WO2016171080A1 - 封止シートおよび太陽電池モジュール - Google Patents

封止シートおよび太陽電池モジュール Download PDF

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Publication number
WO2016171080A1
WO2016171080A1 PCT/JP2016/062119 JP2016062119W WO2016171080A1 WO 2016171080 A1 WO2016171080 A1 WO 2016171080A1 JP 2016062119 W JP2016062119 W JP 2016062119W WO 2016171080 A1 WO2016171080 A1 WO 2016171080A1
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Prior art keywords
sealing sheet
ethylene
mass
solar cell
compounds
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PCT/JP2016/062119
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English (en)
French (fr)
Japanese (ja)
Inventor
貴信 室伏
理恵 大土井
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三井化学東セロ株式会社
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Priority to KR1020177022014A priority Critical patent/KR20170102964A/ko
Priority to JP2016547629A priority patent/JP6035001B1/ja
Priority to CN201680008428.8A priority patent/CN107396640A/zh
Publication of WO2016171080A1 publication Critical patent/WO2016171080A1/ja

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K3/00—Materials not provided for elsewhere
    • C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
    • 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
    • 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
    • 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 sealing sheet and a solar cell module.
  • the solar cell module generally has a configuration of a protective glass (front surface side transparent protective member), a sealing sheet, a solar cell element, a sealing sheet, and a back sheet (back surface side protective member).
  • a protective glass front surface side transparent protective member
  • a sealing sheet a sealing sheet
  • a solar cell element a solar cell element
  • a sealing sheet a sealing sheet
  • a back sheet back surface side protective member
  • Patent Document 1 Japanese Patent Laid-Open No. 2010-532978 discloses a sealing film that is made of an EVA composition containing a cross-linking agent and trimellitic acid ester and has both excellent adhesion and film-forming properties. Yes.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2008-53379 describes that the transparency of the solar cell encapsulating sheet is improved by including a (meth) acrylate compound in the encapsulating sheet.
  • Patent Document 2 Japanese Patent Application Laid-Open No. 2008-53379 describes that the transparency of the solar cell encapsulating sheet is improved by including a (meth) acrylate compound in the encapsulating sheet.
  • this document does not describe that the occurrence of the PID phenomenon of the module can be suppressed.
  • the present invention has been made in view of the above circumstances, and provides a sealing sheet that can suppress the occurrence of the PID phenomenon of a solar cell module.
  • the present inventors diligently studied to provide a sealing sheet that can suppress the occurrence of the PID phenomenon of the solar cell module. As a result, the inventors have found that the use of a specific tri (meth) acrylate compound as a constituent component of the encapsulating sheet can prevent the occurrence of the PID phenomenon of the solar cell module, leading to the present invention.
  • the following sealing sheet and solar cell module are provided.
  • a sealing sheet used for sealing a solar cell element An ethylene / polar monomer copolymer; A crosslinking agent; One or more crosslinking aids selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds; A glycerol tri (meth) acrylate compound represented by the following formula (I): The sealing sheet containing.
  • R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group, and R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2- , and x + y + z is an integer of 2 or more and 20 or less)
  • R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2- , and x + y + z is an integer of 2 or more and 20 or less
  • the content of the glycerin tri (meth) acrylate compound represented by the formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. Stop sheet.
  • a sealing layer to A solar cell module comprising:
  • the solar cell module using the encapsulating sheet of the present invention has little decrease in output and parallel resistance Rsh even after a high voltage is applied, and can maintain power generation characteristics over a long period of time.
  • the sealing sheet of this embodiment is used in order to seal a solar cell element, and ethylene / polar monomer copolymer, a crosslinking agent, a divinyl aromatic compound, a cyanurate compound, and a diallyl compound.
  • 1 type, or 2 or more types of crosslinking adjuvants selected from the group which consists of a triallyl compound, an oxime compound, and a maleimide compound, and the glycerol tri (meth) acrylate compound shown by following formula (I).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group
  • R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 -, -CH 2 CH (CH 3 )-or -CH 2 CH 2-
  • x + y + z is an integer of 2 or more and 20 or less
  • a solar cell module using a sealing sheet containing a glycerin tri (meth) acrylate compound represented by the above formula (I) in addition to an ethylene / polar monomer copolymer, a crosslinking agent, and a crosslinking auxiliary agent is PID. It was found that the occurrence of the phenomenon can be suppressed. That is, the sealing sheet of this embodiment can suppress generation
  • each component which comprises the sealing sheet of this embodiment is demonstrated.
  • the encapsulating sheet of the present embodiment contains an ethylene / polar monomer copolymer.
  • the ethylene / polar monomer copolymer include ethylene / (meth) ethyl acrylate copolymers, ethylene / (meth) methyl acrylate copolymers, ethylene / (meth) propyl propyl copolymers, ethylene ⁇ (Meth) butyl acrylate copolymer, ethylene ⁇ (meth) acrylic acid hexyl copolymer, ethylene ⁇ (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene ⁇ (meth) acrylic acid-2-hydroxy Propylene copolymer, ethylene / (meth) acrylate glycidyl copolymer, ethylene / dimethyl maleate copolymer, ethylene / diethyl maleate copolymer, ethylene / dimethyl fuma
  • the ethylene / polar monomer copolymer is one or two selected from an ethylene / vinyl ester copolymer and an ethylene / unsaturated carboxylic acid ester copolymer from the balance between availability and performance. It is preferable to contain a seed or more, and it is particularly preferable to include an ethylene / vinyl acetate copolymer.
  • the ethylene / vinyl acetate copolymer is a copolymer of ethylene and vinyl acetate, and is usually a random copolymer.
  • the content ratio of the structural unit derived from vinyl acetate in the ethylene / vinyl acetate copolymer is preferably 10% by mass to 47% by mass, and more preferably 13% by mass to 35% by mass.
  • the vinyl acetate content can be measured according to JIS K6730.
  • the ethylene / vinyl acetate copolymer is preferably a binary copolymer consisting only of ethylene and vinyl acetate.
  • ethylene and vinyl acetate for example, vinyl formate, vinyl glycolate, vinyl propionate, vinyl benzoate.
  • a vinyl ester monomer such as acrylic acid, methacrylic acid, ethacrylic acid, or an acrylic monomer such as a salt or alkyl ester thereof; .
  • the amount of the copolymer component other than ethylene and vinyl acetate in the ethylene / vinyl acetate copolymer may be 0.5 mass% or more and 5 mass% or less. preferable.
  • the melt flow rate (MFR) of the ethylene / vinyl acetate copolymer at 190 ° C. and 2160 g load according to ASTM D 1238 is preferably 5 g / 10 min to 45 g / 10 min, more preferably 5 g / 10 min to 40 g / It is 10 minutes or less, more preferably 10 g / 10 minutes or more and 30 g / 10 minutes or less.
  • MFR melt flow rate
  • the MFR of the ethylene / vinyl acetate copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio between the monomer concentration and the hydrogen concentration of the polar monomer in the polymerization system. .
  • the sealing sheet of this embodiment may use, for example, two or more ethylene / vinyl acetate copolymers having different vinyl acetate contents, melt flow rates, etc. When using coalescence, it is preferable that the total amount of these be in the above range.
  • the content of the ethylene / polar monomer copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 100% by mass when the entire resin component contained in the sealing sheet is 100% by mass. It is 95% by mass or more, and particularly preferably 100% by mass.
  • the content of the resin component is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and particularly preferably 90% by mass when the entire sealing sheet is 100% by mass. % Or more.
  • the method for producing the ethylene / polar monomer copolymer is not particularly limited, and can be produced by a known method.
  • a radical generator copolymerization of ethylene, polar monomers, and other copolymerization components as necessary in the presence or absence of a solvent or chain transfer agent at 500 to 4000 atm and 100 to 300 ° C Can be manufactured.
  • the crosslinking agent for example, an organic peroxide can be used.
  • the ethylene / polar monomer copolymer can be cross-linked by containing a cross-linking agent, or the silane coupling agent can be grafted onto the ethylene / polar monomer copolymer. I can do it.
  • the content of the crosslinking agent in the sealing sheet is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 0.2 parts by mass or more and 2 parts by mass with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is not more than part by mass, and more preferably not less than 0.2 part by mass and not more than 1 part by mass.
  • the content of the cross-linking agent is not less than the above lower limit value, the deterioration of the cross-linking characteristics of the sealing sheet is suppressed, and the graft reaction to the main chain of the ethylene / polar monomer copolymer of the silane coupling agent is improved. A decrease in heat resistance and adhesiveness can be suppressed. Further, when the content of the cross-linking agent is not more than the above upper limit value, the generation amount of the decomposition product of the cross-linking agent is further reduced, and generation of bubbles in the sealing sheet can be more reliably suppressed. .
  • the organic peroxide has a half-life of 10 hours or less and a decomposition temperature of 105 ° C. or less. From the viewpoint of safety, it is preferable that the maximum storage temperature is 10 ° C. or higher.
  • organic peroxides examples include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, di-t -Butyl perphthalate, cumene hydroperoxide, t-butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexene, 2,5-dimethyl-2,5-di (t -Butylperoxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1-di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-a
  • 2,5-dimethyl-2,5-di (t-butylperoxy) hexene 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxy- It is preferable to use one or more selected from 2-ethylhexyl carbonate and t-butyl peroxybenzoate.
  • the sealing sheet of the present embodiment has excellent crosslinking characteristics by containing a crosslinking agent, it is not necessary to go through a two-step bonding process of a vacuum laminator and a crosslinking furnace, and at a high temperature in a short time. Can be completed.
  • Crosslinking aid one or more selected from the group consisting of divinyl aromatic compounds, cyanurate compounds, diallyl compounds, triallyl compounds, oxime compounds and maleimide compounds can be used.
  • the content of the crosslinking aid in the encapsulating sheet is preferably 10 parts by mass or less, more preferably 5.0 parts by mass or less, with respect to 100 parts by mass of the ethylene / polar monomer copolymer.
  • the amount is particularly preferably 2.0 parts by mass or less.
  • Examples of the divinyl aromatic compound include divinylbenzene and di-i-propenylbenzene.
  • Examples of the cyanurate compound include triallyl cyanurate and triallyl isocyanurate.
  • Examples of diallyl compounds include diallyl phthalate.
  • Examples of the triallyl compound include pentaerythritol triallyl ether.
  • Examples of the oxime compound include p-quinone dioxime, pp′-dibenzoylquinone dioxime, and the like.
  • Examples of the maleimide compound include m-phenylene dimaleimide.
  • the sealing sheet of this embodiment contains a glycerin tri (meth) acrylate compound represented by the following formula (I).
  • R 1 , R 2 and R 3 are each independently a hydrogen atom or a methyl group
  • R 4 , R 5 and R 6 are each independently —CH (CH 3 ) CH 2 — , —CH 2 CH (CH 3 ) — or —CH 2 CH 2 —
  • x + y + z is an integer of 2 or more and 20 or less.
  • x + y + z is preferably an integer of 3 or more and 6 or less, more preferably 3 or 6.
  • Each of x, y and z is preferably independently 1 or 2.
  • R 1 , R 2 and R 3 in the above formula (I) are preferably all hydrogen atoms.
  • R 1 , R 2, and R 3 are hydrogen atoms, the PID resistance is excellent as compared with a compound that is a methyl group.
  • the glycerin tri (meth) acrylate compound represented by the above formula (I) glycerin propoxytri (meth) acrylate and glycerin ethoxytri (meth) acrylate are preferable, and glycerin propoxytriacrylate and glycerin ethoxytriacrylate are more preferable. .
  • x + y + z in the above formula (I) is preferably an integer of 3 or more, and particularly preferably 3 or 6.
  • a mixture of a compound having x + y + z of 3 and a compound having x + y + z of 6 may be used, or a compound other than x + y + z of 3 or 6 may be mixed by 30% by mass or less.
  • the content of the glycerin tri (meth) acrylate compound represented by the above formula (I) is 0.1 parts by mass or more and 2.0 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. It is particularly preferably 0.1 parts by mass or more and 1.0 part by mass or less.
  • the content of the glycerin tri (meth) acrylate compound is not less than the above lower limit value, the PID resistance of the obtained solar cell module can be further improved.
  • content of a glycerol tri (meth) acrylate compound is below the said upper limit, generation
  • the total content of the crosslinking aid and the glycerin tri (meth) acrylate compound represented by the above formula (I) is preferably 0.2 parts by mass or more with respect to 100 parts by mass of the ethylene / polar monomer copolymer. 5.0 parts by mass or less, more preferably 0.5 parts by mass or more and 3.0 parts by mass or less, and further preferably 0.5 parts by mass or more and 2.0 parts by mass or less.
  • the encapsulating sheet of the present embodiment may appropriately contain various components other than the components detailed above in a range not impairing the object of the present invention.
  • one or two or more additives selected from silane coupling agents, ultraviolet absorbers, light stabilizers, antioxidants and the like can be appropriately contained.
  • the content of the silane coupling agent in the sealing sheet of the present embodiment is preferably 0.1 parts by mass or more and 5 parts by mass or less, more preferably 100 parts by mass of the ethylene / polar monomer copolymer. It is 0.1 mass part or more and 3 mass parts or less, More preferably, it is 0.1 mass part or more and 1.5 mass parts or less.
  • the adhesive strength between the sealing sheet and the other member can be further improved.
  • silane coupling agent when the silane coupling agent is not more than the above upper limit value, methanol and ethanol generated by hydrolysis derived from the methoxy group and ethoxy group of the silane coupling agent are reduced, and bubbles are generated in the sealing sheet. It can suppress more reliably.
  • silane coupling agent examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl.
  • the encapsulating sheet of this embodiment may contain one or two or more additives selected from the group consisting of an ultraviolet absorber, a light stabilizer, and an antioxidant.
  • the total content of these additives is preferably 0.005 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the ethylene / polar monomer copolymer. By making it within this range, the effect of improving the resistance to high temperature and high humidity, heat cycle resistance, weather resistance stability, and heat stability is sufficiently secured, and the transparency and adhesiveness of the sealing sheet are lowered. Can be prevented.
  • Examples of the ultraviolet absorber include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2,2-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2- Benzophenone ultraviolet absorbers such as carboxybenzophenone and 2-hydroxy-4-N-octoxybenzophenone; 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2-hydroxy- Benzotriazole ultraviolet absorbers such as 5-methylphenyl) benzotriazole and 2- (2-hydroxy-5-t-octylphenyl) benzotriazole; salicylic acid esters such as phenyl salicylate and p-octylphenyl salicylate Select from UV absorbers, etc. It is the one or may be used two or more.
  • Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3. , 5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ ]
  • the like selected from hindered amine compounds, hindered piperidine compounds and the like can be used.
  • antioxidants examples include tris (2,4-di-tert-butylphenyl) phosphite, bis [2,4-bis (1,1-dimethylethyl) -6-methylphenyl] ethyl ester phosphorous acid Tetrakis (2,4-di-tert-butylphenyl) [1,1-biphenyl] -4,4′-diylbisphosphonite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphos Phosphite-based antioxidants such as phites; Lactone-based antioxidants such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene; 3,3 ′ , 3 ", 5,5 ', 5" -hexa-tert-butyl-a, a', a "-(methylene-2,4,6-triyl) tri-p-cresol
  • the thickness of the sealing sheet in this embodiment is not specifically limited, 0.01 mm or more and 2 mm or less are preferable, and 0.2 mm or more and 1.2 mm or less are more preferable. When the thickness is within this range, damage to the light-receiving surface side protective member, solar cell element, thin film electrode, etc. in the laminating step can be suppressed, and a high amount of photovoltaic power can be obtained by ensuring sufficient light transmittance. be able to. Furthermore, it is preferable because the solar cell module can be laminated at a low temperature.
  • the sealing sheet of this embodiment may be laminated with other layers as long as the object of the present invention is not impaired.
  • layers such as a hard-coat layer for surface or back surface protection, an adhesion layer, an antireflection layer, a gas barrier layer, and an antifouling layer.
  • layer made of UV curable resin layer made of thermosetting resin
  • layer made of polyolefin resin layer made of carboxylic acid modified polyolefin resin
  • layer made of fluorine-containing resin cyclic olefin (co)
  • examples thereof include a layer made of a polymer and a layer made of an inorganic compound.
  • the thermal shrinkage rate measured according to JIS C2318-1997 is preferably 25% or less, and more preferably 15% or less.
  • Method for producing sealing sheet Although the manufacturing method of the sealing sheet of this embodiment is not particularly limited, various known molding methods (cast molding, extrusion sheet molding, inflation molding, injection molding, compression molding, calendar molding, etc.) can be employed. is there. In particular, extrusion molding and calendar molding are preferable.
  • the manufacturing method of the sealing sheet of this embodiment is not specifically limited, For example, the following method is mentioned. First, an ethylene / polar monomer copolymer, a crosslinking agent, a crosslinking assistant, a glycerin tri (meth) acrylate compound represented by the above formula (I), and other additives as needed are dry blended. . Next, the obtained mixture is supplied from the hopper to the extruder and melt-kneaded at a temperature lower than the one-hour half-life temperature of the crosslinking agent as necessary. Thereafter, a sealing sheet is produced by extrusion from the tip of the extruder into a sheet.
  • the molding can be performed by a known method using a T-die extruder, a calendar molding machine, an inflation molding machine or the like.
  • seat which does not contain a crosslinking agent may be produced by the said method, and a crosslinking agent may be added to the produced sheet
  • melt kneading may be performed at a temperature lower than the one-hour half-life temperature of the lowest crosslinking agent.
  • the sealing sheet of this embodiment is used in order to seal a solar cell element in a solar cell module.
  • seat) in this order is mentioned, it is not specifically limited.
  • the sealing sheet of this embodiment is used for either one or both of the light receiving surface side sealing sheet and the back surface side sealing sheet.
  • the solar cell module 10 includes a plurality of solar cell elements 13, a pair of light-receiving surface side sealing sheet 11 and back surface side sealing sheet 12 that are sealed with the solar cell element 13 interposed therebetween, and a front surface side transparent protective member 14 and a back surface.
  • solar cell element 13 examples include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, and III-V and II-VI compound semiconductors such as gallium-arsenic, copper-indium-selenium, and cadmium-tellurium.
  • Various solar cell elements such as a system can be used.
  • the plurality of solar cell elements 13 are electrically connected in series via an interconnector 16 having a conducting wire and a solder joint.
  • Examples of the surface-side transparent protective member 14 include a glass plate; a resin plate formed of acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like.
  • back surface side protection member (back sheet) 15 examples include single or multilayer sheets such as metals and various thermoplastic resin films. Examples thereof include metals such as tin, aluminum, and stainless steel; inorganic materials such as glass; various thermoplastic resin films formed of polyester, inorganic material-deposited polyester, fluorine-containing resin, polyolefin, and the like.
  • the back surface side protection member 15 may be a single layer or a multilayer.
  • the sealing sheet of the present embodiment exhibits good adhesion to the front surface side transparent protective member 14 and the back surface side protective member 15.
  • the manufacturing method of the solar cell module 10 of this embodiment is not specifically limited, For example, the following method is mentioned.
  • a plurality of solar cell elements 13 that are electrically connected using the interconnector 16 are sandwiched between a pair of light-receiving surface side sealing sheet 11 and back surface side sealing sheet 12, and further, these light receiving surface side sealing sheet 11 and back surface A laminated body is produced by sandwiching the side sealing sheet 12 between the front surface side transparent protective member 14 and the back surface side protective member 15.
  • the laminate is heated to receive the light-receiving surface side sealing sheet 11 and the back surface side sealing sheet 12, the light receiving surface side sealing sheet 11 and the front surface side transparent protective member 14, and the back surface side sealing sheet 12 and the back surface side protective member. 15 is bonded. More specifically, the sealing sheet is heated to such a temperature that the crosslinking agent contained in the sealing sheet is not substantially decomposed and the ethylene / polar monomer copolymer is melted, and the light receiving surface side sealing is performed. The sheet 11 and the rear surface side sealing sheet 12, the light receiving surface side sealing sheet 11 and the front surface side transparent protective member 14, and the rear surface side sealing sheet 12 and the rear surface side protective member 15 are temporarily bonded.
  • the bonding and crosslinking temperature may be a temperature at which a satisfactory crosslinking rate can be obtained and swelling does not occur, and can be in a temperature range of about 100 to 180 ° C., for example.
  • sealing sheets were produced as follows. First, an ethylene / vinyl acetate copolymer (EVA), a crosslinking agent, a crosslinking aid, an acrylate compound, a silane coupling agent, a light stabilizer, and an antioxidant are blended in the formulation shown in Table 1 to obtain a resin composition. Obtained. The obtained resin composition was extrusion molded into a sealing sheet having a thickness of about 450 ⁇ m with an extruder with a T-die.
  • EVA ethylene / vinyl acetate copolymer
  • each component in Table 1 is part by mass.
  • the detail of each component in Table 1 is as follows.
  • EVA ethylene-vinyl acetate copolymer (vinyl acetate content 28% by mass, MFR: 15 g / 10 min)
  • Crosslinking agent t-butylperoxy-2-ethylhexyl carbonate
  • Crosslinking aid triallyl isocyanurate
  • Acrylate compound 1 Glycerol propoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 Wherein R 4 , R 5 and R 6 are —CH (CH 3 ) CH 2 — or —CH 2 CH (CH 3 ) —)
  • Acrylate compound 2 Nonaethylene glycol dimethacrylate
  • Acrylate compound 3 Glycerol ethoxytriacrylate (in formula (I), x + y + z is 3, R 1 , R 2 , R 3 are hydrogen atoms, R 4 , R 5 and R Compound in which 6 is —CH 2 CH 2 — Silane coupling agent:
  • a PET backsheet containing silica-deposited PET as the backsheet cut a portion of the backsheet with a cutter-knife about 2 cm, take out the positive and negative terminals of the cell, and use a vacuum laminator (NPC: LM -110 ⁇ 160-S) was laminated at a heating plate temperature of 150 ° C., a vacuum time of 3 minutes, and a pressurization time of 15 minutes. Thereafter, the sealing sheet and the back sheet that protruded from the glass were cut, an end face sealing material was applied to the glass edge, and an aluminum frame was attached. Thereafter, the cut portion of the terminal portion taken out from the back sheet was cured by applying RTV silicone to obtain a mini module.
  • NPC vacuum laminator
  • This module was set in a constant temperature and humidity chamber at 60 ° C. and 85% Rh, and after waiting for the temperature to rise, it was held for 96 hours while applying ⁇ 1000 V.
  • HARb-3R10-LF manufactured by Matsusada Precision Co., Ltd. was used as the high voltage power source, and FS-214C2 manufactured by ETAC Co., Ltd. was used as the constant temperature and humidity chamber.
  • the IV characteristics of the module are the maximum output power at a light irradiation power density of 1000 W / m 2 using a xenon light source with AM (air mass) 1.5 class A light intensity distribution and PVS-116i-S manufactured by Nisshinbo Mechatronics. P max was evaluated. Furthermore, since the parallel resistance in the dark (dark Rsh) in PID evaluation is the most sensitive parameter for indicating cell deterioration, dark Rsh was also added to the evaluation item. Specifically, the module is installed in a dark room, IV characteristics in the dark are measured using 6242 made by ADC, and dark Rsh is calculated from the slope ( ⁇ V / ⁇ I) of the voltage when the current is near zero. evaluated.
  • the evaluation results were classified as follows. The results are shown in Table 1.
  • the maximum output power P max of the IV characteristic after the test is less than 5% compared to the initial value: A: Output power drop exceeds 5%: B
  • the parallel resistance (dark Rsh) in the dark of IV characteristics after the test is less than 50% of the decrease in dark Rsh: A Dark Rsh reduction exceeds 50%: B
  • P max and dark Rsh were A, it was judged that there was no PID degradation.
  • P max or dark Rsh was B, it was judged that PID was degraded.

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