℃。
上述乙酸乙烯酯系聚合物的酸值优选为0.6mgKOH/g～28.8mgKOH/g、更优选为2mgKOH/g～12mgKOH/g。上述酸值根据JIS K 5601进行测定。
上述乙酸乙烯酯系聚合物的羟值优选为29mgKOH/g～120mgKOH/g、更优选为100mgKOH/g以下。上述羟值可以根据聚合时的羟基单体的实际投料量和固体成分浓度计算出。
上述含固化性官能团的含氟聚合物可通过例如日本特开2004-204205号公报、日本特开2013-177536号公报中公开的方法来制造。
另外，含氟单体单元与乙酸乙烯酯单元的比例为0.16～0.51的新型共聚物可利用溶液聚合法、乳液聚合法、悬浮聚合法或本体聚合法来制造，其中优选利用溶液聚合法得到。
在上述溶液聚合中，可以使用单体、有机溶剂和聚合引发剂。聚合温度通常为0℃～150℃、优选为5℃～95℃。聚合压力通常为0.1MPaG～10MPaG(1kgf/cm 2G～100kgf/cm 2G)。
作为有机溶剂，可以举出：乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸正丁酯、乙酸叔丁酯等酯类；丙酮、甲基乙基酮、环己酮等酮类；己烷、环己烷、辛烷、壬烷、癸烷、十一烷、十二烷、矿物精油等脂肪族烃类；苯、甲苯、二甲苯、萘、溶剂石脑油等芳香族烃类；甲醇、乙醇、叔丁醇、异丙醇、乙二醇单烷基醚等醇类；四氢呋喃、四氢吡喃、二氧六环等环状醚类；二甲基亚砜等；或它们的混合物等。
作为聚合引发剂，可以使用例如：过硫酸铵、过硫酸钾等过硫酸盐类(还可以进一步根据需要合用亚硫酸氢钠、焦亚硫酸钠、环烷酸钴、二甲基苯胺等还原剂)；由氧化剂(例如过氧化铵、过氧化钾等)与还原剂(例如亚硫酸钠等)和过渡金属盐(例如硫酸铁等)形成的氧化还原引发剂类；过氧化乙酰、过氧化苯甲酰等过氧化二酰类；异丙氧基羰基过氧化物、叔丁氧基羰基过氧化物等二烷氧羰基过氧化物类；过氧化甲基乙基酮、过氧化环己酮等过氧化酮类；过氧化氢、叔丁基过氧化氢、氢过氧化枯烯等氢过氧化物类；二叔丁基过氧化物、二枯基过氧化物等二烷基过氧化物类；叔丁基过氧化乙酸酯、叔丁基过氧化新戊酸酯等烷基过氧化酯类；2,2’-偶氮二异丁腈、2,2’-偶氮双(2,4-二甲基戊腈)、2,2’-偶氮二(2-甲基戊腈)、2,2’-偶氮二(2-环丙基丙腈)、2,2’-偶氮二异丁酸二甲酯、2,2’-偶氮二[2-(羟基甲基)丙腈]、4,4’-偶氮二(4-氰基戊烯酸)等偶氮系化合物等。
本发明的组合物含有五亚甲基二异氰酸酯系固化剂。
作为上述五亚甲基二异氰酸酯系固化剂，优选为选自由基于五亚甲基二异氰酸酯(PDI)的封端异氰酸酯化合物(ブロックイソシアネート化合物)以及衍生自五亚甲基二异氰酸酯(PDI)的多异氰酸酯化合物组成的组中的至少一种。
通过使用基于五亚甲基二异氰酸酯(PDI)的封端异氰酸酯(以下也简称为封端异氰酸酯)作为上述多异氰酸酯化合物，可使上述水性分散体具有充分的贮存期(可使用时间)。
作为上述封端异氰酸酯，优选为使衍生自五亚甲基二异氰酸酯的多异氰酸酯化合物(以下也称为多异氰酸酯化合物(II))利用封端化剂反应而得到的物质。
作为上述多异氰酸酯化合物(II)，可以举出例如：五亚甲基二异氰酸酯与3元以上的脂肪族多元醇经加成聚合而得到的加成物、由五亚甲基二异氰酸酯形成的异氰脲酸酯结构体(三聚氰酸酯结构体(nurate structures))以及由五亚甲基二异氰酸酯形成的缩二脲(ビウレット)。
作为上述加成物，例如优选具有如下通式(6)所表示的结构：
【化1】
Figure PCTCN2018116412-appb-000001
(式中，R 4表示碳原子数为3～20的脂肪族烃基。k为3～20的整数)。
上述通式(6)中的R 4为基于上述3元以上的脂肪族多元醇的烃基，更优选碳原子数为3～10的脂肪族烃基，进一步优选碳原子数为3～6的脂肪族烃基。
上述k为与3元以上的脂肪族多元醇的元数对应的数。作为上述k，更优选为3～10的整数、进一步优选为3～6的整数。
上述异氰脲酸酯结构体在分子中具有1个或2个以上如下通式(2)所表示的异氰脲酸酯环。
【化2】
Figure PCTCN2018116412-appb-000002
作为上述异氰脲酸酯结构体，可以举出：通过上述异氰酸酯的三聚化反应而得到的三聚体、通过五聚化反应而得到的五聚体、通过七聚化反应而得到的七聚体等。
其中，优选如下通式(7)所表示的三聚体。
【化3】
Figure PCTCN2018116412-appb-000003
上述缩二脲为具有如下通式(8)所表示的结构的化合物：
【化4】
Figure PCTCN2018116412-appb-000004
该化合物可以通过在与得到上述异氰脲酸酯结构体的情况不同的条件下将五亚甲基二异氰酸酯三聚化来得到。
作为上述封端化剂，优选使用具有活性氢的化合物。作为上述具有活性氢的化合物，优选使用例如选自由醇类、肟类、内酰胺类、活性亚甲基化合物以及吡唑化合物组成的组中的至少一种。
这样，上述封端异氰酸酯为使衍生自五亚甲基二异氰酸酯的多异氰酸酯化合物利用封端化剂反应而得到的物质，上述封端化剂优选为选自由醇类、肟类、内酰胺类、活性亚甲基化合物以及吡唑化合物组成的组中的至少一种。
用于得到上述封端异氰酸酯的多异氰酸酯化合物(II)为五亚甲基二异氰酸酯与3 元以上的脂肪族多元醇的加成物的情况下，作为该3元以上的脂肪族多元醇，具体地说，可以举出甘油、三羟甲基丙烷(TMP)、1,2,6-己三醇、三羟甲基乙烷、2,4-二羟基-3-羟基甲基戊烷、1,1,1-三(双羟基甲基)丙烷、2,2-双(羟基甲基)丁醇-3等3元醇；季戊四醇、双甘油等4元醇；阿拉伯糖醇、核醣醇、木糖醇等5元醇(戊五醇)；山梨糖醇、甘露醇、半乳糖醇、阿洛醇(アロズルシット)等6元醇(己糖醇)等。其中特别优选三羟甲基丙烷、季戊四醇。
通过五亚甲基二异氰酸酯与上述3元以上的脂肪族多元醇的加成聚合，得到上述加成物。
作为与上述多异氰酸酯化合物(II)反应的具有活性氢的化合物，具体地说，可以举出：甲醇、乙醇、正丙醇、异丙醇、甲氧基丙醇等醇类；丙酮肟、2-丁酮肟、环己酮肟等肟类；ε-己内酰胺等内酰胺类；乙酰乙酸甲酯、丙二酸乙酯等活性亚甲基化合物；3-甲基吡唑、3,5-二甲基吡唑、3,5-二乙基吡唑等吡唑化合物等，可以使用它们的1种或2种以上。
其中优选活性亚甲基化合物、肟类，更优选活性亚甲基化合物。
作为上述多异氰酸酯化合物，也可以使用衍生自五亚甲基二异氰酸酯(PDI)的多异氰酸酯化合物(以下也称为多异氰酸酯化合物(III))。作为多异氰酸酯化合物(III)，可以举出作为多异氰酸酯化合物(II)的上述物质。
作为多异氰酸酯化合物(III)的具体例，可以举出三井化学株式会社制造的D370N、D376N、D3725N等。
需要说明的是，对于本发明的组合物，只要含有上述含固化性官能团的含氟聚合物以及上述五亚甲基二异氰酸酯系固化剂，也可以进一步含有其他成分。该其他成分可以使用1种或2种以上。
本发明的组合物中，相对于组合物中的不挥发成分的总量100质量％，上述含固化性官能团的含氟聚合物的含量优选为20质量％～95质量％。
相对于上述含固化性官能团的含氟聚合物中的固化性官能团1当量，上述五亚甲基二异氰酸酯系固化剂的含量为0.1当量～5当量、优选为0.5当量～1.5当量。
更详细地说，上述五亚甲基二异氰酸酯系固化剂与上述含固化性官能团的含氟聚合物的比例为下述比例：相对于上述含固化性官能团的含氟聚合物中的官能团数，上述五亚甲基二异氰酸酯系固化剂中的官能团数为0.1当量～5当量、优选为0.5当量～ 1.5当量、进一步优选为0.7当量～1.2当量。
上述含固化性官能团的含氟聚合物中的固化性官能团的含量可根据单体的种类将NMR、FT-IR、元素分析、荧光X射线分析、中和滴定适当组合来计算出。
需要说明的是，在本说明书中，上述含固化性官能团的含氟聚合物和五亚甲基二异氰酸酯系固化剂的含量各自是以除去溶剂等后的不挥发成分的质量为基准的。
本发明的组合物由于含有上述含固化性官能团的含氟聚合物和五亚甲基二异氰酸酯系固化剂，因而能够形成即使在高压蒸煮测试后也具有与基材良好密合性的涂膜。另外，上述涂膜与EVA之类的密封材层也具有良好密合性。
从与基材的良好密合性的方面出发，本发明的组合物优选进一步含有多元醇化合物。
上述多元醇化合物优选羟值为10～300。通过使上述羟值处于上述范围内，所得到的涂膜与不透水性片材和由EVA形成的密封材层牢固地密合。
上述多元醇化合物优选数均分子量为300～4000。上述数均分子量通过凝胶渗透色谱测定。
从与基材或EVA之类的密封材层的密合性良好的方面出发，上述多元醇化合物优选为选自由含环己烷的多元醇、聚酯多元醇、聚碳酸酯多元醇、聚醚多元醇和聚丁二烯多元醇组成的组中的至少一种。更优选为选自由含环己烷的多元醇、聚酯多元醇、聚醚多元醇和聚丁二烯多元醇组成的组中的至少一种。
在上述组合物中，上述多元醇化合物相对于上述含氟聚合物为0.1质量％以上且小于100质量％。上述多元醇化合物相对于上述含氟聚合物优选为1质量％以上、更优选为5质量％以上、特别优选为20质量％以上，优选为50质量％以下、更优选为40质量％以下。上述多元醇化合物的含量若过多，则涂膜的耐候性可能变差；含量若过少，则涂膜与不透水性片材和由EVA形成的密封材层的密合性可能变差。
作为上述多元醇化合物也可以使用市售品。作为市售品，可以举出例如楠本化成公司制造的Flexorez(フレクソレッゾ)148、Flexorez 188、Flexorez A308、宇部兴产公司制造的ETERNACOLL UH-50、ETERNACOLL UM-90、ADEKA公司制造的ADEKA Polyether P-400、ADEKA Polyol BPX-21、日本曹达公司制造的NISSO-PB GI-1000、GI-2000、GI-3000、BASF公司制造的Sovermol 908、江苏华大公司制造的CMA3190、Croda公司制造的Priplast 3190、宇部兴产株式会社制造的PH50等。
从与基材、EVA之类的密封材层的密合性良好的方面出发，本发明的组合物优选进一步含有三聚氰胺树脂。
作为三聚氰胺树脂，可以优选举出如下得到的化合物和它们的混合物：使作为低级醇的甲醇、乙醇、异丙醇、丁醇、异丁醇等与将三聚氰胺和甲醛缩合得到的羟甲基三聚氰胺衍生物反应，进行醚化，得到该化合物。
作为羟甲基三聚氰胺衍生物，可以举出例如单羟甲基三聚氰胺、二羟甲基三聚氰胺、三羟甲基三聚氰胺、四羟甲基三聚氰胺、五羟甲基三聚氰胺、六羟甲基三聚氰胺等。
作为三聚氰胺树脂的分类，根据烷氧基化的比例可分成完全烷基型、羟甲基型、亚氨基型、羟甲基/亚氨基型，它们均可在本发明中使用。
作为上述三聚氰胺树脂，更优选含苯环的三聚氰胺树脂。
作为上述三聚氰胺树脂的市售品，可以举出美螺丝公司制造的M-85、M-25等。
在本发明的组合物中，上述三聚氰胺树脂相对于上述含氟聚合物优选为0.1质量％～10质量％。更优选为0.1质量％～5质量％、进一步优选为0.1质量％～3质量％。上述三聚氰胺树脂的含量若过多，耐候性可能变差；含量若过少，涂膜的密合性可能变差。
在本发明的组合物中可以进一步根据要求特性混配各种添加剂。作为添加剂，可以举出固化促进剂、颜料、颜料分散剂、消泡剂、流平剂、紫外线吸收剂、光稳定剂、增稠剂、密合改良剂、消光剂等。
作为固化促进剂，可以举出例如有机锡化合物、酸性磷酸酯、酸性磷酸酯与胺的反应物、饱和或不饱和的多元羧酸或其酸酐、有机钛酸酯化合物、胺系化合物、辛酸铅等。
作为固化促进剂可以使用通常的酸催化剂。可以举出例如用二甲基噁唑烷、2-氨基-2-甲基-1-丙醇等胺封闭的酸催化剂、未封闭的十二烷基苯磺酸、对甲苯磺酸、二壬基萘磺酸等。
作为酸催化剂，优选为选自由十二烷基苯磺酸、用胺封闭的十二烷基苯磺酸、对甲苯磺酸、酸性磷酸苯酯、用胺封闭的二壬基萘磺酸和酸性磷酸苯酯组成的组中的至少一种。
在本发明的组合物中，上述固化促进剂相对于上述含氟聚合物优选为0.01质 量％～10质量％。更优选为0.01质量％～5质量％、进一步优选为0.1质量％～3质量％。上述固化促进剂的含量若过多，则可使用时间可能变差；含量若过少，则涂膜与不透水性片材的密合性可能变差。
固化促进剂可以使用1种，也可以合用2种以上。
本发明的组合物优选进一步含有颜料。由此，所得到的固化涂膜的UV屏蔽性优异。另外，从使太阳能电池组件的外观美丽的方面考虑，也强烈希望添加颜料。
作为颜料，具体地说，可以举出：作为白色颜料的二氧化钛、碳酸钙、作为黑色颜料的炭黑、Cu-Cr-Mn合金等复合金属类等无机颜料；酞菁系、喹吖啶酮系或偶氮系等有机颜料等，但并不仅限于这些。
相对于含固化性官能团的含氟聚合物100质量份，颜料的添加量优选为0.1质量份～200质量份、更优选为0.1质量份～160质量份。
本发明的组合物优选进一步含有紫外线吸收剂。由于太阳能电池可在紫外线强的室外长期使用，因而要求有防范背板因紫外线而劣化的对策。若在本发明的组合物中添加紫外线吸收剂，则可对固化涂膜层赋予紫外线吸收功能。
作为紫外线吸收剂，有机系、无机系的任意紫外线吸收剂均可使用。在有机化合物系中，可以举出例如水杨酸酯系、苯并三唑系、二苯甲酮系、氰基丙烯酸酯系等紫外线吸收剂等；在无机系中，优选氧化锌、氧化铈等填料型无机系紫外线吸收剂等。
紫外线吸收剂可以单独使用1种，也可以组合使用2种以上。相对于涂料中的含固化性官能团的含氟聚合物的总量100质量％，紫外线吸收剂的量优选为0.1质量％～15质量％。在紫外线吸收剂的量过少的情况下，无法充分得到耐光性的改良效果；并且即使过多，效果也呈饱和。
本发明的组合物为涂料是优选方式之一。
本发明的组合物可以按照常规方法以溶剂型涂料、水性型涂料、粉体型涂料等形态进行制备。其中，从成膜的容易性、固化性、干燥性的优良性等方面考虑，优选溶剂型涂料的形态。
作为溶剂型涂料中的溶剂，优选有机溶剂，可以举出：乙酸乙酯、乙酸丁酯、乙酸异丙酯、乙酸异丁酯、乙酸溶纤剂、丙二醇甲基醚乙酸酯等酯类；丙酮、甲基乙基酮、甲基异丁基酮、环己酮等酮类；四氢呋喃、二氧六环等环状醚类；N,N-二甲基甲酰胺、N,N-二甲基乙酰胺等酰胺类；二甲苯、甲苯、溶剂石脑油等芳香族烃类；丙二 醇甲醚、乙基溶纤剂等二醇醚类；卡必醇乙酸酯等二甘醇酯类；正戊烷、正己烷、正庚烷、正辛烷、正壬烷、正癸烷、正十一烷、正十二烷、矿物精油等脂肪族烃类；它们的混合溶剂等。
其中更优选酯类，进一步优选乙酸丁酯。
将本发明的组合物制成溶剂型涂料的情况下，相对于涂料的总量100质量％，含固化性官能团的含氟聚合物的浓度优选为5质量％～95质量％、更优选为10质量％～70质量％。
本发明还涉及由上述组合物得到的涂膜。该涂膜可以根据用途将本发明的组合物涂布在适当的基材上并进行固化来形成。固化涂膜在基材上的形成可通过将本发明的组合物根据其涂料形态涂布在基材上来进行。
在涂布形态下的通常条件的温度范围内进行涂布即可，关于固化和干燥，在溶剂型涂料的情况下，在10℃～300℃、通常在100℃～200℃下进行30秒至3天。因而，本发明的组合物用于太阳能电池组件背板的涂布的情况下，作为不透水性片材，即使是Si蒸镀PET片材之类的要回避高温下处理的材料也可没有问题地使用。在固化和干燥后可进行养护，养护通常在20℃～300℃下利用1分钟～3天完成。
在基材上的涂布可以通过将本发明的组合物直接涂布在基材上来进行。
从隐蔽性、耐候性、耐化学药品性、耐湿性良好的方面考虑，优选固化涂膜的膜厚为1μm以上。更优选为3μm以上、进一步优选为5μm以上。出于若过厚则得不到轻量化效果的理由，上限优选为100μm左右、更优选为100μm左右。作为膜厚，特别优选为3μm～40μm。
由本发明的组合物得到的涂膜在高压蒸煮测试后也与基材具有良好密合性，与作为太阳能电池组件的密封材的通常的EVA的密合性优异，不仅如此，而且在卷缠时的耐粘连性性也优异，因而能够特别适合用于通常经卷缠工序制造的太阳能电池组件背板的涂布。
在用于太阳能电池组件背板的涂布的情况下，上述涂膜在不透水性片材等基材的单面或双面形成。
在由本发明的组合物得到的涂膜在基材的单面形成、且该基材的另一面为非涂布面的情况下，该涂膜在卷缠工序中与基材的非涂布面接触。另外，在上述涂膜在基材的单面形成、且在该基材的另一面设置由其它涂料得到的涂膜(后述的不具有固化性 官能团的含氟聚合物涂料的固化涂膜、聚酯涂料的涂膜、底涂层等)或其它片材的情况下，由本发明的组合物得到的涂膜在卷缠工序中与基材上的由其它涂料得到的涂膜或其它片材接触。此外，在由本发明的组合物得到的涂膜在基材的双面形成的情况下，该涂膜在卷缠工序中与在基材的另一面形成的相同种类的涂膜接触。
对于由本发明的组合物得到的涂膜，它们在任一情况下均能够发挥出相对于接触面的优异耐粘连性。
本发明还涉及太阳能电池组件的背板，其具有不透水性片材以及在该不透水性片材的至少一个面上形成的涂膜，该涂膜由上述组合物得到。
上述不透水性片材为按照使水分不会透过到密封材或太阳能电池单元的方式进行设置的层，只要为实质上不会透过水的材料就能够使用，可以举出例如聚碳酸酯树脂、丙烯酸类树脂、甲基丙烯酸类树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)、聚苯乙烯、聚烯烃树脂(聚乙烯、聚丙烯等)、聚卤化乙烯树脂(聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯等)、聚酯树脂(聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等)、聚酰胺树脂(尼龙6、尼龙66、MXD尼龙(间苯二甲胺-己二酸共聚物)等)、具有取代基的烯烃的聚合物(聚乙酸乙烯酯、聚乙烯醇等)、EVA(乙烯-乙烯醇共聚物)、乙烯-四氟乙烯共聚物、聚氨酯树脂(热塑性聚氨酯等)等，也可以将这些材料2种以上合用。从重量、价格、挠性等方面考虑，多使用PET片材、Si蒸镀PET片材、铝或不锈钢等金属薄片材等。其中常使用PET片材。厚度通常为50μm～250μm左右。其中在特别需要防湿性的情况下，常使用Si蒸镀PET片材。厚度通常为10μm～20μm左右。
此外，为了提高与上述涂膜的粘接性，可以对不透水性片材进行现有公知的表面处理。作为表面处理，可示例出例如电晕放电处理、等离子体放电处理、化学处理、金属片材的情况下的喷砂处理等。
在上述不透水性片材上形成上述涂膜的方法如上文所述。
上述涂膜可以仅在上述不透水性片材的单面形成，也可以在双面形成。
由于上述这样的背板与密封材的密合性优异，因而在具备该背板的太阳能电池组件中，在密封材与背板的界面处不易产生空隙，能够更可靠地保护太阳能电池单元。
本发明还涉及一种太阳能电池组件，其具有不透水性片材、形成在该不透水性片材的至少一个面上的涂膜、以及形成在该涂膜之上的密封材层，该涂膜由上述组合物 得到。
作为上述太阳能电池组件的优选结构，例如可举出图1～3所示的结构。
在图1所示的第1结构中，太阳能电池单元1被密封剂层2密封，该密封材层2被表面层3与背板4夹在中间。背板4进一步由不透水性片材5与固化涂膜6构成，该固化涂膜6由本发明的组合物得到。在该第1结构中，固化涂膜6仅设置在密封材层2侧。
上述密封材层2由乙烯/乙酸乙烯酯共聚物(EVA)、聚乙烯醇缩丁醛(PVB)、有机硅树脂、环氧树脂、丙烯酸类树脂等构成。
在上述表面层3通常使用玻璃板，但也可使用树脂片材等柔性材料。
图2所示的第2结构为在不透水性片材5的双面形成固化涂膜6而成的3层结构。
该第2结构中，虽然背板的膜厚增加，但其兼具由密封材层2侧的固化涂膜6带来的密合性以及由与密封材层2相反侧的固化涂膜6带来的耐候性这两方面的优点。
作为3层结构的背板，还可以为如下形成的3层结构的背板：在不透水性片材的一个面上形成由本发明的组合物得到的固化涂膜，在另一个面上形成不具有固化性官能团的含氟聚合物涂料的固化涂膜、含氟聚合物片材、聚酯片材或聚酯涂料的涂膜(其它片材或涂膜)。
图3所示的第3结构为在不透水性片材5的密封材层2侧形成由本发明的组合物得到的固化涂膜6、在与密封材层2相反侧形成有其它涂膜7的结构。
构成涂膜7的材料可以为不具有固化性官能团的含氟聚合物涂料的固化涂膜，可以为含氟聚合物片材，可以为聚酯片材，也可以为聚酯涂料的涂膜。
此外，为了进一步提高上述涂膜与密封材层的粘接性，可以对上述涂膜进行现有公知的表面处理。作为表面处理，可示例出例如电晕放电处理、等离子体放电处理、化学处理、喷砂处理等。
作为上述不具有固化性官能团的含氟聚合物涂料的固化涂膜，可以举出例如日本特开2004-214342号公报中记载的在PVdF中混配四烷氧基硅烷或其部分水解物而成的涂料的固化涂膜、VdF/TFE/CTFE共聚物与含有烷氧基硅烷单元的丙烯酸类树脂的混合涂料的固化涂膜、VdF/TFE/HFP共聚物与含羟基的丙烯酸类树脂的混合涂料的固化涂膜、在VdF/HFP共聚物中混配氨基硅烷偶联剂而成的涂料的固化涂膜等。从 隐蔽性、耐候性、耐化学药品性、耐湿性良好的方面考虑，膜厚通常优选为5μm～300μm。更优选为10μm～100μm、进一步优选为10μm～50μm。在这种情况下，也可以插入底涂层等。
需要说明的是，底涂层的形成使用现有公知的底层涂料用涂料通过常规方法进行。作为底层涂料用的涂料，可以举出例如环氧树脂、氨基甲酸酯树脂、丙烯酸类树脂、有机硅树脂、聚酯树脂等作为代表例。
作为上述含氟聚合物片材，可以举出PVdF片材或PVF片材、PCTFE片材、TFE/HFP/乙烯共聚物片材、TFE/HFP共聚物(FEP)片材、TFE/PAVE共聚物(PFA)片材、乙烯/TFE共聚物(ETFE)片材、乙烯/CTFE共聚物(ECTFE)片材等用于目前背板的含氟聚合物片材。从耐候性良好的方面考虑，通常优选膜厚为5μm～300μm。更优选为10μm～100μm、进一步优选为10μm～50μm。
作为上述聚酯片材，可以直接使用在现有背板中使用的片材，其在不透水性片材5上的粘接可以利用丙烯酸系接合剂、氨基甲酸酯系接合剂、环氧系接合剂、聚酯系接合剂等进行。从耐候性、成本、透明性良好的方面考虑，通常优选膜厚为5μm～300μm。更优选为10μm～100μm、进一步优选为10μm～50μm。
作为上述聚酯涂料，可以举出：使用了采用多元羧酸与多元醇等而成的饱和聚酯树脂的涂料；使用了采用马来酸酐、富马酸等与二醇类而成的不饱和聚酯树脂的涂料等，可通过辊涂、幕涂、喷涂、模涂等涂布方法形成涂膜。从隐蔽性、耐候性、耐化学药品性、耐湿性良好的方面考虑，优选膜厚为5μm～300μm。更优选为10μm～100μm、进一步优选为10μm～50μm。这种情况下，也可以插入底涂层等。
需要说明的是，在本发明的组合物中，除了上述太阳能电池组件用途以外，还可作为建材、内装材等室内用或建材、外装材、汽车、航空器、船舶、电车等室外用的涂料直接涂布至金属、混凝土、塑料等，或者重叠涂布在蚀洗用涂料、防锈涂料、环氧涂料、丙烯酸类树脂涂料、聚酯树脂涂料等底层涂料上。特别是可适合地用于与EVA层密合的涂膜层、或经卷缠工序制造的各种膜或片材材料等。
本发明还涉及一种层积体，其特征在于，其包含基材以及由上述组成物得到的层。由上述组成物得到的层可以通过在基材上涂布上述组成物来形成，也可以通过将上述组成物成型为膜后将上述膜层积在基材上来形成，还可以为将上述组合物固化而成的固化膜。由上述组成物得到的层可以仅在上述基材的单面形成、也可以在双面形成。 上述基材的形状、厚度等根据层积体的用途适宜地调整即可。基材优选由金属、混凝土或塑料构成。
上述基材和由上述组成物得到的层可以直接粘接，也可以隔着底涂层等其他层进行粘接，由于由上述组成物得到的层与上述基材的密合性优异，因而可以直接粘接。上述基材与由上述组成物得到的层进行直接粘接时，能够实现层积体的轻量化。
从隐蔽性、耐候性、耐化学药品性、耐湿性良好的方面考虑，优选由上述组成物得到的层的厚度为1μm以上。更优选为3μm以上、进一步优选为5μm以上。出于若过厚则得不到轻量化效果的理由，上限优选为100μm左右、更优选为100μm左右。作为由上述组成物得到的层的厚度，特别优选为3～40μm。
作为由上述塑料构成的基材的塑料材料，可以举出聚碳酸酯树脂、丙烯酸类树脂、甲基丙烯酸类树脂、丙烯腈-丁二烯-苯乙烯共聚物(ABS树脂)、聚苯乙烯、聚烯烃树脂(聚乙烯、聚丙烯等)、聚卤化乙烯树脂(聚氯乙烯、聚偏二氯乙烯、聚氟乙烯、聚偏二氟乙烯等)、聚酯树脂(聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯等)、聚酰胺树脂(尼龙6、尼龙66、MXD尼龙(间苯二甲胺-己二酸共聚物)等)、具有取代基的烯烃的聚合物(聚乙酸乙烯酯、聚乙烯醇等)、EVA(乙烯-乙烯醇共聚物)、乙烯-四氟乙烯共聚物、聚氨酯树脂(热塑性聚氨酯等)等共聚物。其中优选聚碳酸酯树脂、丙烯酸类树脂、聚氯乙烯、聚对苯二甲酸乙二醇酯、聚氨酯树脂。也可以将这些材料2种以上合用。
另外，为了提高与由上述组成物得到的层的粘接性，可以对基材进行现有公知的表面处理。作为表面处理，可示例出例如电晕放电处理、等离子体放电处理、化学处理、金属片材的情况下的喷砂处理等。
上述层积体可用于建材、内装材、外装材、汽车、航空器、船舶(甲板、舱面、船底等)、电车、储罐、桥梁等。特别是作为车辆内外装部件是有用的。
【发明的效果】
本发明的组合物由于含有上述构成，因而能够形成即使在高压蒸煮测试后还具有与基材良好密合性的涂膜。这样的涂膜作为太阳能电池组件背板的涂膜是极为有用的。
【附图说明】
图1为太阳能电池组件的第1结构的示意性截面图。
图2为太阳能电池组件的第2结构的示意性截面图。
图3为太阳能电池组件的第3结构的示意性截面图。
【具体实施方式】
通过实施例对本发明进行更详细的说明，但本发明并不受该实施例的限定。
表中记载的成分如下。
氟树脂：固化性TFE系共聚物溶液、商品名Zeffle GK570、大金工业株式会社制造
二醇：含环己烷的二醇、商品名Sovermol 908(具有下述结构的化合物)、BASF公司制造
【化5】
Figure PCTCN2018116412-appb-000005
二醇：聚酯二醇、CMA-3190、江苏华大公司制造
消光剂：CP4-8991、Grace Corporation公司制造
含苯环的三聚氰胺树脂：M-85、美螺丝公司制造
固化促进剂(酸催化剂)：CYCAT600、购自Cytec,Inc.的十二烷基苯磺酸的70质量％异丙醇溶液)
PDI系固化剂：D3725N、三井化学株式会社制造
XDI系固化剂：Takenate D120N、三井化学株式会社制造
HDI系固化剂：Sumidur N3300、Sumika Bayer Urethane公司制造
制备例1
在搅拌下将固化性TFE系共聚物溶液(大金工业株式会社制造的Zeffle GK570、 固体成分65质量％、羟值60mgKOH/g、溶剂：乙酸丁酯)202质量份、作为白色颜料的二氧化钛(杜邦公司制造的R960)263.0质量份、乙酸丁酯167.0质量份预混合，之后装入直径1.2mm的玻璃珠632质量份，使用颜料分散机以1500rpm分散1小时。其后利用#80目的筛滤出玻璃珠，在该溶液中加入固化性TFE系共聚物溶液(Zeffle GK570)283.0质量份、乙酸丁酯85.0质量份，制备白色涂料。
在该白色涂料1000质量份中混配二醇(Sovermol 908、BASF公司制造)118.3质量份、消光剂(CP4-8991、Grace Corporation公司制造)47.3质量份、含苯环的三聚氰胺树脂(M-85、美螺丝公司制造)4.7质量份、酸催化剂(CYCAT600、购自Cytec,Inc.的十二烷基苯磺酸的70质量％异丙醇溶液)4.7质量份、固化剂(D3725N、三井化学株式会社制造、NCO含量22.8％)66.2质量份(相对于固化性TFE系共聚物中的固化性官能团1当量，相当于1.0当量)，制备涂料1。
实施例1
作为不透水性片材使用PET膜(东材制造的DS10、厚度250μm。片材A)，对该片材A的单面以2000W进行电晕处理，并利用涂布机按照干燥膜厚为10μm涂布制备例1中制备的涂料1，在150℃干燥2分钟，制作2层结构的背板A1。
接着在该背板A1的涂膜面上以2000W进行电晕处理，在50℃进行48小时养护，之后在该涂膜面上载置EVA树脂片材(福斯特制造的F806P。厚度500μm)，进一步在EVA树脂片材上载置强化玻璃(无锡海达制造、3.2mm厚)，在142℃进行压接，制作3层结构的样品A1(图1所示的方式)。对于该玻璃/EVA/背板粘接样品A1考察密合性(EVA与背板之间)。将结果列于表1。
试验方法和测定方法如下。
(剥离强度)
对于实施例1中得到的玻璃/EVA/背板粘接样品A1，在初期状态和PCT(高压蒸煮测试、121℃、湿度100％RH、2气压)48小时后利用剥离试验测定EVA/背板层间的密合性。将测定样品的EVA/背板部分划出宽1cm×15cm，使用Tensilon(ORIENTEC制)进行180度剥离试验，以N/cm为单位，测定EVA/背板间的粘接强度。
(涂膜破断)
与剥离强度同样地对初期状态和PCT 48小时后的涂膜通过目视进行评价。
(涂膜/PET剥离)
与剥离强度同样地对初期状态和PCT 48小时后的涂膜通过目视进行评价。
(膜厚)
根据JIS C-2151，利用千分尺(Mitutoyo公司制造)进行测定。
实施例2、比较例1～12
除了按表1或表2所记载变更涂料的成分以外，与制备例1同样地制备涂料，与实施例1同样地制作2层结构的背板、玻璃/EVA/背板的粘接样品。
将结果列于表1或表2。
【表1】
Figure PCTCN2018116412-appb-000006
【表2】
Figure PCTCN2018116412-appb-000007
【符号的说明】
1：太阳能电池单元
2：密封材层
3：表面层
4：背板
5：不透水性片材
6：固化涂膜
7：其他涂膜

Claims (15)

  1. 一种组合物，其特征在于，其含有：
    含固化性官能团的含氟聚合物，以及
    五亚甲基二异氰酸酯系固化剂。
  2. 如权利要求1所述的组合物，其中，含固化性官能团的含氟聚合物含有基于含氟单体的聚合单元和基于含固化性官能团单体的聚合单元，该含固化性官能团单体为选自由含羟基单体、含羧基单体、含氨基单体以及硅酮系乙烯基单体组成的组中的至少一种。
  3. 如权利要求2所述的组合物，其中，含氟单体为选自由四氟乙烯、三氟氯乙烯以及偏二氟乙烯组成的组中的至少一种。
  4. 如权利要求1、2或3所述的组合物，其中，该组合物进一步含有多元醇化合物。
  5. 如权利要求1、2或3所述的组合物，其中，该组合物进一步含有三聚氰胺树脂。
  6. 如权利要求1、2或3所述的组合物，其中，该组合物进一步含有多元醇化合物和三聚氰胺树脂。
  7. 如权利要求1、2、3、4、5或6所述的组合物，其中，该组合物进一步含有酸催化剂。
  8. 如权利要求1、2、3、4、5、6或7所述的组合物，其中，该组合物进一步含有颜料。
  9. 如权利要求1、2、3、4、5、6、7或8所述的组合物，其中，该组合物进一步含有紫外线吸收剂。
  10. 如权利要求1、2、3、4、5、6、7、8或9所述的组合物，其中，该组合物为涂料。
  11. 一种涂膜，其特征在于，其是由权利要求1、2、3、4、5、6、7、8、9或10所述的组合物得到的。
  12. 一种层积体，其特征在于，其包含：
    基材，以及
    由权利要求1、2、3、4、5、6、7、8、9或10所述的组成物得到的层。
  13. 如权利要求12所述的层积体，其中，基材由金属、混凝土或塑料构成。
  14. 一种太阳能电池组件背板，其特征在于，其具有：
    不透水性片材；以及
    形成在上述不透水性片材的至少一个面上的涂膜，该涂膜是由权利要求1、2、3、4、5、6、7、8、9或10所述的组合物得到的。
  15. 一种太阳能电池组件，其特征在于，其具有：
    不透水性片材；
    形成在上述不透水性片材的至少一个面上的涂膜，该涂膜是由权利要求1、2、3、4、5、6、7、8、9或10所述的组合物得到的；以及
    形成在上述涂膜之上的密封材层。
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