WO2013024893A1 - Feuille polymère pour cellule photovoltaïque ainsi que son procédé de fabrication et module de cellule photovoltaïque - Google Patents

Feuille polymère pour cellule photovoltaïque ainsi que son procédé de fabrication et module de cellule photovoltaïque Download PDF

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WO2013024893A1
WO2013024893A1 PCT/JP2012/070857 JP2012070857W WO2013024893A1 WO 2013024893 A1 WO2013024893 A1 WO 2013024893A1 JP 2012070857 W JP2012070857 W JP 2012070857W WO 2013024893 A1 WO2013024893 A1 WO 2013024893A1
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polymer
layer
polymer layer
solar cell
mass
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PCT/JP2012/070857
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Japanese (ja)
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健司 勝田
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富士フイルム株式会社
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/04—Polysiloxanes
    • 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 solar cell polymer sheet provided on the opposite side of the solar cell element to the solar light incident side, a method for producing the same, and a solar cell module.
  • a solar cell module has a structure in which a glass / front sheet on which sunlight is incident / a sealant / a solar cell element / a sealant / a backsheet (hereinafter also referred to as BS) is laminated in this order. is doing.
  • a solar cell module generally, a solar cell element is embedded with a resin (sealing material) such as EVA (ethylene-vinyl acetate copolymer), and a solar cell protective sheet is further adhered thereon. Configured to structure.
  • a polyester film, particularly a polyethylene terephthalate (hereinafter referred to as PET) film has been used.
  • a general PET film is likely to peel off on the solar cell.
  • a laminate-type BS in which a weather-resistant film is bonded to the outermost layer side of a base film such as PET has been used for the problem of weather resistance.
  • the laminated laminates the most widely used was a fluorine-based polymer film such as a polyvinyl fluoride film.
  • JP 2010-53317 A discloses a polymer sheet in which a polyethylene terephthalate support having a specific thickness and a weathering layer which is a fluorine-containing polymer layer are laminated by coating.
  • various other functional layers have been laminated on the polymer sheet for solar cells.
  • white inorganic fine particles such as titanium oxide are added to the back sheet, a white layer having light reflection performance is laminated, and the light passing through the cell is diffusely reflected to the cell.
  • the method etc. which improve electric power generation efficiency by returning are described.
  • a polymer layer such as an easy adhesion layer may be provided on the outermost layer of the back sheet.
  • a technique for providing a thermal adhesive layer on a white polyethylene terephthalate film is described in Japanese Patent Application Laid-Open No. 2003-060218.
  • the present situation is that the protective sheet for solar cells, which tends to be multi-layered as described above, is becoming more and more likely to have a problem of adhesion between layers as the number of laminated layers increases. Furthermore, in recent years, solar cells have been used for a long time in harsh places such as outdoors, from the viewpoint of increasing the power generation efficiency of solar cells and from the viewpoint of reducing the cost by integrating and installing them. Also, the durability is required for the adhesion between the layers.
  • Japanese Patent Application Laid-Open No. 05-25361 discloses a compound having a plurality of 2-oxazoline groups in a molecule and a plurality of molecules in a molecule.
  • a curable resin composition containing a compound having a carboxyl group and a catalyst is described.
  • each interlayer required for solar cells in recent years is used. From the viewpoint of adhesiveness, it is still insufficient. Furthermore, further improvement is demanded for improvement in adhesion when a polymer layer containing a polymer such as a fluoropolymer and a silicone polymer is applied.
  • the curable resin composition described in JP-A No. 05-25361 uses a highly reactive compound such as an acrylic resin as a main binder as a compound having a carboxyl group. For this reason, it is difficult to apply the said curable resin composition to the solar cell use as which a weather resistance is requested
  • the present invention has been made in view of the above circumstances, and has excellent adhesion between a polymer substrate and a polymer layer provided on the polymer substrate, and a polymer sheet for solar cells excellent in production suitability. It is an object to provide a manufacturing method thereof and a solar cell module having stable power generation efficiency.
  • ⁇ 2> The solar cell polymer sheet according to ⁇ 1>, wherein the first polymer layer contains an onium compound.
  • ⁇ 3> The polymer sheet for solar cells according to ⁇ 1> or ⁇ 2>, wherein the second polymer layer contains an onium compound.
  • ⁇ 4> The polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 3>, wherein the first polymer layer is an outermost layer.
  • ⁇ 5> The sun according to any one of ⁇ 1> to ⁇ 4>, wherein at least one of the first polymer layer and the second polymer layer contains a water-miscible organic solvent having a boiling point of 99 ° C. or less. It is a polymer sea for batteries.
  • ⁇ 6> The polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 5>, wherein the polymer base material contains an end-capping agent.
  • ⁇ 7> The polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 6>, wherein the polymer base material contains a carbodiimide-based end-capping agent.
  • ⁇ 8> The polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 7>, wherein the polymer substrate contains fine particles that are inorganic particles or organic particles.
  • the polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 8>, wherein the polymer base material has a laminated structure including two or more layers having different content rates of fine particles that are inorganic particles or organic particles. It is.
  • At least one of the first polymer layer and the second polymer layer has a boiling point of 99 ° C. selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, and acetone.
  • the polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 9>, which contains the following water-miscible organic solvent.
  • a step of applying a coating solution having a value greater than 0 and less than 1 and drying, followed by curing to form a second polymer layer, and a fluoropolymer and a silicone polymer are selected on the second polymer layer
  • a step of forming a first polymer layer by applying and drying a coating solution containing at least one binder polymer are selected from the second polymer layer.
  • ⁇ 12> The method for producing a polymer sheet for a solar cell according to ⁇ 11>, wherein the coating liquid used in the step of forming the first polymer layer contains an onium compound.
  • the curing time of the polymer layer in the step of forming the first polymer layer and the step of forming the second polymer layer are both in the range of 1 minute to 30 minutes.
  • ⁇ 11> to ⁇ 13> The manufacturing method of the polymer sheet for solar cells of any one of these.
  • the coating liquid used for forming at least one of the first polymer layer and the second polymer layer is a binder polymer containing a water-miscible organic solvent having a boiling point of 99 ° C. or less in the coating liquid.
  • the coating liquid used for forming at least one of the first polymer layer and the second polymer layer is at least selected from methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, and acetone.
  • the polymer sheet for solar cells according to any one of ⁇ 11> to ⁇ 15> which contains one kind of water-miscible organic solvent having a boiling point of 99 ° C. or less.
  • ⁇ 17> Manufactured by the method for producing the polymer sheet for solar cells according to any one of ⁇ 1> to ⁇ 10> or the polymer sheet for solar cells according to any one of ⁇ 11> to ⁇ 16>. It is a solar cell module provided with the polymer sheet for solar cells made.
  • ⁇ 18> a transparent front substrate on which sunlight is incident, a cell structure portion provided on the front substrate and having a solar cell element and a sealing material for sealing the solar cell element;
  • the polymer sheet for solar cells which was excellent in the adhesiveness of a polymer base material and the polymer layer provided on this polymer base material, and was excellent in manufacture aptitude, and its manufacturing method can be provided.
  • the solar cell module which has the stable electric power generation efficiency can be provided.
  • the amount of each component in the composition when there are a plurality of substances corresponding to each component in the composition, the plurality of the components present in the composition unless otherwise specified. It means the total amount of substance.
  • a numerical range indicated by using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the term “process” is not only an independent process, but is included in the term if the purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
  • the polymer sheet for solar cells of the present invention comprises a first polymer layer containing at least one binder polymer selected from a fluoropolymer and a silicone polymer on a polymer substrate, and the polymer of the first polymer layer.
  • the substrate side includes at least one binder polymer selected from a fluoropolymer and a silicone polymer, and a structural part derived from a crosslinking agent having an oxazoline group that crosslinks the binder polymer, and the oxazoline for the binder polymer
  • the polymer sheet for solar cells which has the 2nd polymer layer whose group equivalent [meq / g] is more than 0 and less than 1.
  • the first polymer layer that is a constituent layer of the polymer sheet is a layer containing at least one binder polymer selected from a fluoropolymer and a silicone polymer
  • the second polymer layer is At least one binder polymer selected from a fluoropolymer and a silicone polymer, and a cross-linking agent having an oxazoline group, and the equivalent [meq / g] of the oxazoline group to the binder polymer is 0
  • the adhesiveness between the polymer layer and the polymer substrate in the present invention is excellent in sustainability.
  • the first polymer layer and / or the second polymer layer contains an onium compound, so that the polymer has excellent adhesion between the polymer layer and the polymer substrate.
  • the solvent resistance of the layer can also be improved.
  • the first and second polymer layers in the present invention may be a weather resistant layer exposed to an external environment, that is, a back layer, when a solar cell module is configured using the polymer sheet for solar cells of the present invention.
  • a weather resistant layer exposed to an external environment, that is, a back layer, when a solar cell module is configured using the polymer sheet for solar cells of the present invention.
  • the first polymer layer is preferably the outermost layer.
  • the polymer sheet for solar cells of the present invention has a polymer substrate.
  • the polymer substrate include polyester, polyolefin such as polypropylene and polyethylene, or fluorine-based polymer such as polyvinyl fluoride.
  • polyester is preferable from the viewpoint of cost and mechanical strength.
  • the polyester used as the polymer substrate (support) in the present invention is a linear saturated polyester synthesized from an aromatic dibasic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof.
  • Specific examples of such polyester include polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, poly (1,4-cyclohexylenedimethylene terephthalate), polyethylene-2,6-naphthalate and the like. Of these, polyethylene terephthalate or polyethylene-2,6-naphthalate is particularly preferable from the viewpoint of balance between mechanical properties and cost.
  • the polyester may be a homopolymer or a copolymer. Further, the polyester may be blended with a small amount of another type of resin such as polyimide.
  • an Sb-based, Ge-based or Ti-based compound as a catalyst from the viewpoint of keeping the carboxyl group content below a predetermined range, and among these, a Ti-based compound is particularly preferable.
  • a Ti-based compound an embodiment is preferred in which the Ti-based compound is polymerized by using it as a catalyst so that the Ti element conversion value is in the range of 1 ppm to 30 ppm, more preferably 3 ppm to 15 ppm.
  • the amount of Ti compound used is within the above range in terms of Ti element, the terminal carboxyl group can be adjusted to the following range, and the hydrolysis resistance of the polymer substrate can be kept low.
  • Examples of the synthesis of polyester using a Ti compound include Japanese Patent Publication No. 8-301198, Japanese Patent No. 2543624, Japanese Patent No. 3335683, Japanese Patent No. 3717380, Japanese Patent No. 3897756, Japanese Patent No. 396226, and Japanese Patent No. 39786666.
  • No. 3, Patent No. 3,996,871, Patent No. 40000867, Patent No. 4053837, Patent No. 4,127,119, Patent No. 4,134,710, Patent No. 4,159,154, Patent No. 4,269,704, Patent No. 4,313,538 and the like can be applied.
  • the carboxyl group content in the polyester is preferably 55 equivalent / t (tons; the same applies hereinafter) or less, more preferably 35 equivalent / t or less.
  • the lower limit of the carboxyl group content is preferably 2 equivalents / t in terms of maintaining adhesion between the layer formed on the polyester (for example, a colored layer).
  • “Equivalent / t” represents a molar equivalent per 1 ton.
  • the carboxyl group content in the polyester can be adjusted by the polymerization catalyst species and the film forming conditions (film forming temperature and time).
  • the polyester in the present invention is preferably solid-phase polymerized after polymerization.
  • Solid-phase polymerization may be a continuous method (a method in which a tower is filled with a resin, which is slowly heated for a predetermined time and then sent out), or a batch method (a resin is charged into a container). , A method of heating for a predetermined time).
  • Japanese Patent No. 2621563, Japanese Patent No. 3121876, Japanese Patent No. 3136774, Japanese Patent No. 3603585, Japanese Patent No. 3616522, Japanese Patent No. 3617340, Japanese Patent No. 3680523, Japanese Patent No. 3717392 are disclosed.
  • the method described in Japanese Patent No. 4167159 can be applied.
  • the temperature of the solid phase polymerization is preferably 170 ° C. or higher and 240 ° C. or lower, more preferably 180 ° C. or higher and 230 ° C. or lower, and further preferably 190 ° C. or higher and 220 ° C. or lower.
  • the solid phase polymerization time is preferably 5 hours to 100 hours, more preferably 10 hours to 75 hours, and still more preferably 15 hours to 50 hours.
  • the solid phase polymerization is preferably performed in a vacuum or in a nitrogen atmosphere.
  • the polyester substrate in the present invention is preferably a biaxially stretched film from the viewpoint of mechanical strength.
  • the polyester base material in the present invention is obtained by melt-extruding the above polyester into a film shape and then cooling and solidifying it with a casting drum to form an unstretched film.
  • the unstretched film is subjected to a longitudinal direction at Tg to (Tg + 60) ° C.
  • a biaxially stretched film that has been stretched once or twice or more so that the total magnification is 3 to 6 times, and then stretched so that the magnification is 3 to 5 times in the width direction at Tg to (Tg + 60) ° C.
  • heat treatment may be performed at 180 to 230 ° C. for 1 to 60 seconds as necessary.
  • the thickness of the polymer substrate is preferably about 25 ⁇ m to 300 ⁇ m. If the thickness is 25 ⁇ m or more, the mechanical strength is good, and if it is 300 ⁇ m or less, it is advantageous in terms of cost.
  • the polyester base material has a tendency that the hydrolysis resistance deteriorates as the thickness increases, and the durability during long-term use tends to decrease.
  • the thickness is 120 ⁇ m or more and 300 ⁇ m or less, and When the carboxyl group content in the polyester is 2 to 35 equivalents / t, the wet heat durability can be further improved.
  • the polymer substrate may contain one or more end capping agents.
  • the content when the polymer substrate contains an end-capping agent is preferably from 0.1% by mass to 10% by mass, more preferably from 0.1% by mass to the total mass of the polymer contained in the polymer substrate. It may be 2% to 5% by weight, more preferably 0.3% to 2% by weight.
  • an end-capping agent that reacts with the terminal carboxyl group is added. Can be effective.
  • the content of the end-capping agent is within the above range, it can be avoided that the end-capping agent acts as a plasticizer for the polymer and the mechanical strength and heat resistance of the polymer substrate are lowered.
  • terminal blocking agent examples include epoxy compounds, carbodiimide compounds, oxazoline compounds, carbonate compounds, and the like.
  • a carbodiimide having high affinity with a polymer suitable for a polymer substrate such as polyester and high end-capping ability is preferred.
  • the end-capping agent (particularly carbodiimide end-capping agent) has a high molecular weight, volatilization during melt film formation can be reduced.
  • the molecular weight is preferably 200 to 100,000 in terms of weight average molecular weight, more preferably 2000 to 80,000, and still more preferably 10,000 to 50,000.
  • the weight average molecular weight of the end-capping agent (particularly carbodiimide end-capping agent) is 100,000 or less, it is easy to uniformly disperse in the polymer, and the weather resistance improving effect can be sufficiently exhibited.
  • the weight average molecular weight of the end-capping agent is 200 or more, volatilization during extrusion and / or film formation can be suppressed, and an effect of improving weather resistance can be exhibited.
  • the carbodiimide terminal blocking agent is a carbodiimide compound having a carbodiimide group.
  • the carbodiimide compound includes a monofunctional carbodiimide and a polyfunctional carbodiimide.
  • monofunctional carbodiimides include dicyclohexylcarbodiimide, diisopropylcarbodiimide, dimethylcarbodiimide, diisobutylcarbodiimide, dioctylcarbodiimide, t-butylisopropylcarbodiimide, diphenylcarbodiimide, di-t-butylcarbodiimide and di- ⁇ -naphthylcarbodiimide.
  • they are dicyclohexyl carbodiimide and diisopropyl carbodiimide.
  • carbodiimide having a polymerization degree of 3 to 15 is preferably used.
  • the terminal blocker is a carbodiimide compound having high heat resistance.
  • a carbodiimide compound used as a terminal blocking agent preferably has a cyclic structure (for example, those described in JP2011-153209A). These can exhibit the same effect as the above high molecular weight carbodiimide even at a low molecular weight. This is because the terminal carboxyl group of the polymer and the cyclic carbodiimide undergo a ring-opening reaction, one of which reacts with this terminal carboxyl group, and the other of the ring-opening reacts with the other terminal carboxyl group to increase the molecular weight, thereby generating an isocyanate gas. It is because it can suppress.
  • the terminal blocking agent which is a carbodiimide compound having a cyclic structure, preferably includes a cyclic structure in which a first nitrogen and a second nitrogen of a carbodiimide group are bonded by a bonding group.
  • the end-capping agent has at least one carbodiimide group adjacent to the aromatic ring, and the first nitrogen and the second nitrogen of the carbodiimide group adjacent to the aromatic ring are bound by a linking group. It is preferably a carbodiimide containing a cyclic structure (also called an aromatic cyclic carbodiimide).
  • the aromatic cyclic carbodiimide may have a plurality of cyclic structures.
  • the aromatic cyclic carbodiimide is preferably an aromatic carbodiimide having no ring structure in which the first nitrogen and the second nitrogen of two or more carbodiimide groups are bonded by a linking group in the molecule, that is, a monocyclic ring. Can be used.
  • the cyclic structure has one carbodiimide group (—N ⁇ C ⁇ N—), and the first nitrogen and the second nitrogen are bonded by a bonding group.
  • One cyclic structure has only one carbodiimide group.
  • the compound may have a plurality of carbodiimide groups.
  • the number of atoms in the cyclic structure is preferably 8 to 50, more preferably 10 to 30, further preferably 10 to 20, and particularly preferably 10 to 15.
  • the number of atoms in the cyclic structure means the number of atoms directly constituting the cyclic structure.
  • the number of atoms is 8 for an 8-membered ring, and the number of atoms is 50 for a 50-membered ring. .
  • the cyclic carbodiimide compound can maintain stability and can be suitable for storage and use.
  • a cyclic carbodiimide compound is 50 or less from a viewpoint which can suppress the cost increase by synthetic difficulty. From this viewpoint, the range of the number of atoms in the cyclic structure is preferably 10 to 30, more preferably 10 to 20, and still more preferably 10 to 15.
  • carbodiimide sealant having a cyclic structure examples include the following compounds. However, the present invention is not limited to the following specific examples.
  • the epoxy end-capping agent is an epoxy compound.
  • the epoxy compound include glycidyl ester compounds and glycidyl ether compounds.
  • glycidyl ester compounds include benzoic acid glycidyl ester, t-Bu-benzoic acid glycidyl ester, P-toluic acid glycidyl ester, cyclohexanecarboxylic acid glycidyl ester, pelargonic acid glycidyl ester, stearic acid glycidyl ester, lauric acid glycidyl ester , Glycidyl palmitate, glycidyl behenate, glycidyl versatate, glycidyl oleate, glycidyl linoleate, glycidyl linolein, glycidyl behenol, glycidyl stearol, diglycidyl terephthalate, isophthalic acid Diglycidyl ester, diglycidyl phthalate, diglycidyl naphthalene dicar
  • the glycidyl ether compound examples include phenyl glycidyl ether, O-phenyl glycidyl ether, 1,4-bis ( ⁇ , ⁇ -epoxypropoxy) butane, 1,6-bis ( ⁇ , ⁇ - Epoxypropoxy) hexane, 1,4-bis ( ⁇ , ⁇ -epoxypropoxy) benzene, 1- ( ⁇ , ⁇ -epoxypropoxy) -2-ethoxyethane, 1- ( ⁇ , ⁇ -epoxypropoxy) -2-benzyl Oxyethane, 2,2-bis- [ politician- ( ⁇ , ⁇ -epoxypropoxy) phenyl] propane and 2,2-bis- (4-hydroxyphenyl) propane and 2,2-bis- (4-hydroxyphenyl) Examples thereof include bisglycidyl polyether obtained by the reaction of bisphenol such as methane and epichlorohydrin. These can use 1 type (s) or 2 or more types.
  • the oxazoline-based end-capping agent is an oxazoline compound.
  • a bisoxazoline compound is preferable. Specifically, 2,2′-bis (2-oxazoline), 2,2′-bis (4-methyl-2-oxazoline), 2,2′-bis (4,4-dimethyl-2-oxazoline), 2,2′-bis (4-ethyl-2-oxazoline), 2,2′-bis (4,4′-diethyl-2-oxazoline), 2,2 '-Bis (4-propyl-2-oxazoline), 2,2'-bis (4-butyl-2-oxazoline), 2,2'-bis (4-hexyl-2-oxazoline), 2,2'- Bis (4-phenyl-2-oxazoline), 2,2′-bis (4-cyclohexyl-2-oxazoline), 2,2′-bis (4-benzyl-2-oxazoline), 2,2
  • 2,2′-bis (2-oxazoline) is most preferably used from the viewpoint of reactivity with polyester.
  • the bisoxazoline compound mentioned above may be used individually by 1 type, or may use 2 or more types together.
  • Such a terminal blocking agent is introduced into the polymer substrate by a method such as kneading into the polymer contained in the polymer substrate.
  • the above effect can be obtained by reacting the end-capping agent and the polymer molecule in direct contact. Even if the end-capping agent is added to the coating layer on the polymer substrate, the polymer and the end-capping agent do not react.
  • the polymer constituting the polymer substrate may contain fine particles that are inorganic particles or organic particles. Thereby, the reflectance (whiteness) of light can be improved and the power generation efficiency of a solar cell can be improved.
  • the average particle size of the fine particles is preferably from 0.1 ⁇ m to 10 ⁇ m, more preferably from 0.1 ⁇ m to 5 ⁇ m, still more preferably from 0.15 ⁇ m to 1 ⁇ m, and the content is from 0% by mass to 50% with respect to the total mass of the polymer.
  • the mass may be 1% by mass, preferably 1% by mass to 10% by mass, and more preferably 2% by mass to 5% by mass.
  • the average particle size of the fine particles is 0.1 ⁇ m to 10 ⁇ m, the whiteness of the polymer substrate is easily set to 50 or more.
  • the content of the particles is 1% by mass or more, the polymer substrate whiteness is easily set to 50 or more.
  • the average particle diameter and content refer to the weighted average value based on the average value of each layer, when a polymer base material is a multilayer structure. That is, the average particle diameter is calculated by (average value of particle diameter of each layer) ⁇ (thickness of each layer / thickness of all layers) for each layer, and the sum is obtained. (Average value of quantity) ⁇ (thickness of each layer / thickness of all layers) is calculated for each layer and indicates the sum total.
  • the average particle size of the fine particles is determined by an electron microscope method. Specifically, the following method is used. The fine particles are observed with a scanning electron microscope, the magnification is appropriately changed according to the size of the fine particles, and the photographed image is enlarged and copied. Next, the outer circumference of each particle is traced for at least 200 fine particles selected at random. The equivalent circle diameter of the particles is measured from these trace images with an image analyzer. The average of the measured values is defined as the average particle size.
  • the fine particles may be either inorganic particles or organic particles, or a combination of both. Thereby, the reflectance of light can be improved and the power generation efficiency of a solar cell can be improved.
  • Suitable inorganic particles include, for example, wet and dry silica, colloidal silica, calcium carbonate, aluminum silicate, calcium phosphate, alumina, magnesium carbonate, zinc carbonate, titanium oxide, zinc oxide (zinc white), antimony oxide, and oxidation.
  • the titanium oxide may be either anatase type or rutile type.
  • the surface of the fine particles may be subjected to an inorganic surface treatment using alumina, silica or the like, or may be subjected to an organic surface treatment using a silicon compound or alcohol.
  • titanium dioxide is preferable, and when the polymer base material contains this, the polymer sheet can exhibit excellent durability even under light irradiation.
  • the elongation at break is preferably 35% or more, more preferably 40% or more. Since the polymer sheet of this embodiment can suppress photodecomposition and deterioration, it is more suitable as a back surface protective film for solar cells used outdoors.
  • Titanium dioxide includes those having a rutile crystal structure and those having an anatase crystal structure.
  • the anatase type has a very high spectral reflectance of ultraviolet rays, whereas the rutile type has a characteristic that the absorption rate of ultraviolet rays is large (spectral reflectance is small).
  • the present inventor pays attention to such a difference in spectral characteristics in the crystal form of titanium dioxide, and can improve the light resistance in the polymer sheet for protecting the back surface of the solar cell by utilizing the ultraviolet absorption performance of rutile titanium dioxide. I found out that I can do it.
  • excellent film durability under light irradiation can be obtained without substantially adding other ultraviolet absorbers. Therefore, problems such as contamination due to bleeding out of the ultraviolet absorbent and a decrease in adhesion are unlikely to occur.
  • the fine particles are mainly composed of rutile type titanium dioxide
  • the mass of the rutile type titanium dioxide in the total titanium dioxide particles exceeds 50% by mass with respect to the total mass of the titanium dioxide particles.
  • the amount of anatase type titanium dioxide in all the titanium dioxide particles with respect to the total titanium dioxide particle mass is 10 mass% or less, More preferably, it is 5 mass% or less, Most preferably, it is 0 mass% or less.
  • the content of the anatase type titanium dioxide is not more than the above upper limit value, the amount of rutile type titanium dioxide in the total titanium dioxide particles can be ensured, so that the ultraviolet absorption performance can be ensured.
  • Rutile titanium dioxide and anatase titanium dioxide can be distinguished by X-ray structure diffraction and spectral absorption characteristics.
  • the surface of the rutile titanium dioxide fine particles may be subjected to an inorganic surface treatment using alumina, silica or the like, or an organic surface treatment using a silicon compound or alcohol.
  • particle size adjustment, coarse particle removal, and the like may be performed using a purification process.
  • industrial means for the purification process include pulverizing means such as a jet mill and a ball mill, and classification means such as dry or wet centrifugation.
  • the organic fine particles that can be contained in the polymer substrate are preferably those that can withstand the heat during film formation.
  • fine particles made of a cross-linked resin specific examples include fine particles made of polystyrene cross-linked with divinylbenzene.
  • a master batch method (MB method: (3) above) including mixing polyester resin and fine particles in an extruder in advance is preferable.
  • a method can be employed in which MB and the fine particles, which have not been dried in advance, are introduced into an extruder and degassed moisture and air.
  • the increase in the acid value of the polymer can be suppressed by preparing MB using a polymer that has been slightly dried in advance. Examples of such a method include a method of extruding while degassing, a method of extruding without sufficiently degassing with a sufficiently dried polymer, and the like.
  • the drying conditions are preferably 100 ° C. to 200 ° C., more preferably 120 ° C. to 180 ° C., for 1 hour or longer, more preferably 3 hours or longer, and further preferably 6 hours or longer. Thereby, it is sufficiently dried so that the moisture content of the polymer such as polyester is preferably 50 ppm or less, more preferably 30 ppm or less.
  • the premixing method is not particularly limited, and may be a batch method or a single-screw or biaxial or more kneading extruder. When producing MB while degassing, melt the polymer at a temperature of 250 ° C.
  • the polymer base material may contain a large number of fine cavities (voids) inside. Thereby, higher whiteness can be suitably obtained.
  • the apparent specific gravity is 0.7 or more and 1.3 or less, preferably 0.9 or more and 1.3 or less, more preferably 1.05 or more and 1.2 or less.
  • the apparent specific gravity is 0.7 or more, the polymer sheet has a waist and can be easily processed during the production of the solar cell module. If the apparent specific gravity is 1.3 or less, the mass of the polymer sheet is small, which can contribute to weight reduction of the solar cell.
  • the fine cavities can be formed from a thermoplastic resin that is incompatible with the fine particles and / or a polymer constituting the polymer substrate described later.
  • the term “cavity derived from a thermoplastic resin that is incompatible with the fine particles or polymer” means that there are voids around the fine particles or the thermoplastic resin. For example, it is confirmed by a cross-sectional photograph of the polymer substrate by an electron microscope. can do.
  • the resin that can be added to the polymer base material for forming a cavity is preferably a resin that is incompatible with the polymer constituting the polymer base material, which can scatter light and increase the light reflectance.
  • preferable incompatible resins include polyolefin resins such as polyethylene, polypropylene, polybutene, and polymethylpentene, polystyrene resins, polyacrylate resins, polycarbonate resins, and polyacrylonitrile resins. , Polyphenylene sulfide resin, polysulfone resin, cellulose resin, and fluorine resin. These incompatible resins may be homopolymers or copolymers, and two or more incompatible resins may be used in combination.
  • polyolefin resins and polystyrene resins such as polypropylene and polymethylpentene having a low surface tension are preferable, and polymethylpentene is more preferable. Since polymethylpentene has a relatively large difference in surface tension from polyester and a high melting point, it has a low affinity with polyester and easily forms voids (cavities) in the polyester film-forming process.
  • the amount thereof is 0% by mass to 30% by mass with respect to the entire polymer substrate, more preferably 1% by mass to 20% by mass, and still more preferably 2%.
  • the range is from mass% to 15 mass%.
  • the content is 30% by mass or less, the apparent density of the entire polymer base material can be secured, so that film breakage or the like hardly occurs during stretching, and good productivity can be obtained.
  • the average particle size of the fine particles is preferably 0.1 ⁇ m to 10 ⁇ m, more preferably 0.1 ⁇ m to 5 ⁇ m, and still more preferably 0.15 ⁇ m to 1 ⁇ m.
  • the content of the fine particles is 0 to 50% by mass, preferably 1 to 10% by mass, and more preferably 2 to 5% by mass with respect to the total mass of the polymer substrate. When the content is 50% by mass or less, a decrease in mechanical strength due to voids can be avoided.
  • the polymer constituting the polymer substrate is polyester, preferable fine particles include those having a low affinity with polyester, specifically, barium sulfate and the like.
  • the polymer substrate may be a single layer or may have a laminated structure of two or more layers.
  • a high whiteness a layer with a lot of voids and fine particles
  • a low whiteness layer a layer with a small amount of voids and fine particles.
  • the light reflection efficiency can be increased in a layer containing a large amount of voids or fine particles, a decrease in mechanical strength (embrittlement) is likely to occur due to voids or fine particles, and it is preferable to combine with a layer having low whiteness to compensate for this.
  • a layer with high whiteness for the outer layer of a polymer base material it is preferable to use a layer with high whiteness for the outer layer of a polymer base material, and it may be used for one side of a polymer base material, and may be used for both surfaces of a polymer base material.
  • a high white layer using titanium dioxide as fine particles is used as the outer layer of the polymer base material, titanium dioxide has a UV absorbing ability, so that the effect of improving the light resistance of the polymer base material can be obtained.
  • One suitable polymer base material is a polymer base material having a laminated structure including two or more layers having different contents of fine particles, which are inorganic particles or organic particles.
  • the content of fine particles is preferably 5% by mass or more and 50% by mass or less, and more preferably 6% by mass or more and 20% by mass or less with respect to the mass of the entire layer.
  • the apparent specific gravity of the high whiteness layer is preferably 0.7 or more and 1.2 or less, more preferably 0.8 or more and 1.1 or less.
  • the content of fine particles with respect to the mass of the entire layer is preferably 0% by mass or more and less than 5% by mass, more preferably 1% by mass or more and 4% by mass. % Or less is more preferable.
  • the low whiteness layer When the high whiteness layer is a layer formed by cavity formation, the low whiteness layer preferably has an apparent specific gravity of 0.9 or more and 1.4 or less and has a higher apparent specific gravity than the high white layer, and more preferably. Has an apparent specific gravity of 1.0 to 1.3 and higher than that of the high white layer.
  • the low white layer may not contain fine particles or cavities.
  • the white polymer substrate may have, a high white layer / low white layer, a high white layer / low white layer / high white layer, a high white layer / low white layer / high white layer / low white layer, high Examples include white layer / low white layer / high white layer / low white layer / high white layer.
  • the thickness ratio of each layer in the laminated structure is not particularly limited, but the thickness of each layer is preferably 1% or more and 99% or less, more preferably 2% or more and 95% or less of the total layer thickness. Within this range, it is easy to obtain the effects of improving the reflection efficiency and imparting light resistance (UV).
  • the thickness of all layers of the polymer substrate is not particularly limited as long as it can be formed as a film, but is usually in the range of 20 ⁇ m to 500 ⁇ m, preferably 25 ⁇ m to 300 ⁇ m.
  • a so-called coextrusion method using two or three or more melt extruders is preferably used as a laminating method for producing a polymer substrate having a laminating structure.
  • a fluorescent brightener such as thiofediyl to increase the whiteness of the white polymer substrate.
  • a preferable addition amount is 0.01% by mass or more and 1% by mass or less, more preferably 0.05% by mass or more and 0.5% by mass or less, and further preferably 0.1% by mass with respect to the total mass of the white polymer substrate. % Or more and 0.3% by mass or less. If it is 0.01% by mass or more, the effect of improving the light reflectivity is easily obtained, and if it is 1% by mass or less, it is possible to avoid a decrease in reflectance due to yellowing due to thermal decomposition during extrusion.
  • a fluorescent whitening agent for example, OB-1 (trade name) manufactured by Eastman Kodak Co., Ltd. can be used.
  • the white polymer substrate has an illuminance of 100 mW / cm 2, a temperature of 60 ° C., a relative humidity of 50% RH, an irradiation time of 48 hours, and a yellowish change amount ( ⁇ b value) after 5 hours of ultraviolet irradiation. It is preferable that it is less than.
  • the ⁇ b value is more preferably less than 4 and even more preferably less than 3. This is useful in that the color change can be reduced even if it is irradiated with sunlight for a long time. Such an effect is prominent in a solar battery module in which a polymer sheet is laminated on a solar battery cell as a back sheet, particularly when irradiated from the polymer sheet side.
  • the polymer substrate is preferably in a form in which surface treatment is performed by corona treatment, flame treatment, low-pressure plasma treatment, atmospheric pressure plasma treatment, or ultraviolet treatment.
  • corona treatment By performing these surface treatments, it is possible to further improve the adhesion (adhesiveness) when exposed to a humid heat environment.
  • corona treatment a more excellent adhesive improvement effect can be obtained.
  • These surface treatments can increase adhesion by increasing carboxyl groups and hydroxyl groups on the surface of polymer substrates (for example, polyester substrates).
  • crosslinking agents especially oxazoline or carbodiimide compounds that are highly reactive with carboxyl groups
  • stronger adhesiveness can be obtained. This is more remarkable in the case of corona treatment.
  • Corona treatment is usually performed by applying high frequency and high voltage between a metal roll (dielectric roll) coated with a derivative and an insulated electrode to cause dielectric breakdown of the air between the electrodes. Is ionized to generate a corona discharge between the electrodes. And it performs by passing a polymer base material between this corona discharge.
  • the corona treatment conditions are preferably a gap clearance of 1 to 3 mm between the electrode and the dielectric roll, a frequency of 1 to 100 kHz, and an applied energy of about 0.2 to 5 kV ⁇ A ⁇ min / m 2. .
  • the polymer sheet for solar cells of the present invention has a first polymer layer containing at least one binder polymer selected from a fluoropolymer and a silicone polymer.
  • the first polymer layer is a layer that can function as a weather-resistant layer.
  • the first polymer layer contains at least one binder polymer selected from a fluoropolymer and a silicone polymer (hereinafter sometimes referred to as “specific binder” as appropriate).
  • the specific binder is contained as a main binder.
  • the main binder in the first polymer layer is a binder having the largest content in the first polymer layer.
  • the fluoropolymer and the silicone polymer may be used alone or in combination of two or more. Moreover, when using together a fluoropolymer and a silicone polymer, you may select and use together 2 or more types of polymers from any one of a fluoropolymer and a silicone polymer, or it is 1 type from both a fluoropolymer and a silicone polymer. Or you may select 2 or more types and use together.
  • the fluoropolymer that can be contained as the specific binder in the first polymer layer is not particularly limited as long as it is a polymer having a repeating unit represented by-(CFX1-CX2X3)-(however, X1, X2, and X3 are A hydrogen atom, a fluorine atom, a chlorine atom, or a perfluoroalkyl group having 1 to 3 carbon atoms).
  • fluoropolymers examples include polytetrafluoroethylene (hereinafter sometimes referred to as PTFE), polyvinyl fluoride (hereinafter sometimes referred to as PVF), and polyvinylidene fluoride (hereinafter referred to as PVDF). ), Polychloroethylene trifluoride (hereinafter sometimes referred to as PCTFE), polytetrafluoropropylene (hereinafter sometimes referred to as HFP), and the like.
  • PTFE polytetrafluoroethylene
  • PVF polyvinyl fluoride
  • PVDF polyvinylidene fluoride
  • PCTFE Polychloroethylene trifluoride
  • HFP polytetrafluoropropylene
  • These fluoropolymers may be a homopolymer obtained by polymerizing a single monomer, or may be a copolymer obtained by copolymerizing two or more kinds. Examples thereof include a copolymer of tetrafluoroethylene and tetrafluoropropylene (abbreviated as P (TFE / HFP)), a copolymer of tetrafluoroethylene and vinylidene fluoride (abbreviated as P (TFE / VDF)), etc. Can be mentioned.
  • the specific binder used in the first polymer layer may be a polymer obtained by copolymerizing a fluorocarbon monomer represented by-(CFX1-CX2X3)-and another monomer (non-fluorine-containing monomer).
  • fluorocarbon monomers include ethylene tetrafluoride, ethylene trifluoride, vinylidene fluoride, vinyl fluoride, hexafluoropropylene, fluorine-containing alkyl vinyl ethers (eg, perfluoroethyl vinyl ether), fluorine-containing esters. Etc. (perfluorobutyl methacrylate, etc.).
  • non-fluorine-containing monomer examples include ethylene, alkyl vinyl ether (eg, ethyl vinyl ether, cyclohexyl vinyl ether), and carboxylic acid (eg, acrylic acid, methacrylic acid, hydroxybutyme vinyl ether, etc.).
  • the fluoropolymer is a polymer obtained by copolymerizing a fluorocarbon monomer and a non-fluorine-containing monomer
  • the content of the fluorine-containing monomer with respect to the total mass of the fluoropolymer is preferably 30% by mass to 98% by mass, The amount is preferably 40 to 80% by mass.
  • the proportion of the fluorine-containing monomer is 30% by mass or more. Further, from the viewpoint of polymerization stability, it is preferably 98% by mass or less.
  • Examples of polymers obtained by copolymerization of fluorocarbon monomers and non-fluorine-containing monomers are copolymers of tetrafluoroethylene and ethylene (abbreviated as P (TFE / E)), copolymer of tetrafluoroethylene and propylene.
  • Copolymer (abbreviated as P (TFE / P)), copolymer of tetrafluoroethylene and vinyl ether (abbreviated as P (TFE / VE)), copolymer of tetrafluoroethylene and perfluorovinyl ether (P (TFE / FVE)) Abbreviation), a copolymer of chlorotrifluoroethylene and vinyl ether (abbreviated as P (CTFE / VE)), a copolymer of chlorotrifluoroethylene and perfluorovinyl ether (abbreviated as P (CTFE / FVE)), tetrafluoro Hexafluoropropylene, a copolymer obtained by copolymerizing ethylene, ethylene and acrylic acid Copolymer formed by copolymerizing tetrafluoroethylene, copolymer formed by copolymerizing hexafluoropropylene, tetrafluoroethylene and
  • a copolymer a copolymer formed by copolymerizing chlorotrifluoroethylene, perfluoroethyl vinyl ether and methacrylic acid, a copolymer formed by copolymerizing chlorotrifluoroethylene and ethyl vinyl ether, and chlorotrifluoroethylene Copolymers of ethyl vinyl ether and methacrylic acid, copolymers of vinylidene fluoride, methyl methacrylate and methacrylic acid, vinyl fluoride, ethyl acrylate and acrylic acid. And the like.
  • a copolymer obtained by copolymerizing chlorotrifluoroethylene and perfluoroethyl vinyl ether a copolymer obtained by copolymerizing chlorotrifluoroethylene, perfluoroethyl vinyl ether and methacrylic acid
  • chlorotrifluoro Copolymer made by copolymerizing ethylene and ethyl vinyl ether Copolymer made by copolymerizing chlorotrifluoroethylene, ethyl vinyl ether and methacrylic acid
  • a copolymer obtained by copolymerizing vinyl fluoride, ethyl acrylate and acrylic acid a copolymer obtained by copolymerizing vinyl fluoride, ethyl acrylate and acrylic acid.
  • a copolymer obtained by copolymerizing chlorotrifluoroethylene and ethyl vinyl ether and a copolymer obtained by copolymerizing chlorotrifluoroethylene, ethyl vinyl ether and methacrylic acid are more preferable.
  • fluoropolymers may be used by dissolving the polymer in an organic solvent or by dispersing polymer fine particles in water. The latter is preferred because of its low environmental impact.
  • water dispersions of fluoropolymers are described in, for example, JP-A Nos. 2003-231722, 2002-20409, and No. 9-194538.
  • the molecular weight of the fluorine-based polymer can be about 2000 to 1000000 in terms of polystyrene-converted weight average molecular weight, and preferably about 3000 to 300000.
  • the silicone polymer that can be contained in the first polymer layer is a polymer having a (poly) siloxane structure in the molecule.
  • the “siloxane structure” means a structure containing at least one siloxane bond.
  • Polysiloxane structure means a structure in which a plurality of siloxane bonds are continuous.
  • the term “(poly) siloxane structure” encompasses siloxane structures and polysiloxane structures within its scope.
  • the expressions “the polymer has a siloxane structure in the molecule” and “the polymer has a (poly) siloxane structure in the molecule” mean that the polymer contains a siloxane structure or a polysiloxane structure in the molecule.
  • the silicone polymer has a (poly) siloxane structural unit represented by the following general formula (1) as a (poly) siloxane structure, as a (poly) siloxane structure.
  • R1 and R2 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.
  • R1 and R2 may be the same or different, and the plurality of R1 and R2 may be the same or different from each other.
  • n represents an integer of 1 or more.
  • R1 and R2 May be the same or different and each represents a hydrogen atom, a halogen atom, or a monovalent organic group.
  • n- is a (poly) siloxane segment derived from various (poly) siloxanes having a linear, branched or cyclic structure.
  • halogen atom represented by R1 and R2 examples include a fluorine atom, a chlorine atom, and an iodine atom.
  • the “monovalent organic group” represented by R1 and R2 is a group that can be covalently bonded to the Si atom, and may be unsubstituted or may have a substituent.
  • Examples of the monovalent organic group include an alkyl group (e.g., methyl group, ethyl group), an aryl group (e.g., phenyl group), an aralkyl group (e.g., benzyl group, phenylethyl), and an alkoxy group (e.g.
  • Methoxy group, ethoxy group, propoxy group, etc. Methoxy group, ethoxy group, propoxy group, etc.), aryloxy group (eg, phenoxy group etc.), mercapto group, amino group (eg: amino group, diethylamino group etc.), amide group and the like.
  • R1 and R2 are each independently a hydrogen atom, a chlorine atom, a bromine atom, an unsubstituted or substituted carbon number of 1 to 4 in terms of adhesion to an adjacent layer and durability in a wet heat environment.
  • the n is preferably 1 to 5000, and more preferably 1 to 1000.
  • — (Si (R1) (R2) —O) n—” ((poly) siloxane structural unit represented by the general formula (1)) in the silicone polymer
  • hydrolysis of dimethyldimethoxysilane Containing hydrolyzed condensate containing condensate, hydrolyzed condensate containing hydrolyzed condensate of dimethyldimethoxysilane / ⁇ -methacryloxytrimethoxysilane, hydrolyzed condensate of dimethyldimethoxysilane / vinyltrimethoxysilane Hydrolysis condensate, hydrolysis condensate containing dimethyldimethoxysilane / 2-hydroxyethyltrimethoxysilane hydrolysis condensate, dimethyldimethoxysilane / 3-glycidoxypropyltriethoxysilane hydrolyzed condensate Hydrolysis condensate, dimethyldimethoxysilane / dipheny
  • hydrolyzed condensate containing hydrolyzed condensate of dimethyldimethoxysilane / ⁇ -methacryloxytrimethoxysilane hydrolyzed condensate of dimethyldimethoxysilane / diphenyl / dimethoxysilane ⁇ -methacryloxytrimethoxysilane Hydrolysis condensates are preferred.
  • the ratio of “— (Si (R1) (R2) —O) n—” (the (poly) siloxane structural unit represented by the general formula (1)) in the polymer is based on the total mass of the polymer. It is preferably 15 to 85% by mass.
  • the strength of the surface of the first polymer layer is improved, the occurrence of scratches due to scratching, scratching, etc. is prevented, and adhesion with an adjacent layer and durability in a humid heat environment are also achieved. From the standpoint of superiority, the range of 20 to 80% by mass is more preferable. When the ratio of the (poly) siloxane structural unit is 15% by mass or more, the strength of the surface of the first polymer layer is improved, and scratches caused by scratches, scratches, collisions of flying pebbles, etc. can be prevented, Moreover, it can be excellent in adhesiveness with adjacent materials such as the second polymer layer.
  • the mass of the (poly) siloxane structural unit represented by the general formula (1) in the molecular chain is as follows. It preferably contains 15 to 85% by mass in proportion and 85 to 15% by mass of non-siloxane structural units in mass proportion.
  • the silicone polymer is a copolymer having a (poly) siloxane structural unit and another structural unit, a moiety of “— (Si (R1) (R2) —O) n—” in the silicone polymer (general formula
  • the molecular weight of the (poly) siloxane structural unit represented by (1) is about 30,000 to 1,000,000, preferably about 50,000 to 300,000 in terms of polystyrene-converted weight average molecular weight.
  • a siloxane compound including polysiloxane in its range
  • a compound selected from a non-siloxane monomer or a non-siloxane polymer are copolymerized and represented by the general formula (1)
  • a block copolymer having a poly) siloxane structural unit and a non-siloxane structural unit is preferred.
  • the siloxane compound and the non-siloxane monomer or non-siloxane polymer to be copolymerized may be one kind alone or two or more kinds.
  • the non-siloxane structural unit copolymerized with the (poly) siloxane structural unit (derived from the non-siloxane monomer or non-siloxane polymer) is not particularly limited except that it does not have a siloxane structure, and is arbitrary. Any of the polymer segments derived from the polymer may be used. Examples of the polymer (precursor polymer) that is a precursor of the polymer segment include various polymers such as a vinyl polymer, a polyester polymer, and a polyurethane polymer. Among these, vinyl polymers and polyurethane polymers are preferable, and vinyl polymers are particularly preferable because they are easy to prepare and have excellent hydrolysis resistance.
  • the vinyl polymer include various polymers such as an acrylic polymer, a carboxylic acid vinyl ester polymer, an aromatic vinyl polymer, and a fluoroolefin polymer.
  • an acrylic polymer is particularly preferable from the viewpoint of design flexibility.
  • Monomers constituting the acrylic polymer include acrylic acid esters (eg, ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate, etc.) or methacrylic acid esters (eg, methyl methacrylate, butyl methacrylate, hydroxyethyl acrylate).
  • examples of monomers include carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid, styrene, acrylonitrile, vinyl acetate, acrylamide, and divinylbenzene.
  • carboxylic acids such as acrylic acid, methacrylic acid, and itaconic acid
  • styrene acrylonitrile
  • vinyl acetate vinyl acetate
  • acrylamide divinylbenzene.
  • Butyl methacrylate, hydroxyethyl acrylate, acrylic acid or methacrylic acid are preferred.
  • acrylic polymer examples include methyl methacrylate / ethyl acrylate / acrylic acid copolymer, methyl methacrylate / ethyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid copolymer, methyl methacrylate / butyl acrylate / 2- Examples thereof include a bidoxyethyl methacrylate / methacrylic acid / ⁇ -methacryloxytrimethoxysilane copolymer or a methyl methacrylate / ethyl acrylate / glycidyl methacrylate / acrylic acid copolymer.
  • the polymer constituting the non-siloxane structural unit may be used alone or in combination of two or more. Furthermore, the individual polymers may be homopolymers or copolymers.
  • the molecular weight of the polymer that is a precursor of the polymer segment constituting the non-siloxane structural unit is about 3000 to 1000000 in terms of polystyrene-converted weight average molecular weight, and more preferably about 5000 to 300000.
  • the precursor polymer constituting the non-siloxane structural unit preferably contains at least one of an acid group and a neutralized acid group and / or a hydrolyzable silyl group.
  • the vinyl polymer includes, for example, (a) a vinyl monomer containing an acid group and a vinyl monomer containing a hydrolyzable silyl group and / or a silanol group.
  • the precursor polymer can be produced and obtained using, for example, the method described in paragraph Nos. 0021 to 0078 of JP-A-2009-52011.
  • the silicone polymer may be used alone or in combination with other polymers.
  • the content ratio of the polymer containing the (poly) siloxane structure in the present invention is preferably 30% by mass or more, more preferably 60% by mass or more of the total binder amount.
  • the content ratio of the polymer containing the (poly) siloxane structure is 30% by mass or more, thereby improving the strength of the surface of the layer, preventing the occurrence of scratches due to scratching or scratching, and adhesion to the polymer substrate. In addition, it is more excellent in durability under humid heat environment.
  • the molecular weight of the silicone polymer is preferably 5,000 to 100,000, and more preferably 10,000 to 50,000.
  • a method such as a method of hydrolyzing and condensing a silane compound having the structural unit represented by the general formula (1) in which R2 is a hydrolyzable group can be used.
  • the silane compound used in the method (ii) include various silane compounds, and alkoxysilane compounds are particularly preferable.
  • the silicone polymer by the method (i) for example, water and a catalyst are added to the mixture of the precursor polymer and the polysiloxane as necessary, and the temperature is about 20 to 150 ° C. for about 30 minutes to 30 hours ( (Preferably, the reaction can be performed at 50 to 130 ° C. for 1 to 20 hours).
  • various silanol condensation catalysts such as an acidic compound, a basic compound, and a metal containing compound, can be added.
  • water and a silanol condensation catalyst are added to a mixture of a precursor polymer and an alkoxysilane compound, and a temperature of about 20 to 150 ° C. for 30 minutes to 30 minutes. It can be prepared by performing hydrolysis condensation for about an hour (preferably at 50 to 130 ° C. for 1 to 20 hours).
  • silicone polymer examples include a hydrolysis condensate in which the (poly) siloxane structural unit contains a hydrolysis condensate of dimethyldimethoxysilane / ⁇ -methacryloxytrimethoxysilane, dimethyldimethoxysilane / diphenyl / dimethoxysilane ⁇ -methacrylate.
  • the polymer structure part copolymerized with the (poly) siloxane structural unit is ethyl acrylate, butyl acrylate, hydroxyethyl acrylate, 2-ethylhexyl acrylate methyl methacrylate, methyl methacrylate, butyl More preferable examples include composite polymers that are acrylic polymers composed of monomer components selected from methacrylate, hydroxyethyl acrylate, acrylic acid, and methacrylic acid.
  • a hydrolysis condensate containing a hydrolysis condensate of dimethyldimethoxysilane / ⁇ -methacryloxytrimethoxysilane and a monomer component selected from methyl methacrylate, ethyl acrylate, acrylic acid, and methacrylic acid.
  • the composite polymer which is an acrylic polymer is mentioned.
  • silicone polymer for example, SERATE series produced by DIC Corporation [eg, SERATE WSA1070 (polysiloxane structural unit content ratio: 30% by mass acrylic / silicone Resin, WSA 1060 (polysiloxane structural unit content ratio: 75 mass%), etc.], Asahi Kasei Chemicals H7600 series (H7650, H7630, H7620 etc.), JSR Co., Ltd. inorganic / acrylic composite An emulsion or the like can be used.
  • SERATE series produced by DIC Corporation
  • SERATE WSA1070 polysiloxane structural unit content ratio: 30% by mass acrylic / silicone Resin
  • WSA 1060 polysiloxane structural unit content ratio: 75 mass%), etc.
  • Asahi Kasei Chemicals H7600 series H7650, H7630, H7620 etc.
  • JSR Co., Ltd. inorganic / acrylic composite An emulsion or the like can be used.
  • binder polymers other than specific binders such as an acrylic resin, a polyester resin, a polyurethane resin, and a polyolefin resin, in the range which does not exceed 50 mass% of all the binders in a 1st polymer layer.
  • the total content of the binder polymer including the specific binder in the first polymer layer is preferably 60 to 95% by mass, more preferably 75 to 95% by mass, and particularly preferably 80 to 93% by mass.
  • the 1st polymer layer in this invention has the structure part derived from the crosslinking agent which bridge
  • crosslinking agent capable of crosslinking between the binder polymers.
  • a compound having an oxazoline group is preferable.
  • the compound having an oxazoline group include 2-vinyl-2-oxazoline, 2-vinyl-4-methyl-2-oxazoline, 2-vinyl-5-methyl-2-oxazoline, 2-isopropenyl-2- Oxazoline, 2-isopropenyl-4-oxazoline, 2-isopropenyl-4-methyl-2-oxazoline, 2-isopropenyl-5-ethyl-2-oxazoline, 2,2′-bis- (2-oxazoline), 2,2'-methylene-bis- (2-oxazoline), 2,2'-ethylene-bis- (2-oxazoline), 2,2'-trimethylene-bis- (2-oxazoline), 2,2'- Tetramethylene-bis- (2-oxazoline), 2,2′-hexamethylene-bis- (2-oxazoline), 2,2′-octamethylene-bis
  • the compound having an oxazoline group as a copolymer include a copolymer of 2-isopropenyl-2-oxazoline, methoxypolyethylene glycol methacrylate and methyl acrylate, 2-isopropenyl-2-oxazoline, Copolymer composed of methoxypolyethylene glycol methacrylate and methyl methacrylate, copolymer composed of 2-isopropenyl-2-oxazoline, methoxypolyethylene glycol methacrylate and ethyl acrylate, 2-isopropenyl-2-oxazoline
  • a copolymer comprising monoesterified product of methacrylic acid and polyethylene glycol and methyl methacrylate, 2-isopropenyl-4-oxazoline, methoxypolyethylene glycol methacrylate and methyl methacrylate Copolymers mention may be made of a copolymer comprising 2-isopropenyl-4-oxazoline and acrylic acid me
  • Epocros K2010E, K2020E, K2030E, WS-500, WS-700 can be used as commercially available compounds having an oxazoline group.
  • the compound having an oxazoline group in the first polymer layer may be only one type, or two or more types may be used in combination.
  • an epoxy-based, isocyanate-based, melamine-based, or carbodiimide-based crosslinking agent may be used in combination as long as the effects of the present invention are not impaired.
  • the first polymer layer includes a cross-linked structure by a cross-linking agent
  • 0.5 to 50% by mass of a cross-linking agent-derived structural portion is included with respect to the specific binder contained in the first polymer layer. It is more preferable to include a structural part derived from 30% by mass of the crosslinking agent, and it is particularly preferable to include a structural part derived from 5 to 20% by mass of the crosslinking agent.
  • the addition amount of the crosslinking agent is 0.5% by mass or more, a sufficient crosslinking effect is obtained while maintaining the strength and adhesiveness of the first polymer layer, and when it is 50% by mass or less, Long pot life.
  • the first polymer layer preferably contains an onium compound from the viewpoint of improving solvent resistance.
  • onium compounds examples include ammonium salts, sulfonium salts, oxonium salts, iodonium salts, phosphonium salts, nitronium salts, nitrosonium salts, diazonium salts, and the like.
  • the onium compound include, for example, monoammonium phosphate, diammonium phosphate, ammonium chloride, ammonium sulfate, ammonium nitrate, ammonium p-toluenesulfonate, ammonium sulfamate, ammonium imidodisulfonate, tetrabutylammonium chloride, benzyl chloride Ammonium salts such as trimethylammonium chloride, triethylbenzylammonium chloride, tetrabutylammonium tetrafluoride, tetrabutylammonium hexafluoride, tetrabutylammonium perchlorate, tetrabutylammonium sulfate; trimethylsulfonium iodide, trimethyl boron tetrafluoride Sulfonium, boron tetrafluoride diphenylmethylsulf
  • Only one kind of onium compound in the first polymer layer may be used, or two or more kinds may be used in combination.
  • the content of the onium compound in the first polymer layer is preferably 0.5% by mass to 10% by mass with respect to the total amount of the binder polymer contained in the first polymer layer, and 1% by mass to 5% by mass. % Is more preferable.
  • the first polymer layer may contain at least one water-miscible organic solvent having a boiling point of 99 ° C. or lower.
  • the organic solvent having a low boiling point By containing the organic solvent having a low boiling point, the crosslinking reaction between the polymer containing the specific binder contained in the first polymer layer and the compound having an oxazoline group is promoted, and the solvent resistance is further improved.
  • Water-miscible means having water solubility, and is a property to be arbitrarily mixed with water.
  • a boiling point of 99 ° C. or lower means that it is easier to remove than water, which is the main solvent in a coating solution that is suitably prepared as an aqueous coating solution, and a solvent component that is more easily removed from the system than water. It is estimated that the cross-linking reaction is improved by inclusion.
  • the water-miscible organic solvent having a boiling point of 99 ° C. or lower is not particularly limited except for the boiling point.
  • alcohol solvents monohydric alcohols and dihydric or higher polyhydric alcohols
  • ketone solvents ketone solvents
  • ether solvents A solvent an ester solvent, etc.
  • an ester solvent etc.
  • Examples of the alcohol solvent include methyl alcohol (bp: 65 ° C.), ethyl alcohol (bp: 78 ° C.), n-propyl alcohol (bp: 97 ° C.), i-propyl alcohol (bp: 82 ° C.), t -Butyl alcohol (bp: 82 ° C.) and the like, and monovalent alcohols having 1 to 3 carbon atoms are preferred.
  • the ketone solvent include ketone compounds having 3 to 5 carbon atoms such as acetone (bp: 56 ° C.), methyl ethyl ketone (bp: 80 ° C.), 2-butanone (bp: 79.5 ° C.), and the like. .
  • ether solvent examples include diethyl ether (bp: 35 ° C.), tetrahydrofuran (bp: 66 ° C.), and the like.
  • ester solvent examples include ethyl acetate (bp: 70 ° C.) and isopropyl acetate (bp: 88-91 ° C.). The “bp” indicates a boiling point.
  • the water-miscible organic solvent is a monohydric alcohol having 1 to 3 carbon atoms and 3 to 3 carbon atoms from the viewpoint of improving the cross-linking reactivity between the polymer and the oxazoline-based cross-linking agent, and hence the solvent resistance.
  • a solvent selected from 5 ketone compounds is preferable, and methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, or acetone is more preferable.
  • the first polymer layer contains a water-miscible organic solvent having a boiling point of 99 ° C. or less, only one type may be used, or two or more types may be used in combination.
  • the content of the water-miscible organic solvent contained in the polymer layer is the total of the binder polymer including the specific binder contained in the first polymer layer. 0.0001 mass% to 30 mass% is preferable with respect to the mass, and 0.1 to 5 mass% is more preferable. Since water-miscible organic solvents are volatilized, the storage environment is preferably within a closed container at room temperature for one week.
  • a surfactant In the first polymer layer, a surfactant, a filler or the like may be further added as necessary.
  • the surfactant that can be used for the first polymer layer a known surfactant such as an anionic or nonionic surfactant can be used.
  • the addition amount is preferably 0.1 to 15 mg / m2, more preferably 0.5 to 5 mg / m2.
  • the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of repellency is suppressed and good layer formation is obtained, and when it is 15 mg / m 2 or less, adhesion can be performed satisfactorily.
  • a filler may be further added to the first polymer layer.
  • Known fillers such as colloidal silica and titanium dioxide can be used as the filler.
  • the addition amount of the filler is preferably 20% by mass or less, more preferably 15% by mass or less, with respect to the binder contained in the first polymer layer. When the addition amount of the filler is 20% by mass or less, the planar shape of the first polymer layer can be kept better.
  • the thickness of the first polymer layer in the present invention is preferably in the range of 0.8 ⁇ m to 12 ⁇ m, particularly preferably in the range of about 1.0 ⁇ m to 10 ⁇ m.
  • the first polymer layer is preferably the outermost layer of the polymer sheet for solar cells of the present invention.
  • the polymer sheet for solar cells of the present invention includes at least one binder polymer selected from a fluoropolymer and a silicone polymer, and a structural portion derived from a crosslinking agent having an oxazoline group that crosslinks the binder polymer, and It has the 2nd polymer layer whose equivalent [meq / g] of the said oxazoline group with respect to a binder polymer is more than 0 and less than 1.
  • the second polymer layer is a layer that can function as a weather-resistant layer together with the first polymer layer.
  • the second polymer layer can be formed using other components depending on the case, and the components differ depending on the application.
  • the first polymer layer can constitute an undercoat layer, a colored layer that bears the function of reflecting sunlight, imparting appearance design, and the like.
  • the second polymer layer may be, for example, a layer that improves the adhesion between the polymer substrate and the first polymer layer, that is, a layer that functions as a so-called undercoat layer.
  • the second polymer layer can be configured as a reflective layer that reflects sunlight toward the incident side, for example.
  • the second polymer layer can be constituted by further using a colorant such as a white pigment.
  • the second polymer layer includes at least one binder polymer selected from a fluoropolymer and a silicone polymer.
  • the at least one binder polymer selected from the fluoropolymer and silicone polymer contained in the second polymer layer is synonymous with the specific binder contained in the first polymer layer as the main binder, and the details thereof are also the same. .
  • the details of the content of the specific binder polymer are the same as in the case of the first polymer layer except that the “first polymer layer” is replaced with “second polymer layer”.
  • the same specific binder that can be contained in the first polymer layer can be suitably applied.
  • the specific binder contained in the second polymer layer may be the same as or different from the specific binder contained in the first polymer layer.
  • the total content of the binder polymer including the specific binder in the second polymer layer is preferably 60 to 95% by mass, more preferably 75 to 95% by mass, and particularly preferably 80 to 93% by mass.
  • the 2nd polymer layer in this invention has the structure part derived from the crosslinking agent which bridge
  • a compound having an oxazoline group is applied to the second polymer layer as a crosslinking agent.
  • the compound having an oxazoline group in the second polymer layer the same compound as the compound having an oxazoline group in the first polymer layer can be suitably applied.
  • Only one type of compound having an oxazoline group in the second polymer layer may be used, or two or more types may be used in combination.
  • the equivalent [meq / g] of the oxazoline group to the specific binder in the second polymer layer is more than 0 and less than 1, and preferably 0.45 or more and less than 1.
  • the equivalent [meq / g] of the oxazoline group to the specific binder is in the above range, the adhesion between the polymer substrate and the polymer layer provided thereon can be specifically improved.
  • an epoxy-based, isocyanate-based, melamine-based, or carbodiimide-based crosslinking agent may be used in combination as long as the effects of the present invention are not impaired.
  • the second polymer layer preferably includes a structural part derived from a crosslinking agent in an amount of 0.5 to 50% by mass based on the specific binder (main binder) of the second polymer layer. More preferably, it contains a structural part derived from an agent, and particularly preferably contains a structural part derived from 5 to 20% by mass of a crosslinking agent.
  • a crosslinking agent 0.5% by mass or more with respect to the specific binder (main binder) of the second polymer layer, sufficient crosslinking is performed while maintaining the strength and adhesiveness of the second polymer layer. An effect is acquired and the pot life of a coating liquid can be kept long as it is 50 mass% or less.
  • the second polymer layer preferably contains an onium compound from the viewpoint of improving solvent resistance.
  • Examples of the onium compound that can be applied to the second polymer layer include the same onium compounds that can be applied to the first polymer layer.
  • Only one kind of onium compound in the second polymer layer may be used, or two or more kinds may be used in combination.
  • the content of the onium compound in the second polymer layer is preferably 0.5% by mass to 10% by mass with respect to the total amount of the binder polymer contained in the second polymer layer, and 1% by mass to 5% by mass. % Is more preferable.
  • the second polymer layer may contain at least one water-miscible organic solvent having a boiling point of 99 ° C. or lower.
  • the water-miscible organic solvent having a boiling point of 99 ° C. or less that can be contained in the second polymer layer is synonymous with the water-miscible organic solvent having a boiling point of 99 ° C. or less that can be contained in the first polymer layer. Is the same.
  • the details of the content of the water-miscible organic solvent having a boiling point of 99 ° C. or lower are the same as in the case of the first polymer layer except that “first polymer layer” is read as “second polymer layer”.
  • Specific examples of the water-miscible organic solvent having a boiling point of 99 ° C. or lower are preferably the same as the specific binder that can be contained in the first polymer layer.
  • the water-miscible organic solvent having a boiling point of 99 ° C. or less contained in the second polymer layer may be the same as or different from the specific binder contained in the first polymer layer.
  • surfactant a known surfactant such as an anionic or nonionic surfactant can be used.
  • the amount added is preferably 0.1 to 10 mg / m 2, more preferably 0.5 to 3 mg / m 2.
  • the addition amount of the surfactant is 0.1 mg / m 2 or more, generation of a repellency is suppressed and good layer formation is obtained, and when it is 10 mg / m 2 or less, the polymer substrate and the first polymer layer, etc. Adhesion with other layers can be performed satisfactorily.
  • a filler may be further added to the second polymer layer.
  • Known fillers such as colloidal silica and titanium dioxide can be used as the filler.
  • the addition amount of the filler is preferably 20% by mass or less, more preferably 15% by mass or less per binder contained in the second polymer layer. When the addition amount of the filler is 20% by mass or less, the planar shape of the second polymer layer can be kept better.
  • the thickness of the second polymer layer is preferably 0.05 ⁇ m to 10 ⁇ m. If the thickness of the second polymer layer is 0.05 ⁇ m or more, the durability is sufficient, and a sufficient adhesive force between the polymer substrate and the first polymer layer can be secured. On the other hand, when the thickness of the second polymer layer is 10 ⁇ m or less, the surface shape is hardly deteriorated, and the adhesive force with other layers such as the first polymer layer is sufficient. When the thickness of the second polymer layer is in the range of 0.05 ⁇ m to 10 ⁇ m, both the durability and the surface shape of the second polymer layer are compatible, and the adhesion between the polymer substrate and the first polymer layer is improved. In particular, a range of about 1.0 ⁇ m to 10 ⁇ m is preferable.
  • the first and second polymer layers in the present invention are a back layer (weather-resistant layer).
  • the back layer is supported. It is the back surface protective layer distribute
  • the first and second polymer layers contain a specific binder, adhesion to the polymer substrate and adhesion between the polymer layers are improved, and further, deterioration resistance in a humid heat environment is obtained. . Therefore, the form in which the first polymer layer in the present invention is disposed as the outermost layer farthest from the polymer substrate is preferable.
  • pigments used in the colored layer may include pigments used in the colored layer in addition to the surfactants and fillers described above. Details of these other components and pigments and preferred embodiments will be described later.
  • the first polymer layer in the present invention may be a colored layer (preferably a reflective layer). In this case, the first polymer layer further contains a pigment.
  • the second polymer layer may be a colored layer (preferably a reflective layer). In this case, the second polymer layer further contains a pigment.
  • the colored layer may further include other components such as various additives as necessary.
  • the case where the first polymer layer is a colored layer may be referred to as a first colored layer
  • the case where the second polymer layer is a colored layer may be referred to as a second colored layer. Only one of the first polymer layer and the second polymer layer may be a colored layer, or both may be colored layers. The following description is common to the first and second colored layers.
  • the colored layer As a function of the colored layer, first, by reflecting the light that has passed through the solar cells and reaches the back sheet without being used for power generation out of the incident light, and returns the solar cells to the solar cells, Increasing the power generation efficiency, secondly, improving the decorativeness of the appearance when the solar cell module is viewed from the side on which sunlight enters (front side), and the like.
  • a back sheet can be seen around the solar cell, and by providing a colored layer on the back sheet, the decorativeness can be improved and the appearance can be improved.
  • the colored layer in the present invention can contain at least one pigment.
  • the pigment include inorganic pigments such as titanium dioxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc, ultramarine blue, bitumen, and carbon black, and organic pigments such as phthalocyanine blue and phthalocyanine green. It can be appropriately selected and contained.
  • a white pigment when the polymer layer is formed as a reflective layer that reflects light that has entered the solar cell and passed through the solar cell and returns it to the solar cell, a white pigment is preferable.
  • the white pigment titanium dioxide, barium sulfate, silicon oxide, aluminum oxide, magnesium oxide, calcium carbonate, kaolin, talc and the like are preferable.
  • the content of the pigment in the colored layer is preferably in the range of 2.5 g / m 2 to 8.5 g / m 2.
  • the pigment content is 2.5 g / m 2 or more, necessary coloring can be obtained, and reflectance and decorative properties can be effectively provided.
  • the content of the pigment in the colored layer is 8.5 g / m 2 or less, the surface state of the colored layer is easily maintained, and the film strength is excellent.
  • the pigment content is more preferably in the range of 4.5 g / m 2 to 8.0 g / m 2.
  • the average particle diameter of the pigment is preferably 0.03 ⁇ m to 0.8 ⁇ m in volume average particle diameter, more preferably about 0.15 ⁇ m to 0.5 ⁇ m. When the average particle size is within the above range, the light reflection efficiency is high.
  • the average particle diameter is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
  • the content of the binder component (including the specific binder) is preferably in the range of 15 to 200% by mass, preferably 17 to 100% by mass with respect to the pigment. % Range is more preferred.
  • the content of the binder is 15% by mass or more, the strength of the colored layer is sufficiently obtained, and when it is 200% by mass or less, the reflectance and the decorativeness can be kept good.
  • the light reflectance at 550 nm on the surface on which the colored layer and the easy-adhesion layer described later are provided is preferably 75% or more.
  • the light reflectivity is the ratio of the amount of light incident from the surface of the easy-adhesion layer to the amount of incident light reflected from the reflection layer and emitted again from the easy-adhesion layer.
  • light having a wavelength of 550 nm is used as the representative wavelength light.
  • the light reflectance can be adjusted to 75% or more by controlling the content of the colorant in the range of 2.5 to 30 g / m2.
  • the polymer sheet for solar cells of the present invention may have other functional layers in addition to the polymer substrate and the first and second polymer layers.
  • an undercoat layer and an easy adhesion layer can be provided.
  • an undercoat layer may be provided between the polymer substrate (support) and the second polymer layer.
  • the thickness of the undercoat layer is preferably in the range of 2 ⁇ m or less, more preferably 0.05 ⁇ m to 2 ⁇ m, and still more preferably 0.1 ⁇ m to 1.5 ⁇ m. When the thickness is 2 ⁇ m or less, the planar shape can be kept good. Moreover, it is easy to ensure required adhesiveness because thickness is 0.05 micrometer or more.
  • the undercoat layer can contain a binder.
  • a binder for example, polyester, polyurethane, acrylic resin, polyolefin, or the like can be used.
  • epoxy, isocyanate, melamine, carbodiimide, oxazoline and other crosslinking agents, anionic and nonionic surfactants, silica and other fillers are added to the undercoat layer. Also good.
  • the method for applying the undercoat layer and the solvent of the coating solution used there is no particular limitation on the method for applying the undercoat layer and the solvent of the coating solution used.
  • a coating method for example, a gravure coater or a bar coater can be used.
  • the solvent used for the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a solvent may be used individually by 1 type and may be used in mixture of 2 or more types.
  • the coating may be performed on the polymer substrate after biaxial stretching, or may be performed by stretching in a direction different from the initial stretching after coating on the polymer substrate after uniaxial stretching. Furthermore, you may extend
  • the polymer sheet for solar cells of this invention is a method which can contact the said sealing agent of the battery side board
  • the polymer sheet for solar cells of the present invention may further be provided with a colored layer (preferably a reflective layer) substantially free of the specific binder.
  • the colored layer in this case (hereinafter sometimes referred to as a third colored layer) contains at least a polymer component other than the specific binder and a pigment, and further contains other components such as various additives as necessary. Can be configured.
  • the details of the pigment and various additives are as described above for the case where the first or second polymer layer is formed as a colored layer.
  • the polymer component other than the specific binder is not particularly limited and can be appropriately selected according to the purpose.
  • the term “substantially free” means that the specific binder is not actively contained in the colored layer. Specifically, the content of the specific binder in the colored layer is 15% by mass or less. Preferably, the specific binder is not contained (the content is 0 (zero) mass%).
  • the polymer sheet for solar cells of the present invention is further provided with an easily adhesive layer.
  • the easy-adhesion layer is particularly preferably provided on the colored layer.
  • the easy-adhesion layer is a layer for firmly bonding the solar cell polymer sheet to a sealing material (preferably EVA) for sealing a solar cell element (hereinafter also referred to as a power generation element) of the battery side substrate (battery body). It is.
  • the easy-adhesion layer can be constituted using a binder and inorganic fine particles, and may further comprise other components such as additives as necessary.
  • the easy-adhesion layer is 10 N / cm or more (preferably 20 N / cm or more) with respect to an ethylene-vinyl acetate (EVA: ethylene-vinyl acetate copolymer) -based sealing material that seals the power generation element of the battery side substrate. It is preferable that it is comprised so that it may have the adhesive force of (). When the adhesive force is 10 N / cm or more, it is easy to obtain wet heat resistance capable of maintaining adhesiveness.
  • the adhesive strength can be adjusted by adjusting the amount of the binder and inorganic fine particles in the easy-adhesive layer, or applying a corona treatment to the surface of the back sheet that is bonded to the sealing material.
  • the easy-adhesion layer can contain at least one binder.
  • the binder suitable for the easy-adhesive layer include polyester, polyurethane, acrylic resin, polyolefin, and the like. Among these, acrylic resin and polyolefin are preferable from the viewpoint of durability. As the acrylic resin, a composite resin of acrylic and silicone is also preferable.
  • Examples of preferred binders include Chemipearl S-120 and S-75N (both manufactured by Mitsui Chemicals, Inc.) as specific examples of polyolefins, and Jurimer ET-410 and SEK-301 (both Nippon Pure Chemicals, Inc.) as specific examples of acrylic resins.
  • a composite resin of acrylic and silicone Ceranate WSA1060, WSA1070 (both manufactured by DIC Corporation) and H7620, H7630, H7650 (both manufactured by Asahi Kasei Chemicals Corporation) and the like can be given.
  • the content of the binder in the easy-adhesion layer is preferably in the range of 0.05 to 5 g / m2. In particular, the range of 0.08 to 3 g / m 2 is more preferable.
  • the binder content is 0.05 g / m 2 or more, a desired adhesive force is easily obtained, and when it is 5 g / m 2 or less, a better surface shape is obtained.
  • the easily adhesive layer can contain at least one kind of inorganic fine particles.
  • the inorganic fine particles include silica, calcium carbonate, magnesium oxide, magnesium carbonate, and tin oxide.
  • fine particles of tin oxide and silica are preferable in that the decrease in adhesiveness when exposed to a humid heat atmosphere is small.
  • the particle size of the inorganic fine particles is preferably about 10 to 700 nm, more preferably about 20 to 300 nm in terms of volume average particle size. When the particle size is within this range, better easy adhesion can be obtained.
  • the particle size is a value measured by a laser analysis / scattering particle size distribution measuring apparatus LA950 (manufactured by Horiba, Ltd.).
  • the shape of the inorganic fine particles is not particularly limited, and any shape such as a spherical shape, an irregular shape, or a needle shape can be used.
  • the content of the inorganic fine particles is in the range of 5 to 400% by mass with respect to the binder in the easy-adhesive layer.
  • the content of the inorganic fine particles is 5% by mass or more, good adhesiveness can be maintained when exposed to a moist heat atmosphere, and when it is 400% by mass or less, the surface state of the easily adhesive layer is more favorable.
  • the content of inorganic fine particles is preferably in the range of 50 to 300% by mass.
  • the easily adhesive layer can contain at least one crosslinking agent.
  • the crosslinking agent suitable for the easily adhesive layer include epoxy-based, isocyanate-based, melamine-based, carbodiimide-based, and oxazoline-based crosslinking agents.
  • an oxazoline-based cross-linking agent is particularly preferable from the viewpoint of ensuring adhesiveness after wet heat aging.
  • Specific examples of the oxazoline-based crosslinking agent include the same specific examples as described in the above-mentioned polymer layer section.
  • the content of the crosslinking agent in the easy-adhesive layer is preferably 5 to 50% by mass, more preferably 20 to 40% by mass, based on the binder in the easy-adhesive layer.
  • the content of the crosslinking agent is 5% by mass or more, a good crosslinking effect can be obtained, and the strength and adhesiveness of the colored layer can be maintained.
  • the content is 50% by mass or less, the pot life of the coating liquid Can be kept long.
  • the easily adhesive layer may further contain a known matting agent such as polystyrene, polymethylmethacrylate, or silica, or a known surfactant such as anionic or nonionic.
  • a known matting agent such as polystyrene, polymethylmethacrylate, or silica
  • a known surfactant such as anionic or nonionic.
  • the easy-adhesive layer can be formed by a method in which a polymer sheet having easy adhesive properties is bonded to a substrate, or a method by coating. Especially, the method by application
  • a coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
  • the coating solvent used for preparing the coating solution may be water or an organic solvent such as toluene or methyl ethyl ketone.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • the thickness of the easy-adhesion layer is not particularly limited, but is usually preferably 0.05 to 8 ⁇ m, more preferably 0.1 to 5 ⁇ m.
  • the thickness of the easy-adhesion layer is 0.05 ⁇ m or more, necessary easy adhesion can be suitably obtained, and when it is 8 ⁇ m or less, the surface shape becomes better.
  • the easy-adhesion layer needs to be transparent so as not to reduce the effect of the colored layer.
  • the polymer sheet for solar cells of the present invention has an adhesive force with the sealing material after storage for 48 hours in an atmosphere of 120 ° C. and 100% RH, with respect to the adhesive force with the sealing material before storage, It is preferable that it is 75% or more.
  • the polymer sheet for solar cells of the present invention includes a predetermined amount of binder and a predetermined amount of inorganic fine particles with respect to the binder, and has an adhesive force of 10 N / cm or more with respect to the EVA-based sealing material.
  • the method for producing the polymer sheet for solar cells of the present invention is not particularly limited, but can be suitably produced by the following method for producing a polymer sheet for solar cells of the present invention.
  • the method for producing a polymer sheet for a solar cell of the present invention comprises, on a polymer substrate, at least one binder polymer selected from a fluoropolymer and a silicone polymer, and a crosslinking agent having an oxazoline group, and Applying a coating solution having an equivalent [meq / g] of the oxazoline group to the binder polymer of more than 0 and less than 1 and drying and then curing to form a second polymer layer (second step) And a coating liquid containing at least one binder polymer selected from a fluoropolymer and a silicone polymer is applied onto the second polymer layer and dried to form the first polymer layer. Forming (first polymer layer forming step).
  • the polymer sheet for solar cell of the present invention can form the first and second polymer layers of the present invention and, if necessary, an easily adhesive layer on a polymer substrate. Any method may be used.
  • the first and second coating solutions for polymer layer are coating solutions containing the essential components and optional components described above. Details of the polymer substrate and the components constituting each coating liquid are as described above.
  • the first and second polymer layer coating solutions for example, a gravure coater or a bar coater can be used.
  • the polymer layer coating solution is applied directly on the surface of the polymer substrate or through an undercoat layer having a thickness of 2 ⁇ m or less, and the polymer layer (for example, a colored layer (preferably a reflective layer) Layer) or back layer).
  • the first and second polymer layers can be formed by a method in which a polymer sheet is bonded to a polymer substrate, a method in which the polymer layer is coextruded when forming the polymer substrate, a method by coating, or the like.
  • coating is preferable at the point which is easy and can form in a thin film with uniformity.
  • a coating method for example, a known coating method such as a gravure coater or a bar coater can be used.
  • the coating solution for the polymer layer may be an aqueous system using water as an application solvent, or a solvent system using an organic solvent such as toluene or methyl ethyl ketone. Among these, from the viewpoint of environmental burden, it is preferable to use water as a solvent.
  • a coating solvent may be used individually by 1 type, and may mix and use 2 or more types.
  • the polymer layer coating solution is preferably an aqueous coating solution in which 50% by mass or more, preferably 60% by mass or more, of the solvent contained therein is water.
  • the aqueous coating solution is preferable in terms of environmental load, and is advantageous in that the environmental load is particularly reduced when the ratio of water is 50% by mass or more.
  • the proportion of water in the coating liquid for the polymer layer is preferably larger from the viewpoint of environmental load, and more preferably 90% by weight or more of water is contained in the total solvent.
  • the polymer layer coating solution contains a “water-miscible organic solvent having a boiling point of 99 ° C. or lower” described later as an organic solvent
  • the amount of “water-miscible organic solvent having a boiling point of 99 ° C. or lower” is as described above.
  • the “water-miscible organic solvent having a boiling point of 99 ° C. or lower” is adjusted to an amount satisfying the content range.
  • One of the preferred embodiments of the coating liquid for the polymer layer is that 0.1% by mass to 30% by mass of a water-miscible organic solvent having a boiling point of 99 ° C. or less based on the total mass of the binder polymer contained in the coating liquid. % Water-based coating solution. It is preferable that at least one of the first polymer layer and the second polymer layer is formed using the aqueous coating solution. When the content of the water-miscible organic solvent in the coating solution for forming the polymer layer is 30% by mass or less, it is advantageous in terms of precipitation, filterability, and solvent environment.
  • the content of the water-miscible organic solvent in the coating solution for forming a polymer layer is 0.1% by mass to 30% by mass, more preferably 0.1% by mass to 10% by mass, more preferably, with respect to the binder polymer.
  • the content is preferably 0.1% by mass to 5% by mass.
  • the content of the water-miscible organic solvent is 0.1% by mass or more, it means that the water-miscible organic solvent is positively contained, and it is easy to remain in the formed layer.
  • the preferred range of the content of the water-miscible organic solvent in the coating liquid for forming a polymer layer is the same for the coating liquid for forming either the first polymer layer or the second polymer layer.
  • water-miscible organic solvent having a boiling point of 99 ° C. or lower include the same specific examples as described in the section of the polymer layer.
  • the second polymer layer is dried under desired conditions after the application of the coating solution for the polymer layer, and the dried coating film is further cured. Also about a 1st polymer layer, after drying on desired conditions, it is preferable to harden the coating film after drying further.
  • a heating method is suitable.
  • the heating temperature is not particularly limited, but is preferably 50 ° C to 200 ° C, more preferably 150 ° C to 200 ° C.
  • the curing time for curing the first or second polymer layer is preferably 1 minute to 30 minutes, and the production suitability is more preferably 1 minute to 2 minutes.
  • the first polymer layer and the second polymer layer in the present invention are formed in forming the first polymer layer and the second polymer layer.
  • the aspect which forms a 2nd polymer layer on a polymer base material, and forms a 1st polymer layer on this 2nd polymer layer following this is mentioned.
  • the curing time for forming the first polymer layer and the second polymer layer can be set to 1 to 2 minutes. That is, in the present invention, a polymer layer having sufficient adhesion can be formed even when the curing time is set to a relatively short time as described above. Further, when the first polymer layer and the second polymer layer further contain an onium compound, the solvent resistance as well as sufficient adhesion can be improved. Thus, the polymer sheet for solar cells of the present invention has excellent production suitability.
  • the solar cell module of the present invention is configured by providing the polymer sheet for solar cell of the present invention described above or the polymer sheet for solar cell manufactured by the method for manufacturing the polymer sheet for solar cell described above.
  • a solar cell element that converts light energy of sunlight into electric energy is disposed between the transparent front substrate on which sunlight enters and the polymer sheet for solar cells of the present invention described above.
  • the solar cell element is sealed and bonded with a sealing material such as ethylene-vinyl acetate between the front substrate and the back sheet. That is, a cell structure portion having a solar cell element and a sealing material for sealing the solar cell element is provided between the front substrate and the back sheet.
  • the transparent substrate only needs to have a light-transmitting property through which sunlight can be transmitted, and can be appropriately selected from base materials that transmit light. From the viewpoint of power generation efficiency, the higher the light transmittance, the better.
  • a transparent resin such as an acrylic resin, or the like can be suitably used.
  • Solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as copper-indium-gallium-selenium, copper-indium-selenium, cadmium-tellurium, gallium-arsenic, and II Various known solar cell elements such as a group VI compound semiconductor can be applied.
  • PET-1, PET-2, PET-3, PET-4, and PET-5 were prepared as follows.
  • Step 2 Preparation of polymer pellets Subsequently, 0.3% by mass of ethylene glycol was added to the polycondensation reaction tank to which the esterification reaction product had been transferred, with respect to the resulting polymer. After stirring for 5 minutes, an ethylene glycol solution of cobalt acetate and manganese acetate was added in the resulting polymer so that the cobalt element equivalent value and the manganese element equivalent value were 30 ppm and 15 ppm, respectively. After further stirring for 5 minutes, a 2% by mass ethylene glycol solution of a titanium alkoxide compound was added so that the converted value of titanium element was 5 ppm in the resulting polymer to obtain a low polymer.
  • Step 3 Solid phase polymerization- The pellets obtained above were held in a vacuum vessel maintained at 40 Pa at a temperature of 220 ° C. for 30 hours for solid phase polymerization.
  • Step 4 Production of film-like polymer substrate (support)-
  • the pellets after undergoing solid-phase polymerization as described above were melted at 280 ° C. and cast on a metal drum to produce an unstretched base having a thickness of 2.5 mm. Thereafter, the film was stretched 3 times in the longitudinal direction at 90 ° C., and further stretched 3.3 times in the transverse direction at 120 ° C.
  • PET-1 biaxially stretched polyethylene terephthalate support having a thickness of 300 ⁇ m was obtained.
  • the carboxyl group content of PET-1 was 14 eq / t.
  • the carboxyl group content of the polyethylene terephthalate support was determined by the following method.
  • the amount of potassium hydroxide solution required for titration was set to ymL, and the carboxyl group content (COOH group content) of the biaxially stretched PET support was determined by the following formula (A).
  • the carboxyl group content in PET-2 to 5 described later was also determined in the same manner as in PET-1.
  • Carboxyl group content (eq / t) 0.01 ⁇ y / w Formula (A)
  • the titanium dioxide fine particles are observed with a scanning electron microscope (SEM), the magnification is appropriately changed according to the size of the particles, and a photograph taken is enlarged and copied. Next, the major axis and minor axis of each particle are measured for at least 100 randomly selected fine particles. The average value of the major axis and the minor axis is defined as the particle size of the particle. The particle diameter of each particle is determined, and the average value of 100 particles is defined as the average particle diameter of the titanium dioxide fine particles.
  • PET-5 As shown below, using the solid phase polymerized pellets obtained by the production of PET-1 and the master batch pellets (MB-III) obtained by the production of PET-4, respectively, A layer, B Except for coextrusion of layer C and layer C, a 250- ⁇ m thick double-stretched polyethylene terephthalate support (PET-5) having a laminated structure of layer A, layer B and layer C was prepared in the same manner as in step 4 in the production of PET-1. ) The thicknesses of the A layer, the B layer, and the C layer are as shown below. The carboxyl group content of PET-5 was 15 eq / t.
  • (A layer) Pellets Solid-phase-polymerized pellets obtained in the production of PET-1 are used alone. Thickness: about 50 ⁇ m (B layer) Pellets: Mixed pellets obtained by mixing 64% by mass of solid phase polymerized pellets obtained in the production of PET-1 and 36% by mass of master batch pellets (MB-III) are used. Thickness: about 150 ⁇ m (C layer) Pellets: Solid-phase-polymerized pellets obtained in the production of PET-1 are used alone. Thickness: about 50 ⁇ m
  • each polymer sheet of Examples and Comparative Examples was prepared as follows.
  • Example 1-1 A reflective layer, an easy-adhesion layer, and first and second polymer layers were formed on the PET-1 obtained above as follows to produce a polymer sheet of Example 1-1.
  • ⁇ Formation of reflective layer> Preparation of pigment dispersion- Components in the following composition were mixed, and the mixture was subjected to a dispersion treatment for 1 hour by a dynomill type disperser.
  • ⁇ Composition of coating solution 1> The above pigment dispersion: 80.0 parts-Polyacrylic resin aqueous dispersion: 19.2 parts (Binder: Jurimer ET410, manufactured by Nippon Pure Chemicals Co., Ltd., solid content: 30% by mass) Polyoxyalkylene alkyl ether: 3.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1% by mass) Oxazoline compound (crosslinking agent, H-1) 2.0 parts (Epocross WS-700, manufactured by Nippon Shokubai Chemical Industry Co., Ltd., solid content: 25% by mass) ⁇ Distilled water: 7.8 parts
  • the obtained coating solution 1 for the reflective layer was coated on the above PET-1 and dried at 180 ° C. for 1 minute to form a white layer (reflective layer) having a titanium dioxide content of 6.5 g / m 2 as a pigment layer. Formed.
  • Corona treatment was performed on the side of PET-1 where the reflective layer and the easy-adhesion layer were not formed under the following conditions.
  • the second polymer layer coating solution A obtained from the following was applied so that the binder amount was 5.1 g / m 2 in terms of wet coating amount, and at 150 ° C. for 2 minutes. It was dried and cured to form a second polymer layer having a dry thickness of 8.5 ⁇ m.
  • the first polymer layer coating solution B obtained from the following was applied such that the binder amount was 1.3 g / m 2 in terms of wet coating amount, and dried at 150 ° C. for 2 minutes. Cured and dried to form a first polymer layer having a thickness of 1.6 ⁇ m.
  • Second coating liquid A for polymer layer Components in the following composition were mixed to prepare a second coating liquid A for polymer layer.
  • [Preparation of Coating Solution B for First Polymer Layer] Components in the following composition were mixed to prepare a first coating liquid B for polymer layer.
  • ⁇ Composition of coating solution> Fluoropolymer aqueous dispersion (Obligard SW0011F, AGC Co-Tech Co., Ltd., solid content concentration 36.1% by mass) ⁇ ⁇ ⁇ 45.9 parts ⁇
  • Crosslinking agent having oxazoline group (Epocross WS-700, Nippon Shokubai Chemical Industry Co., Ltd.) 7.7 parts, polyoxyalkylene alkyl ether ... 2.0 parts (Naroacty CL95, manufactured by Sanyo Chemical Industries, solid content: 1) mass%) -The above pigment dispersion ... 33.0 parts-Distilled water ... 11.4 parts
  • Example 1-1 the specific binder and the oxazoline group were added so that the equivalent amount (meq / g) of the oxazoline group to the binder in the second polymer layer and the first polymer layer was a value described in Table 1.
  • Polymer sheets of Examples 1-2 to 1-3 and Comparative Examples 1-1 to 1-6 were produced in the same manner as Example 1-1 except that the amount of the crosslinking agent to be used was changed.
  • Examples 2-1 to 2-3, Comparative Examples 2-1 to 2-6 In Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-6, the fluoropolymer aqueous dispersion used for the first polymer layer was replaced with a silicone polymer aqueous dispersion (Ceranate WSA1070, DIC Corporation). Examples 2-1 to 2--2 are the same as Examples 1-1 to 1-3 and Comparative Examples 1-1 to 1-6 except that the solid content concentration was changed to 37.4% by mass. 3 and polymer sheets of Comparative Examples 2-1 to 2-6 were produced.
  • each of the polymer sheets of Examples 1-1 to 1-3 and Examples 2-1 to 2-3 is a polymer having excellent adhesion in comparison with the comparative example. It turns out that it is a sheet. Moreover, it turns out that the polymer sheet of each Example is excellent also about production suitability.
  • Examples 3-1 to 3-13 For the second polymer layer coating solution A and the first polymer layer coating solution B used in Example 1-2, the onium compounds listed in Table 2 were further added to the binder ratios listed in Table 2 ( Polymer sheets of Examples 3-1 to 3-13 were produced in the same manner as in Example 1-2 except that the content was changed so that the amount was (mass%).
  • Example 4-1 to 4-11 For the second polymer layer coating solution A and the first polymer layer coating solution B used in Example 2-2, the onium compounds listed in Table 2 were further added to the binder ratios listed in Table 2 ( Polymer sheets of Examples 4-1 to 4-11 were produced in the same manner as in Example 2-2, except that the content was added so that the amount was (mass%).
  • Examples 5-1 to 5-5 The specific binder and the oxazoline group so that the equivalent amount (meq / g) of the oxazoline group to the binder is the value described in Table 3 with respect to the first polymer layer coating solution used in Example 4-3.
  • ethanol a water-miscible organic solvent having a boiling point of 99 ° C. or lower
  • the binder ratio see Table 3
  • Examples 5-6 to 5-9 With respect to the first polymer layer coating solution used in Example 4-3, a specific binder and an oxazoline group are included so that the equivalent (meq / g) of the oxazoline group to the binder is a value described in Table 3. A cross-linking agent and an onium compound were used, and ethanol (water-miscible organic solvent having a boiling point of 99 ° C. or lower) was added so as to have a binder ratio (% by mass) shown in Table 3, and the film thickness. Polymer sheets of Examples 5-6 to 5-9 were produced in the same manner as Example 4-3 except that was changed as described in Table 3.
  • Examples 5-10 to 5-13 Ethanol (a water-miscible organic solvent having a boiling point of 99 ° C. or less) was further added to the first polymer layer coating solution used in Examples 5-6 to 5-9 to the binder ratio (mass) shown in Table 3. %), Polymer sheets of Examples 5-10 to 5-13 were produced in the same manner as in Examples 5-6 to 5-9.
  • Examples 5-14 to 5-15 Except for adjusting the amount of distilled water with respect to the first polymer layer coating solution used in Examples 5-10 to 5-11, the liquid concentrations (mass%) shown in Table 3 were obtained. In the same manner as in Examples 5-10 to 5-11, polymer sheets of Examples 5-14 to 5-15 were produced.
  • Examples 5-16 to 5-19 In the same manner as in Example 5-11 except that the polymer substrate (PET-1) used in Example 5-11 was changed to the polymer substrate shown in Table 3, Examples 5-16 to 5-5 Seventeen polymer sheets were prepared. The polymer substrate (PET-1) used in Example 5-11 was changed to the polymer substrate shown in Table 3, and the Ti content in the second polymer layer was changed as shown in Table 3. Except for the above, polymer sheets of Examples 5-18 to 5-19 were produced in the same manner as Example 5-11.
  • Example 3-1 to 3-13, Examples 4-1 to 4-11, and Example 5 which further contain an onium compound in the first and second polymer layers It can be seen that each of the polymer sheets of -1 to 5-19 is excellent in solvent resistance and adhesiveness. Moreover, it turns out that the polymer sheet of each Example is excellent also about production suitability.
  • Example 6-1 3 mm thick tempered glass, EVA sheet (SC50B manufactured by Mitsui Chemicals Fabro Co., Ltd.), crystalline solar cell, EVA sheet (SC50B manufactured by Mitsui Chemicals Fabro Co., Ltd.), Example 1-1
  • the polymer sheets prepared in (1) were superposed in this order, and hot-pressed using a vacuum laminator (Nisshinbo Co., Ltd., vacuum laminating machine) to adhere to EVA.
  • the polymer sheet prepared in Example 1-1 was disposed so that the easy-adhesion layer was in contact with the EVA sheet.
  • the adhesion method is as follows. In this way, a crystalline solar cell module was produced.
  • Example 6-1 polymer sheets were prepared as Examples 1-2 to 1-3, Examples 2-1 to 2-3, Examples 3-1 to 3-11, and Examples 4-1 to 4-11.
  • a solar cell module of Examples 6-2 to 6-46 was produced in the same manner as Example 5-1, except that the polymer sheet prepared in Examples 5-1 to 5-19 was used. did. When the power generation operation was performed using the obtained solar cell module, all showed good power generation performance as a solar cell.

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Abstract

L'invention concerne une feuille polymère pour cellule photovoltaïque, laquelle possède, sur un substrat polymère: une première couche polymère contenant au moins un liant polymère choisi dans le groupe comprenant des fluoropolymères et des polymères de silicone; une deuxième couche polymère qui, côté substrat polymère de la première couche polymère, contient une fraction structurelle dérivée d'un agent de réticulation possédant au moins un liant polymère choisi dans le groupe comprenant des fluoropolymères et des polymères de silicone ainsi qu'un groupe oxazoline réticulant ce liant polymère, le poids équivalent [meq/g] du groupe oxazoline par rapport au liant polymère étant supérieur à 0 et inférieur à 1.
PCT/JP2012/070857 2011-08-17 2012-08-16 Feuille polymère pour cellule photovoltaïque ainsi que son procédé de fabrication et module de cellule photovoltaïque WO2013024893A1 (fr)

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JP2019207900A (ja) * 2016-09-30 2019-12-05 富士フイルム株式会社 太陽電池用バックシート及びその製造方法、並びに、太陽電池モジュール及びそのリサイクル方法
JP2017130685A (ja) * 2017-03-27 2017-07-27 東洋インキＳｃホールディングス株式会社 太陽電池用裏面保護シート、その製造方法および太陽電池モジュール

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JPH0598014A (ja) * 1991-03-27 1993-04-20 General Electric Co <Ge> エポキシ官能性フルオロシリコ―ン
JP2003021908A (ja) * 2001-07-09 2003-01-24 Fuji Photo Film Co Ltd 平版印刷版の製版方法
JP2007077177A (ja) * 2005-09-09 2007-03-29 Toyo Ink Mfg Co Ltd 塗料組成物及び水性塗料組成物
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JP5389531B2 (ja) * 2009-03-23 2014-01-15 ユニチカ株式会社 封止用保護シートおよび太陽電池モジュール
JP2011029397A (ja) * 2009-07-24 2011-02-10 Fujifilm Corp 太陽電池用バックシート及びその製造方法
JP5734569B2 (ja) * 2010-01-18 2015-06-17 富士フイルム株式会社 太陽電池用バックシート及びその製造方法、並びに太陽電池モジュール

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JPH0598014A (ja) * 1991-03-27 1993-04-20 General Electric Co <Ge> エポキシ官能性フルオロシリコ―ン
JPH0525361A (ja) * 1991-07-17 1993-02-02 Nippon Shokubai Co Ltd 硬化性樹脂組成物
JP2003021908A (ja) * 2001-07-09 2003-01-24 Fuji Photo Film Co Ltd 平版印刷版の製版方法
JP2007077177A (ja) * 2005-09-09 2007-03-29 Toyo Ink Mfg Co Ltd 塗料組成物及び水性塗料組成物
JP2011146659A (ja) * 2010-01-18 2011-07-28 Fujifilm Corp 太陽電池バックシート用フィルム及びその製造方法

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