WO2021039397A1 - 太陽電池封止材用樹脂組成物、太陽電池封止材、太陽電池封止材の製造方法および太陽電池モジュール - Google Patents

太陽電池封止材用樹脂組成物、太陽電池封止材、太陽電池封止材の製造方法および太陽電池モジュール Download PDF

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WO2021039397A1
WO2021039397A1 PCT/JP2020/030671 JP2020030671W WO2021039397A1 WO 2021039397 A1 WO2021039397 A1 WO 2021039397A1 JP 2020030671 W JP2020030671 W JP 2020030671W WO 2021039397 A1 WO2021039397 A1 WO 2021039397A1
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solar cell
resin composition
cell encapsulant
ethylene
carboxylic acid
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PCT/JP2020/030671
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English (en)
French (fr)
Japanese (ja)
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敬 永山
佳那 久木田
紀彦 佐藤
礒川　素朗
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三井・ダウポリケミカル株式会社
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Priority to KR1020227010355A priority Critical patent/KR102713972B1/ko
Priority to JP2021542718A priority patent/JP7311613B2/ja
Priority to DE112020004111.5T priority patent/DE112020004111T5/de
Priority to CN202080060539.XA priority patent/CN114302912B/zh
Publication of WO2021039397A1 publication Critical patent/WO2021039397A1/ja

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
    • C08G59/4207—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/544—Silicon-containing compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0876—Salts thereof, i.e. ionomers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0869—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen with unsaturated acids, e.g. [meth]acrylic acid; with unsaturated esters, e.g. [meth]acrylic acid esters
    • C08L23/0884—Epoxide-containing esters
    • 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
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10F—INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
    • H10F19/00—Integrated devices, or assemblies of multiple devices, comprising at least one photovoltaic cell covered by group H10F10/00, e.g. photovoltaic modules
    • H10F19/80—Encapsulations or containers for integrated devices, or assemblies of multiple devices, having photovoltaic cells
    • H10F19/804—Materials of encapsulations
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a resin composition for a solar cell encapsulant, a solar cell encapsulant, a method for manufacturing a solar cell encapsulant, and a solar cell module.
  • Photovoltaic power generation has become widespread as a clean energy source.
  • Photovoltaic power generation directly converts solar energy into electrical energy using a semiconductor (solar cell element) such as a silicon cell.
  • a semiconductor solar cell element
  • the solar cell element is sandwiched between sealing materials to protect the solar cell element and prevent foreign matter from entering the solar cell element and moisture from entering the solar cell element.
  • the solar cell encapsulant that encloses the solar cell element functions as a protective material for the solar cell element, creep resistance that does not easily flow even if the module temperature rises due to sunlight is required. Further, in order not to reduce the conversion efficiency of the solar cell, high transparency (light transmittance) is required. In addition, in order to protect the solar cell module member for a long period of time, various properties such as low moisture permeability, high volume resistance, heat resistance, weather resistance, and high adhesiveness are required.
  • Patent Document 1 Japanese Patent Laid-Open No. 2014-95083
  • Patent Document 2 Japanese Patent Laid-Open No. 2013-177506
  • Patent Document 1 describes at least one resin (A) selected from an ethylene-vinyl acetate copolymer and an ethylene-aliphatic unsaturated thermoplastic acid copolymer, and the above resin (A) and an ethylene-aliphatic unsaturated resin.
  • a solar cell encapsulating resin sheet including an inner layer made of B) and a surface layer made of the resin (A) laminated on the inner layer is described.
  • Patent Document 2 describes a resin encapsulating sheet for a solar cell in which a resin is softened and adhered to the resin. It contains at least one kind of ionizing radiation crosslinked resin selected from the group consisting of ethylene-aliphatic unsaturated carboxylic acid ester copolymer, and gel content is obtained by irradiating the ionized radiation crosslinked resin with ionizing radiation.
  • a resin sealing sheet for a solar cell having a rate of 2 to 65% by mass and a heat shrinkage rate at 90 ° C. of 15% or less is described.
  • thermoplastic resin The technical standards required for various properties of solar cell encapsulants are becoming higher and higher.
  • the present inventors have found the following problems with respect to a solar cell encapsulant using a thermoplastic resin.
  • the solar cell encapsulant using the thermoplastic resin is inferior in creep resistance above the melting point of the thermoplastic resin. It has been clarified that if the creep resistance is improved by designing the melting point of the thermoplastic resin to be high, the transparency may be deteriorated. That is, the present inventors have found that there is room for improvement in the conventional thermoplastic solar cell encapsulant from the viewpoint of improving transparency and creep resistance in a well-balanced manner.
  • the present invention has been made in view of the above circumstances, and provides a resin composition for a solar cell encapsulant capable of obtaining a solar cell encapsulant having an excellent balance of transparency and creep resistance. Is.
  • the present inventors have made extensive studies to achieve the above problems. As a result, by combining the ionomer of the ethylene / unsaturated carboxylic acid-based copolymer containing two or more kinds of metal ions and the ethylene-based copolymer containing an epoxy group, the above trade-off relationship can be improved. We have found that the transparency and creep resistance of the solar cell encapsulant can be improved in a well-balanced manner, and have arrived at the present invention.
  • the following resin composition for a solar cell encapsulant, a solar cell encapsulant, a method for manufacturing a solar cell encapsulant, and a solar cell module are provided.
  • a resin composition used for forming a solar cell encapsulant contains an ionomer (A) of an ethylene / unsaturated carboxylic acid-based copolymer and an epoxy group-containing ethylene-based copolymer (B).
  • the metal ions constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer are lithium ion, potassium ion, sodium ion, silver ion, copper ion, calcium ion, magnesium ion, zinc ion, aluminum ion, and barium.
  • the metal ion constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer contains a first metal ion and a second metal ion different from the first metal ion.
  • the first metal ion contains at least one metal ion selected from the group consisting of sodium ion, lithium ion, potassium ion and magnesium ion.
  • the resin composition for a solar cell encapsulant according to the above [3] The value obtained by multiplying the number of moles of the first metal ion in the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer by the valence by the number of moles of the second metal ion multiplied by the valence.
  • a resin composition for a solar cell encapsulant having a ratio of 0.10 or more and 10.0 or less [5] In the resin composition for a solar cell encapsulant according to any one of the above [1] to [4]. The content of the epoxy group-containing ethylene-based copolymer (B) is less than 10.0% by mass when the total content of the resin composition for the solar cell encapsulant is 100% by mass. Resin composition for. [6] In the resin composition for a solar cell encapsulant according to any one of the above [1] to [5]. A resin composition for a solar cell encapsulant further containing a silane coupling agent (C).
  • C silane coupling agent
  • the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) is a binary copolymer of ethylene and unsaturated carboxylic acid (A1), and ethylene, unsaturated carboxylic acid and unsaturated carboxylic acid ester.
  • a resin composition for a solar cell encapsulant which comprises at least one unsaturated carboxylic acid constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer selected from acrylic acid and methacrylic acid.
  • a resin composition for a solar cell encapsulant which comprises at least one unsaturated carboxylic acid constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer selected from acrylic acid and methacrylic acid.
  • the epoxy group-containing ethylene-based copolymer (B) includes ethylene / glycidyl (meth) acrylate copolymer, ethylene / glycidyl (meth) acrylate / vinyl acetate copolymer, and ethylene / glycidyl (meth) acrylate.
  • the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer when the total of the constituent units constituting the ethylene / unsaturated carboxylic acid-based copolymer is 100% by mass, it is derived from the unsaturated carboxylic acid.
  • a resin composition for a solar cell encapsulant whose constituent unit is 5% by mass or more and 35% by mass or less. [12] In the resin composition for a solar cell encapsulant according to any one of the above [1] to [11].
  • a resin composition for a solar cell encapsulant wherein the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer has a neutralization degree of 5% or more and 95% or less.
  • the resin composition for a solar cell encapsulant according to any one of the above [1] to [12]. At least a part of the carboxy group of the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer reacts with at least a part of the epoxy groups of the epoxy group-containing ethylene-based copolymer (B) to crosslink.
  • Method A 120 mm ⁇ 75 mm ⁇ 0.4 mm film composed of the resin composition for a solar cell encapsulant is obtained. Next, the obtained film was sandwiched between 120 mm ⁇ 75 mm ⁇ 3.2 mm glass plates, held in a vacuum at 150 ° C. for 3 minutes with a vacuum laminator, and pressed at 0.1 MPa (gauge pressure) for 5 minutes to obtain a laminated glass. obtain.
  • the haze of the obtained laminated glass is measured with a haze meter according to JIS K7136: 2000.
  • a method for producing a solar cell encapsulant which comprises a step of extruding the resin composition for a solar cell encapsulant according to any one of the above [1] to [16] into a sheet.
  • Resin composition for solar cell encapsulant The resin composition for solar cell encapsulant according to the present embodiment (hereinafter, also referred to as resin composition (P)) is used for forming the solar cell encapsulant.
  • Ionomer (A) contains two or more metal ions.
  • the transparency of the solar cell encapsulant using a thermoplastic resin may deteriorate when trying to improve the creep resistance. That is, the present inventors have found that the solar cell encapsulant using a thermoplastic resin has room for improvement from the viewpoint of improving transparency and creep resistance in a well-balanced manner.
  • the present inventors have made extensive studies to achieve the above problems. As a result, the above trade-off can be achieved by combining the ionomer (A), which is an ethylene / unsaturated carboxylic acid-based copolymer containing two or more kinds of metal ions, and the epoxy group-containing ethylene-based copolymer (B). It was found that the relationship can be improved and the transparency and creep resistance of the obtained solar cell encapsulant can be improved in a well-balanced manner. That is, the resin composition (P) according to the present embodiment contains an ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) containing two or more kinds of metal ions and an epoxy group-containing ethylene-based copolymer (B). By including,, the performance balance between the transparency and creep resistance of the obtained solar cell encapsulant can be improved.
  • the ionomer (A) is an ethylene / unsaturated carboxylic acid-based copolymer containing two or more kinds
  • the resin composition (P) contains an ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) and an epoxy group-containing ethylene-based copolymer (B) to obtain a solar cell seal.
  • the stop material at least a part of the carboxy group of the ethylene / unsaturated carboxylic acid-based copolymer (A) and the epoxy group of the epoxy group-containing ethylene-based copolymer (B) react with each other. A crosslinked structure is formed.
  • the mechanical properties and heat resistance of the obtained solar cell encapsulant can be improved.
  • the creep resistance of the solar cell encapsulant can be improved.
  • the resin composition contains the epoxy group-containing ethylene-based copolymer (B), the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) and the epoxy group-containing ethylene-based copolymer (B) are usually contained. ), Gels are likely to be generated in the obtained solar cell encapsulant. Therefore, the transparency and appearance of the obtained solar cell encapsulant usually tend to deteriorate.
  • the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) contains two or more kinds of metal ions, the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) and the ionomer (A)
  • the rapid cross-linking reaction with the epoxy group-containing ethylene-based copolymer (B) can be suppressed, and the cross-linking reaction can proceed gently.
  • the generation of gel can be suppressed, and as a result, the transparency and appearance of the solar cell encapsulant can be improved.
  • the solar cell encapsulant having an excellent balance of transparency and creep resistance can be obtained by using the resin composition for the solar cell encapsulant according to the present embodiment. ..
  • the total content of the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) and the epoxy group-containing ethylene-based copolymer (B) is the resin composition.
  • the whole of (P) is 100% by mass, it is preferably 60% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.
  • the total content of the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) and the epoxy group-containing ethylene-based copolymer (B) is within the above range, the transparency of the obtained solar cell encapsulant is obtained. , The balance between creep resistance, insulation, rigidity, water resistance, mechanical properties, heat resistance, handleability, workability, and PID resistance of the obtained solar cell module can be further improved.
  • the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment has at least a part of the carboxyl group of the polymer obtained by copolymerizing ethylene and at least one of the unsaturated carboxylic acids. It is a resin neutralized with metal ions.
  • the ethylene / unsaturated carboxylic acid-based copolymer include a copolymer containing ethylene and an unsaturated carboxylic acid, a copolymer containing ethylene, an unsaturated carboxylic acid, and an unsaturated carboxylic acid ester, and the like. Can be done.
  • Examples of the unsaturated carboxylic acid constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment include acrylic acid, methacrylic acid, 2-ethylacrylic acid, crotonic acid, and maleic acid. Examples thereof include fumaric acid, itaconic acid, maleic anhydride, fumaric anhydride, itaconic anhydride, monomethyl maleate, and monoethyl maleate.
  • the unsaturated carboxylic acid preferably contains at least one selected from acrylic acid and methacrylic acid from the viewpoint of productivity and hygiene of the ethylene / unsaturated carboxylic acid-based copolymer.
  • unsaturated carboxylic acids may be used alone or in combination of two or more.
  • an ethylene / unsaturated carboxylic acid system containing the above-mentioned unsaturated carboxylic acid such as acrylic acid or methacrylic acid as a constituent unit in an ionomer of one type alone or two or more types of ethylene / unsaturated carboxylic acid type copolymers. It is also possible to add a copolymer to obtain an ethylene / unsaturated carboxylic acid-based copolymer ionomer (A).
  • a resin composition (P) is obtained by further adding an ethylene / unsaturated carboxylic acid-based copolymer to an ionomer of an ethylene / unsaturated carboxylic acid-based copolymer containing two or more kinds of metal ions to obtain an ionomer (A). ), While maintaining good processability (film-forming property), higher adhesiveness can be exhibited, and the performance balance between transparency and water resistance can be further improved.
  • particularly preferable ethylene / unsaturated carboxylic acid-based copolymers are ethylene / (meth) acrylic acid copolymer and ethylene / (meth) acrylic acid / (meth) acrylic acid ester copolymer.
  • the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer when the total number of structural units constituting the ethylene / unsaturated carboxylic acid-based copolymer is 100% by mass, it is derived from ethylene.
  • the constituent unit to be obtained is preferably 65% by mass or more and 95% by mass or less, and more preferably 75% by mass or more and 92% by mass or less.
  • the structural unit derived from ethylene is at least the above lower limit value, the heat resistance, mechanical strength, water resistance, processability, etc. of the obtained solar cell encapsulant can be further improved.
  • the structural unit derived from ethylene is not more than the above upper limit value, the transparency, flexibility, adhesiveness and the like of the obtained solar cell encapsulant can be further improved.
  • the unsaturated carboxylic acid when the total amount of the constituent units constituting the ethylene / unsaturated carboxylic acid-based copolymer is 100% by mass, the unsaturated carboxylic acid
  • the structural unit derived from the acid is preferably 5% by mass or more and 35% by mass or less, and more preferably 8% by mass or more and 25% by mass or less.
  • the structural unit derived from the unsaturated carboxylic acid is at least the above lower limit value, the transparency, flexibility, adhesiveness, etc. of the obtained solar cell encapsulant can be further improved.
  • the structural unit derived from the unsaturated carboxylic acid is not more than the above upper limit value, the heat resistance, mechanical strength, water resistance, processability and the like of the obtained solar cell encapsulant can be further improved.
  • the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment preferably contains 100% by mass of all the constituent units constituting the ethylene / unsaturated carboxylic acid-based copolymer. It may contain a structural unit derived from other copolymerizable monomers of 0% by mass or more and 30% by mass or less, more preferably 0% by mass or more and 25% by mass or less. Other copolymerizable monomers include unsaturated esters such as vinyl acetate, vinyl esters such as vinyl propionate; methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (meth) acrylic.
  • Examples thereof include unsaturated carboxylic acid esters such as isobutyl acid, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate. It is preferable that the structural unit derived from the other copolymer monomer is contained within the above range because the flexibility of the obtained solar cell encapsulant is improved.
  • Examples of the metal ion constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment include lithium ion, potassium ion, sodium ion, silver ion, copper ion, calcium ion, and magnesium ion. , Zinc ion, aluminum ion, barium ion, beryllium ion, strontium ion, tin ion, lead ion, iron ion, cobalt ion and nickel ion.
  • the metal ions constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment contain a first metal ion and a second metal ion different from the first metal ion, and the first The metal ion contains at least one metal ion selected from the group consisting of sodium ion, lithium ion, potassium ion and magnesium ion, and the second metal ion contains zinc ion, copper ion, iron ion, aluminum ion, silver ion and cobalt. More preferably, it contains at least one metal ion selected from the group consisting of ions and nickel ions.
  • the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer and the epoxy group-containing ethylene-based copolymer (B) undergo a rapid cross-linking reaction. It can be further suppressed, and as a result, the processability of the solar cell encapsulant can be improved, and the generation of gel generated in the solar cell encapsulant sheet can be suppressed, and as a result, the solar cell can be suppressed. The transparency and appearance of the encapsulant can be further improved.
  • the metal ions constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer contain the first metal ion and the second metal ion, the metal ions are not ethylene.
  • the number of moles of the ion x the valence of the second metal ion) / (the number of moles of the first metal ion x the valence of the first metal ion)) balances the transparency and water resistance of the obtained solar cell encapsulant. From the viewpoint of making it better, it is preferably 0.10 or more, more preferably 0.15 or more, and further preferably 0.20 or more. Further, in the resin composition (P) according to the present embodiment, the second metal is obtained by multiplying the number of moles of the first metal ion in the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer by the valence.
  • the ratio of the number of moles of ions multiplied by the valence is preferably 10.0 or less from the viewpoint of improving the balance between transparency and water resistance of the obtained solar cell encapsulant. It is more preferably 0 or less, further preferably 4.0 or less, even more preferably 3.0 or less, and particularly preferably 2.5 or less.
  • the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) is, for example, the ethylene / unsaturated carboxylic acid-based copolymer ionomer 1 and the ionomer 1.
  • the mixing ratio of the ethylene / unsaturated carboxylic acid-based copolymer ionomer 1 and the ethylene / unsaturated carboxylic acid-based copolymer ionomer 2 the ethylene / unsaturated carboxylic acid-based copolymer can be adjusted.
  • the ratio of the first metal ion and the second metal ion in the ionomer (A) of the above can be easily adjusted.
  • the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) balances the flexibility, transparency and creep resistance of the obtained solar cell encapsulant.
  • the ionomer (A1) which is a binary copolymer of ethylene and unsaturated carboxylic acid
  • the ionomer which is a ternomer of a ternary copolymer of ethylene, unsaturated carboxylic acid and unsaturated carboxylic acid ester (A1). It is preferable to include A2).
  • the content of ionomer (A1) which is a binary copolymer of ethylene and unsaturated carboxylic acid, is the flexibility of the obtained solar cell encapsulant.
  • the content of ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer in the resin composition (P) is 100% by mass, It is preferably 40% by mass or more and 99% by mass or less, more preferably 50% by mass or more and 95% by mass or less, and further preferably 60% by mass or more and 90% by mass or less.
  • the content of ionomer (A2) which is a ternary copolymer of ethylene, unsaturated carboxylic acid, and unsaturated carboxylic acid ester, is the obtained solar cell encapsulant.
  • the content of the ethylene / unsaturated carboxylic acid copolymer (A) in the resin composition (P) is set to 100% by mass. When this is done, it is preferably 1% by mass or more and 60% by mass or less, more preferably 5% by mass or more and 50% by mass or less, and further preferably 10% by mass or more and 40% by mass or less.
  • the content of the unsaturated carboxylic acid ester in the ionomer (A2) of the ternary copolymer of ethylene, the unsaturated carboxylic acid and the unsaturated carboxylic acid ester constitutes the ethylene / unsaturated carboxylic acid-based copolymer.
  • the whole constituent unit is 100% by mass, it is preferably more than 0% by mass and 30% by mass or less, more preferably 1% by mass or more and 25% by mass or less, and further preferably 3% by mass or more and 20% by mass or less.
  • Examples of the unsaturated carboxylic acid ester in the ionomer (A2) of the ternary copolymer of ethylene, unsaturated carboxylic acid and unsaturated carboxylic acid ester include methyl (meth) acrylate and ethyl (meth) acrylate. , (Meta) propyl acrylate, isobutyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like. Among these, at least one selected from isobutyl meta) acrylate and n-butyl (meth) acrylate is preferable.
  • the degree of neutralization of the ethylene / unsaturated carboxylic acid copolymer (A) according to the present embodiment is not particularly limited, but the flexibility, adhesiveness, mechanical strength, and processability of the obtained solar cell encapsulant are not particularly limited. From the viewpoint of improving the above, 95% or less is preferable, 90% or less is more preferable, and 80% or less is further preferable. Further, the degree of neutralization of the ethylene / unsaturated carboxylic acid-based copolymer (A) according to the present embodiment is not particularly limited, but the transparency, heat resistance, water resistance, etc. of the obtained solar cell encapsulant can be improved.
  • the degree of neutralization of the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer is neutralized by metal ions among all the carboxyl groups contained in the ethylene / unsaturated carboxylic acid-based copolymer. Refers to the proportion (%) of carboxyl groups.
  • the method for producing the ethylene / unsaturated carboxylic acid-based copolymer constituting the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment is not particularly limited, and the ethylene / unsaturated carboxylic acid-based copolymer can be produced by a known method. it can. For example, it can be obtained by radical copolymerizing each polymerization component under high temperature and high pressure. Further, the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer according to the present embodiment can be obtained by reacting the ethylene / unsaturated carboxylic acid-based copolymer with a metal compound. Further, as the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer, a commercially available one may be used.
  • the melt mass flow rate (MFR) of the ethylene / unsaturated carboxylic acid-based copolymer ionomer (A) measured under the conditions of 190 ° C. and a load of 2160 g according to JIS K7210: 1999 is 0. It is preferably 0.01 g / 10 minutes or more and 50 g / 10 minutes or less, more preferably 0.1 g / 10 minutes or more and 30 g / 10 minutes or less, and 0.1 g / 10 minutes or more and 19 g / 10 minutes or less. Is particularly preferred.
  • the processability of the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer can be further improved.
  • the MFR is not more than the above upper limit value, the heat resistance and mechanical strength of the obtained solar cell encapsulant can be further improved.
  • the content of the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer in the resin composition (P) according to the present embodiment is as follows, when the total amount of the resin composition (P) is 100% by mass. It is preferably 50.0% by mass or more and 99.9% by mass or less, more preferably 70.0% by mass or more and 99.5% by mass or less, still more preferably 80.0% by mass or more and 99.5% by mass or less, still more preferably. Is 90.0% by mass or more and 99.0% by mass or less.
  • the content of ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer is within the above range, the transparency, creep resistance, interlayer adhesiveness, insulating property, and rigidity of the obtained solar cell encapsulant are obtained. , Water resistance, and performance balance such as PID resistance of the obtained solar cell module can be further improved.
  • Epoxy group-containing ethylene copolymer (B) examples include a glycidyl group-containing ethylene-based copolymer.
  • examples of the glycidyl group-containing ethylene-based copolymer include ethylene / glycidyl (meth) acrylate copolymer, ethylene / glycidyl (meth) acrylate / vinyl acetate copolymer, and ethylene / glycidyl (meth) acrylate.
  • At least one selected from (meth) acrylic acid ester copolymers and the like can be mentioned.
  • the epoxy group-containing ethylene-based copolymer (B) contains a polymerizable group such as glycidyl (meth) acrylate, vinyl glycidyl ether, 1,2-epoxy-4-vinylcyclohexane, and 3,4-epoxycyclohexylmethylmethacrylate and an epoxy. It is obtained by copolymerizing a monomer having a group with ethylene. Further, an epoxy group may be introduced by graft-polymerizing a monomer having an epoxy group on an ethylene-based copolymer.
  • the content ratio of the structural unit derived from the monomer such as glycidyl (meth) acrylate in the epoxy group-containing ethylene-based copolymer (B) is 100% by mass of the entire structural unit constituting the epoxy group-containing ethylene-based copolymer. In terms of%, it is preferably 2% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and further preferably 3% by mass or more and 15% by mass or less.
  • the content ratio of the structural unit derived from the monomer such as glycidyl (meth) acrylate is equal to or higher than the above lower limit value, the creep resistance of the obtained solar cell encapsulant and the interlayer adhesiveness of the solar cell module become better.
  • (meth) glycidyl acrylate represents one or both of glycidyl methacrylate and glycidyl acrylate.
  • the "ethylene-based copolymer" in the epoxy group-containing ethylene-based copolymer (B) means that a structural unit derived from ethylene is the main component.
  • the “main component” here means that the content of the “ethylene-derived constituent unit” is the highest among all the constituent units.
  • the ratio of the structural units derived from ethylene is the structural unit derived from glycidyl (meth) acrylate. It means that it is larger than the structural unit derived from vinyl acetate.
  • the proportion of the "ethylene-derived constituent unit" in the epoxy group-containing ethylene-based copolymer (B) is preferably 40 when the total of the constituent units constituting the epoxy group-containing ethylene-based copolymer is 100% by mass. It is mass% or more, more preferably 50% by mass or more, further preferably 55% by mass or more, and preferably 90% by mass or less, more preferably 80% by mass or less, still more preferably 75% by mass or less.
  • the epoxy group-containing ethylene-based copolymer can further contain ethylene and other monomer units other than the monomer having an epoxy group.
  • Examples of other monomers include vinyl esters such as vinyl acetate and vinyl propionate; acrylic acid esters, methacrylic acid esters, etacrylic acid esters, crotonic acid esters, fumaric acid esters, maleic acid esters, maleic anhydride esters, itaconic acid esters, and the like.
  • Examples thereof include unsaturated carboxylic acid esters such as anhydrous itaconic acid ester.
  • ester group examples include an alkyl ester group having 1 to 12 carbon atoms, and more specifically, a methyl ester, an ethyl ester, an n-propyl ester, an isopropyl ester, an n-butyl ester, an isobutyl ester, and a secondary butyl ester.
  • 2-Ethylhexyl ester, isooctyl ester and other alkyl ester groups can be exemplified.
  • at least one selected from vinyl acetate and (meth) acrylic acid ester is preferable.
  • a constitution further derived from vinyl acetate examples thereof include copolymers containing at least one of a unit and a constituent unit derived from (meth) acrylic acid ester.
  • the content ratio of the structural unit derived from vinyl ester such as vinyl acetate and the structural unit derived from unsaturated carboxylic acid ester such as (meth) acrylic acid ester is the total of the structural units constituting the epoxy group-containing ethylene-based copolymer.
  • it is preferably 40% by mass or less, and more preferably 30% by mass or less.
  • the lower limit of the content ratio of the constituent unit derived from vinyl ester such as vinyl acetate and the constituent unit derived from unsaturated carboxylic acid ester such as (meth) acrylic acid ester is not particularly limited, but both epoxy group-containing ethylene-based copolymers.
  • the total amount of the constituent units constituting the polymer is 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, and further preferably 15% by mass or more.
  • the content ratio of the structural unit derived from vinyl ester such as vinyl acetate or the structural unit derived from unsaturated carboxylic acid ester such as (meth) acrylic acid ester is preferably in the range of 5 to 40% by mass, further 10 The range of about 30% by mass is preferable, and the range of 15 to 30% by mass is particularly preferable.
  • the epoxy group-containing ethylene-based copolymer (B) can be used alone or in combination of two or more having different copolymerization ratios.
  • the content of the epoxy group-containing ethylene-based copolymer (B) in the resin composition (P) according to the present embodiment is preferably 10.
  • the total content of the resin composition (P) is 100% by mass. It is less than 0% by mass, more preferably 5.0% by mass or less, still more preferably 3.0% by mass or less.
  • the content of the epoxy group-containing ethylene-based copolymer (B) is within the above range, the obtained solar cell encapsulant has creep resistance, transparency, adhesiveness, moisture resistance, insulation, flexibility, and so on. The performance balance between heat resistance and processability can be further improved.
  • the lower limit of the content of the epoxy group-containing ethylene-based copolymer (B) in the resin composition (P) according to the present embodiment is not particularly limited, but may be, for example, 0.1% by mass or more. , 0.5% by mass or more.
  • the resin composition (P) according to the present embodiment preferably further contains a silane coupling agent (C) from the viewpoint of further improving the interlayer adhesiveness of the obtained solar cell module.
  • a silane coupling agent (C) examples include a silane coupling agent having a vinyl group, an amino group or an epoxy group and a hydrolyzing group such as an alkoxy group.
  • silane coupling agents (C) may be used alone or in combination of two or more.
  • a silane coupling agent having an amino group, a silane coupling agent having a dimethoxy group, and a silane coupling agent having a trimethoxy group are preferable from the viewpoint of further improving the interlayer adhesion of the obtained solar cell module.
  • Asilane coupling agents having an amino group and a dimethoxy group are more preferable.
  • the interlayer adhesion of the obtained solar cell module can be further improved by using a silane coupling agent having an amino group, but the amino group of the silane coupling agent having an amino group is ethylene-non-ethylene.
  • the silane coupling agent is immobilized on the ethylene / unsaturated carboxylic acid-based copolymer, and at the other functional group in the silane coupling agent. Since a certain alkoxy group reacts with a functional group on the surface of a base material such as glass, it is considered that a more excellent solar cell encapsulant can be obtained due to its adhesiveness to glass or the like.
  • silane coupling agent having an amino group examples include N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and N- (2-aminoethyl) -3-aminopropylmethyldimethoxy.
  • the content of the silane coupling agent (C) is the same as that of the resin composition (P) from the viewpoint of further improving the interlayer adhesiveness of the obtained solar cell module.
  • the whole is 100% by mass, it is preferably 0.001% by mass or more and 5% by mass or less, more preferably 0.005% by mass or more and 2% by mass or less, and further preferably 0.01% by mass or more and 1% by mass or less. is there.
  • the content of the silane coupling agent having an amino group is the resin composition (P) from the viewpoint of further improving the interlayer adhesion of the obtained solar cell module.
  • the content of the silane coupling agent (C) in the solution is 100% by mass, it is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, and further preferably 70% by mass or more. It is 100% by mass or less.
  • the resin composition (P) includes an ionomer (A) of an ethylene / unsaturated carboxylic acid-based copolymer and an epoxy group-containing ethylene-based copolymer (within a range not impairing the object of the present invention.
  • Ingredients other than B) and the silane coupling agent (C) can be contained.
  • Other components are not particularly limited, but are, for example, plasticizers, antioxidants, ultraviolet absorbers, wavelength converters, antioxidants, surfactants, colorants, light stabilizers, foaming agents, lubricants, crystal nuclei.
  • Agents crystallization accelerators, crystallization retardants, catalyst deactivators, heat ray absorbers, heat ray reflectors, heat dissipation agents, thermoplastic resins, thermosetting resins, inorganic fillers, organic fillers, impact resistance improvers , Slip agent, cross-linking agent, cross-linking aid, tackifier, processing aid, mold release agent, hydrolysis inhibitor, heat stabilizer, anti-blocking agent, antifogging agent, flame retardant, flame retardant aid, light diffusion Examples thereof include agents, antibacterial agents, anti-corrosion agents, dispersants and other resins.
  • the other components may be used alone or in combination of two or more.
  • the haze measured by the following method is preferably less than 3.5%, more preferably less than 3.0%.
  • the transparency of the obtained solar cell encapsulant can be improved.
  • the type of metal ion in the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer and the ethylene / non-ethylene in the resin composition (P) according to the present embodiment is preferably adjusted.
  • the lower limit of the haze of the resin composition (P) according to the present embodiment is not particularly limited, but is, for example, 0.01% or more.
  • Method A 120 mm ⁇ 75 mm ⁇ 0.4 mm film composed of the resin composition (P) according to the present embodiment is obtained. Next, the obtained film was sandwiched between 120 mm ⁇ 75 mm ⁇ 3.2 mm glass plates, held in a vacuum at 150 ° C. for 3 minutes with a vacuum laminator, and pressed at 0.1 MPa (gauge pressure) for 5 minutes to form a laminated glass. obtain. Next, the haze of the obtained laminated glass is measured with a haze meter according to JIS K7136: 2000.
  • the creep distance measured by the following method is preferably less than 5 mm, more preferably 1 mm or less.
  • the creep distance is not more than the upper limit value, the creep resistance of the obtained solar cell encapsulant can be improved.
  • the type of metal ion in the ionomer (A) of the ethylene / unsaturated carboxylic acid-based copolymer and the ethylene in the resin composition (P) according to the present embodiment are used.
  • the types and proportions of the unsaturated carboxylic acid-based copolymer ionomer (A) and the epoxy group-containing ethylene-based copolymer (B) may be appropriately adjusted.
  • the lower limit of the creep distance of the resin composition (P) according to the present embodiment is preferably 0 mm.
  • Method A 180 mm ⁇ 160 mm ⁇ 0.4 mm film composed of the resin composition (P) according to the present embodiment is obtained. Next, the two obtained films were overlapped, sandwiched between 180 mm ⁇ 180 mm ⁇ 3.2 mm float glass with a 2 cm shift, vacuum held at 150 ° C. for 3 minutes with a vacuum laminator, and pressed at 0.1 MPa (gauge pressure) for 5 minutes. To obtain a laminated glass. Next, one of the obtained laminated glasses is fixed so that the other glass can be freely displaced, and the displacement length of the glass after 200 hours at 105 ° C. is measured.
  • the adhesive strength to the glass plate measured by the following method is preferably 10 N / 15 mm or more, more preferably 20 N / 15 mm or more, and 30 N / 15 mm or more. Is particularly preferable.
  • the adhesive strength to the glass plate is at least the lower limit value, the interlayer adhesiveness of the obtained solar cell module can be improved.
  • the ethylene / unsaturated carboxylic acid copolymer ionomer (A) and the silane coupling agent (C) in the resin composition (P) according to the present embodiment May be adjusted as appropriate.
  • a 120 mm ⁇ 75 mm ⁇ 0.4 mm film composed of the resin composition (P) according to the present embodiment is obtained.
  • the obtained film was laminated on the tin surface of a glass plate of 120 mm ⁇ 75 mm ⁇ 3.9 mm, vacuum-held at 160 ° C. for 690 seconds with a vacuum laminator, and pressed at 0.06 MPa (gauge pressure) for 15 minutes.
  • the film is adhered to the tin surface of the glass plate.
  • the film is separated from the glass plate at a tensile speed of 100 mm / min at a peel angle of 180 °, and the maximum stress is calculated as the adhesive strength (N / 15 mm) to the glass plate.
  • the solar cell encapsulant according to the present embodiment includes a layer composed of the resin composition (P) according to the present embodiment.
  • the solar cell encapsulant according to the present embodiment may have a single-layer structure or a multi-layer structure having two or more layers. More specifically, the solar cell encapsulant according to the present embodiment may be a single-layered film composed of one layer composed of the resin composition (P) according to the present embodiment. It may be a multi-layered film composed of two or more layers of the resin composition (P) according to the present embodiment, or at least one layer of the resin composition (P) according to the present embodiment. It may be a multi-layered film having at least one layer and a layer other than the layer composed of the resin composition (P) according to the present embodiment.
  • the solar cell encapsulant according to the present embodiment has a multi-layer structure, it has a two-layer structure in which two outer layers (hereinafter, also referred to as adhesive layers) are laminated, and at least one outer layer is according to the present embodiment. It has a two-layer structure composed of the resin composition (P), or a three-layer structure including an intermediate layer and two outer layers formed on both sides of the intermediate layer so as to sandwich the intermediate layer. At least one of the intermediate layers is preferably a three-layer structure composed of the resin composition (P) according to the present embodiment, and the above three-layer structure is more preferable from the viewpoint of achieving both transparency and adhesiveness, and an outer layer.
  • the intermediate layer has a three-layer structure composed of the resin composition (P) according to the present embodiment.
  • the composition of the resin composition (P) according to the present embodiment and the type of ionomer contained in each layer may be the same or different.
  • the thickness of the solar cell encapsulant according to the present embodiment is, for example, 0.001 mm or more and 10 mm or less, preferably 0.01 mm or more and 5 mm or less, and more preferably 0.05 mm or more and 2 mm or less.
  • the thickness of the solar cell encapsulant is at least the above lower limit, the mechanical strength of the solar cell encapsulant can be improved. Further, when the thickness of the solar cell encapsulant is not more than the above upper limit value, the transparency and interlayer adhesiveness of the obtained solar cell encapsulant can be further improved.
  • the layer composed of the resin composition (P) according to the present embodiment may be used as an outer layer or an intermediate layer. ..
  • the thickness of the outer layer is arbitrary, but the thickness a of the outer layer is preferably in the range of 1 ⁇ m to 500 ⁇ m, and is preferably 10 ⁇ m. It is more preferably in the range of about 500 ⁇ m, and particularly preferably in the range of 20 ⁇ m to 300 ⁇ m.
  • the thickness a is 1 ⁇ m or more, the adhesive strength can be further improved, and when it is 500 ⁇ m or less, the transparency is more excellent.
  • the thickness of the intermediate layer in the total layer thickness may be thick in terms of transparency.
  • the thickness b of the intermediate layer can be freely set within a range in which the preferable total thickness of 0.1 mm to 10 mm is subtracted from the preferable thickness a of the outer layer.
  • the thickness ratio (a / b) between the outer layer (thickness a) and the intermediate layer (thickness b) is 1/20 to It is preferably 5/1, more preferably 1/15 to 3/1, and even more preferably 1/10 to 3/1.
  • the thickness a of the outer layers is the average value of the thicknesses of the two outer layers.
  • the method for producing the solar cell encapsulant according to the present embodiment is not particularly limited, and a conventionally known production method can be used.
  • Examples of the method for producing the solar cell encapsulant according to the present embodiment include a press molding method, an extrusion molding method, a T die molding method, an injection molding method, a compression molding method, a cast molding method, a calendar molding method, and an inflation molding method. Etc. can be used.
  • the extrusion molding method is preferable. That is, the solar cell encapsulant according to the present embodiment can be obtained, for example, by a manufacturing method including a step of extruding the resin composition (P) according to the present embodiment into a sheet.
  • the processing temperature in the extrusion step is not particularly limited, but is preferably less than 220 ° C., more preferably less than 200 ° C. from the viewpoint of suppressing the crosslinking reaction.
  • FIG. 1 is a cross-sectional view schematically showing an example of the structure of the solar cell module 1 according to the embodiment of the present invention.
  • the solar cell module 1 according to the present embodiment includes, for example, a solar cell element 3, a sealing resin layer 5 composed of a solar cell sealing material according to the present embodiment for sealing the solar cell element 3. To be equipped.
  • the solar cell module 1 according to the present embodiment may further include a substrate 2, a protective material 4, etc. to which sunlight is incident, if necessary.
  • the substrate 2 to which sunlight is incident may be simply referred to as the substrate 2.
  • the solar cell module 1 according to the present embodiment can be manufactured, for example, by fixing the solar cell element 3 sealed with the solar cell encapsulant according to the present embodiment on the substrate 2.
  • a solar cell module 1 various types can be exemplified.
  • a structure such as a substrate / sealing material / solar cell element / sealing material / protective material sandwiched between sealing materials from both sides of the solar cell element; a solar cell formed in advance on the surface of a substrate such as glass.
  • the element is configured as a substrate / solar cell element / sealing material / protective material; a solar cell element formed on the inner peripheral surface of the substrate, for example, an amorphous solar cell element is sputtered on a fluororesin-based sheet, etc.
  • the protective material 4 is referred to as a lower protective material because it is provided on the side opposite to the substrate 2 side of the solar cell module 1, that is, the lower part when the substrate 2 on which sunlight is incident is the upper part of the solar cell module 1.
  • the solar cell element 3 examples include silicon-based devices such as single crystal silicon, polycrystalline silicon, and amorphous silicon, group III-V such as gallium-arsenide, copper-indium-selenium, copper-indium-gallium-selenium, and cadmium-tellu.
  • group III-V such as gallium-arsenide
  • copper-indium-selenium copper-indium-gallium-selenium
  • cadmium-tellu Various solar cell elements such as II-VI group compound semiconductor systems can be used.
  • the solar cell encapsulant according to the present embodiment is particularly useful for encapsulating an amorphous silicon solar cell element and a heterojunction type solar cell element of amorphous silicon and single crystal silicon.
  • a plurality of solar cell elements 3 are electrically connected in series via an interconnector 6.
  • the substrate 2 constituting the solar cell module 1 according to the present embodiment examples include glass, acrylic resin, polycarbonate, polyester, and fluorine-containing resin.
  • the protective material 4 (lower protective material) is a single or multi-layer sheet such as a metal or various thermoplastic resin films, for example, a metal such as tin, aluminum or stainless steel, an inorganic material such as glass, polyester or an inorganic material vapor deposition.
  • a metal such as tin, aluminum or stainless steel
  • an inorganic material such as glass, polyester or an inorganic material vapor deposition.
  • One-layer or multi-layer sheets such as polyester, fluorine-containing resin, and polyolefin can be exemplified.
  • the solar cell encapsulant according to the present embodiment exhibits good adhesiveness to the substrate 2 or the protective material 4.
  • the manufacturing method of the solar cell module 1 is not particularly limited, and examples thereof include the following methods. First, a plurality of solar cell elements 3 electrically connected using the interconnector 6 are sandwiched between solar cell encapsulants, and these solar cell encapsulants are further sandwiched between the substrate 2 and the protective material 4 to prepare a laminate. To do. Next, the solar cell module 1 is obtained by heating and pressurizing the laminate and adhering the members together.
  • Resin-C Ethylene / methacrylic acid / i-butyl acrylate copolymer (methacrylic acid content: 10% by mass, i-butyl acrylate content: 10% by mass) Zn ionomer (neutralization degree: 70%, MFR (JIS K7210) : Measured in accordance with 1999 under the condition of 190 ° C.
  • Resin-D Ethylene / methacrylic acid copolymer (methacrylic acid content: 15% by mass) Na ionomer (neutralization degree: 54%, measured in accordance with MFR (JIS K7210: 1999) at 190 ° C. and 2160 g load.
  • Resin-E Ethylene / n-butyl acrylate / glycidyl methacrylate copolymer (n-butyl acrylate content: 21% by mass, glycidyl methacrylate content: 9% by mass, according to JIS K7210: 1999, 190 ° C., 2160 g load Measured under the conditions of): 8 g / 10 minutes)
  • Resin-F Ethylene / n-butyl acrylate / glycidyl methacrylate copolymer (n-butyl acrylate content: 28% by mass, glycidyl methacrylate content: 5.3% by mass, according to JIS K7210: 1999, 190 ° C., Measured under the condition of 2160g load): 12g / 10 minutes)
  • Silane coupling agent having an amino group (N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane)
  • Examples 1 to 3 and Comparative Examples 1 to 4 Each material was melt-kneaded at 160 ° C. at the blending ratios shown in Table 1 to obtain resin compositions. Next, the obtained resin composition was extruded under the conditions of an extruder die outlet resin temperature of 160 ° C. and a processing speed of 1.2 to 1.3 m / min to seal a sheet-shaped solar cell having a thickness of 0.4 mm. Each stop material was obtained.
  • the unit (phr) of the blending amount of the silane coupling agent (SCA) and the epoxy group-containing ethylene-based copolymer (resin-E, resin-F) is for both ethylene and unsaturated carboxylic acid-based copolymers. The mass part is shown when the total of ionomers of a polymer is 100 parts by mass.
  • the solar cell encapsulants of Examples 1 to 3 were excellent in transparency, creep resistance, interlayer adhesiveness, and appearance performance balance.
  • the solar cell encapsulants of Comparative Examples 1 to 4 were inferior in transparency, creep resistance, interlayer adhesiveness, and appearance performance balance.

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PCT/JP2020/030671 2019-08-30 2020-08-12 太陽電池封止材用樹脂組成物、太陽電池封止材、太陽電池封止材の製造方法および太陽電池モジュール WO2021039397A1 (ja)

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JP2021542718A JP7311613B2 (ja) 2019-08-30 2020-08-12 太陽電池封止材用樹脂組成物、太陽電池封止材、太陽電池封止材の製造方法および太陽電池モジュール
DE112020004111.5T DE112020004111T5 (de) 2019-08-30 2020-08-12 Harzzusammensetzung für Solarzellen-Einkapselungsmaterial, Solarzellen-Einkapselungsmaterial, Herstellungsverfahren für Solarzellen-Einkapselungsmaterial und Solarzellenmodul
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JP7311613B2 (ja) 2023-07-19
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