WO2016052070A1 - 封止シート、太陽電池モジュールおよび封止シートの製造方法 - Google Patents

封止シート、太陽電池モジュールおよび封止シートの製造方法 Download PDF

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WO2016052070A1
WO2016052070A1 PCT/JP2015/075091 JP2015075091W WO2016052070A1 WO 2016052070 A1 WO2016052070 A1 WO 2016052070A1 JP 2015075091 W JP2015075091 W JP 2015075091W WO 2016052070 A1 WO2016052070 A1 WO 2016052070A1
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sealing sheet
ethylene
solar cell
copolymer
sealing
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PCT/JP2015/075091
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English (en)
French (fr)
Japanese (ja)
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佐藤　理絵
洋文 善光
理恵 田中
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三井化学東セロ株式会社
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Priority to KR1020177007673A priority Critical patent/KR20170044176A/ko
Priority to JP2016551674A priority patent/JP6371403B2/ja
Priority to CN201580051824.4A priority patent/CN106715571A/zh
Publication of WO2016052070A1 publication Critical patent/WO2016052070A1/ja

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    • 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
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • 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
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • 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
    • 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, a solar cell module, and a manufacturing method of the sealing sheet.
  • solar cells are attracting attention as a means of generating energy that is clean and free from depletion.
  • a solar cell When a solar cell is used outdoors such as a roof portion of a building, it is generally used in the form of a solar cell module.
  • Said solar cell module is manufactured by the following procedures, for example. First, protective sheet for solar cell module (front surface side transparent protective member) / sealing layer (sealing sheet) / solar cell element / sealing layer (sealing sheet) / protective sheet for solar cell module (back side protective member) Are laminated in this order to form a laminate. Next, the obtained laminate is pressed and heated to be integrated. Thereafter, the solar cell module is manufactured by crosslinking and curing the sealing sheet.
  • the solar cell element further includes an electrode for taking out the generated electric power. Since an increase in resistance or short circuit of the electrode leads to a decrease in the amount of power generation, the electrode is required to have durability that does not deteriorate even after long-term use.
  • an ethylene / vinyl acetate copolymer (EVA) film is widely used since it is excellent in transparency, flexibility, adhesiveness, and the like (Patent Document 1). reference).
  • the sealing sheet for forming the sealing layer is required to have a performance that hardly causes the metal contained in the electrode to move even when a voltage is applied for a long time in an outdoor environment.
  • the present inventors diligently studied to provide a sealing sheet having excellent long-term reliability. As a result, the inventors have found that by reducing the amount of copper element contained in the sealing sheet, it is possible to realize a sealing layer in which migration of electrode metal hardly occurs even in long-term use.
  • the manufacturing method of the sealing sheet, solar cell module, and sealing sheet shown below is provided.
  • a sealing sheet used for sealing a solar cell element It consists of a resin composition containing a crosslinkable resin and copper element, The sealing sheet whose content of the said copper element in the said sealing sheet measured by ICP emission analysis is 1.0 ppb or less with respect to the said sealing sheet whole.
  • a sealing sheet, wherein the crosslinkable resin contains at least one selected from an ethylene / ⁇ -olefin copolymer and an ethylene / vinyl acetate copolymer.
  • the sealing sheet which further contains the 1 type, or 2 or more types of additive selected from the group which consists of a ultraviolet absorber, a light stabilizer, and a heat stabilizer.
  • a solar cell module comprising: [11] In the solar cell module according to [10] above, A solar cell module, wherein the solar cell element includes a silver electrode.
  • the sealing sheet in this embodiment is used in order to seal a solar cell element, and consists of a resin composition containing a crosslinkable resin and a copper element.
  • the content of the said copper element in the said sealing sheet measured by ICP emission analysis is 1.0 ppb or less with respect to the said whole sealing sheet, Preferably it is 0.8 ppb or less, Especially Preferably it is 0.5 ppb or less.
  • the content of the copper element in the sealing sheet is not more than the above upper limit value, migration of the electrode metal can be suppressed even during long-term use.
  • content of the copper element in the said sealing sheet is 0.001 ppb or more, for example.
  • the content of the copper element in the encapsulating sheet can be measured by, for example, wet-decomposing the encapsulating sheet, followed by constant volume with pure water, and ICP emission analysis using an ICP emission analyzer.
  • the inventors of the present invention have intensively studied the factors that cause the metal contained in the electrode to migrate in the sealing sheet. As a result, the following knowledge was obtained.
  • the sealing layer formed by the sealing sheet is in contact with the electrode and is generally molded from a resin composition containing a crosslinkable resin.
  • This resin composition may contain several ppm of a metal element derived from a crosslinkable resin synthesis catalyst and various additives, for example, an aluminum element. Conventionally, such a metal element has been considered to have a small effect on the electrode metal.
  • the present inventor has found that the migration of the electrode metal is caused even in a small amount of copper element among metal elements. That is, the present inventors have found for the first time that the copper element mixed in the sealing sheet has an influence on the migration of the electrode metal, and have reached the present invention.
  • Crosslinkable resin examples include an ethylene / ⁇ -olefin copolymer containing ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, a high-density ethylene resin, and a low-density ethylene.
  • Epoxy copolymer Ethylene / (meth) ethyl acrylate copolymer, ethylene / (meth) methyl acrylate copolymer, ethylene / (meth) propyl propyl copolymer, ethylene / butyl (meth) acrylate Copolymer, ethylene / (meth) acrylic acid hexyl copolymer, ethylene / (meth) acrylic acid-2-hydroxyethyl copolymer, ethylene / (meth) acrylic acid-2-hydroxypropyl copolymer, ethylene / Ethylene / (meth) acrylic acid ester copolymers such as (meth) acrylic acid glycidyl copolymer; ethylene / (meth) Ethylene / ethylenic unsaturated copolymer such as crylic acid copolymer, ethylene / maleic acid copolymer, ethylene / fumaric acid copolymer, ethylene
  • an ethylene / ⁇ -olefin copolymer composed of ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, which can be crosslinked with a crosslinking agent such as an organic peroxide, a low density ethylene resin, and a medium density ethylene Resin, ultra-low density ethylene resin, ethylene / cyclic olefin copolymer, ethylene / ⁇ -olefin / cyclic olefin copolymer, ethylene / ⁇ -olefin / non-conjugated polyene copolymer, ethylene / ⁇ -olefin / conjugated polyene Copolymers, ethylene / aromatic vinyl copolymers, olefin resins such as ethylene / ⁇ -olefin / aromatic vinyl copolymers, ethylene / unsaturated carboxylic anhydride copolymers, ethylene / ⁇ -olefin / unsaturated
  • An ethylene / ⁇ -olefin copolymer comprising ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, a low density ethylene resin, an ultra low density ethylene resin, an ethylene / ⁇ -olefin / non-conjugated polyene copolymer, an ethylene / ⁇ -olefin / conjugated polyene copolymer, ethylene / unsaturated carboxylic anhydride copolymer, ethylene / ⁇ -olefin / unsaturated carboxylic anhydride copolymer, ethylene / epoxy-containing unsaturated compound copolymer, ethylene / ⁇ -Selected from ethylene / unsaturated carboxylic acid copolymers such as olefin / epoxy-containing unsaturated compound copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, and ethylene / methacrylic acid copolymer. It
  • An ethylene / ⁇ -olefin copolymer comprising ethylene and an ⁇ -olefin having 3 to 20 carbon atoms, a low density ethylene resin, an ultra low density ethylene resin, an ethylene / ⁇ -olefin / non-conjugated polyene copolymer, an ethylene / One kind selected from ethylene / unsaturated carboxylic acid copolymer such as ⁇ -olefin / conjugated polyene copolymer, ethylene / vinyl acetate copolymer, ethylene / acrylic acid copolymer, ethylene / methacrylic acid copolymer Or it is more preferable to use 2 or more types. Among these, at least one selected from ethylene / ⁇ -olefin copolymers and ethylene / vinyl acetate copolymers is particularly preferably used. In the present embodiment, the above-described resins may be used alone or blended.
  • the content of the crosslinkable resin in the encapsulating sheet in the present embodiment is preferably 80% by mass or more, more preferably 90% by mass when the entire resin component contained in the encapsulating sheet is 100% by mass. More preferably, it is 95% by mass or more, and preferably 100% by mass.
  • the ⁇ -olefin of the ethylene / ⁇ -olefin copolymer comprising ethylene and an ⁇ -olefin having 3 to 20 carbon atoms used as the crosslinkable resin in the present embodiment is usually an ⁇ -olefin having 3 to 20 carbon atoms. Can be used singly or in combination of two or more. Among these, ⁇ -olefins having 10 or less carbon atoms are preferable, and ⁇ -olefins having 3 to 8 carbon atoms are particularly preferable.
  • ⁇ -olefins examples include propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, and 4-methyl-1-pentene. , 1-octene, 1-decene, 1-dodecene and the like. Among these, propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene and 1-octene are preferable because of their availability.
  • the ethylene / ⁇ -olefin copolymer may be a random copolymer or a block copolymer, but a random copolymer is preferred from the viewpoint of flexibility.
  • the ethylene / ⁇ -olefin copolymer is an aromatic vinyl compound such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o, p-dimethylstyrene, methoxystyrene, vinylbenzoic acid, vinyl.
  • Styrenes such as methyl benzoate, vinyl benzyl acetate, hydroxystyrene, p-chlorostyrene, divinylbenzene; 3-phenylpropylene, 4-phenylpropylene, ⁇ -methylstyrene, cyclic olefins having 3 to 20 carbon atoms, such as , Cyclopentene, cycloheptene, norbornene, 5-methyl-2-norbornene and the like may be used in combination.
  • the polymerization of the ethylene / ⁇ -olefin copolymer can be carried out by any of the conventionally known gas phase polymerization methods, liquid phase polymerization methods such as slurry polymerization methods, solution polymerization methods, metallocene catalysts, Ziegler-Natta catalysts, Polymerization can be performed using a conventionally known olefin polymerization catalyst such as a vanadium catalyst.
  • the ethylene / ⁇ -olefin copolymer may be a copolymer comprising ethylene, an ⁇ -olefin having 3 to 20 carbon atoms, and a non-conjugated polyene.
  • the ⁇ -olefin is the same as described above, and examples of the non-conjugated polyene include 5-ethylidene-2-norbornene (ENB), 5-vinyl-2-norbornene (VNB), and dicyclopentadiene (DCPD). These non-conjugated polyenes can be used alone or in combination of two or more.
  • the ethylene / ⁇ -olefin copolymer preferably satisfies the following requirements a1 and a2.
  • the density of the ethylene / ⁇ -olefin copolymer measured in accordance with ASTM D1505 is preferably 0.865 g / cm 3 or more and 0.884 g / cm 3 or less, more preferably 0.866 g / cm 3. 3 or more and 0.883 g / cm 3 or less, more preferably 0.866 g / cm 3 or more and 0.880 g / cm 3 or less, and particularly preferably 0.867 g / cm 3 or more and 0.880 g / cm 3 or less.
  • the density of the ethylene / ⁇ -olefin copolymer can be adjusted by a balance between the content ratio of ethylene units and the content ratio of ⁇ -olefin units. That is, when the content ratio of the ethylene unit is increased, the crystallinity is increased and a high density ethylene / ⁇ -olefin copolymer can be obtained. On the other hand, when the content ratio of the ethylene unit is lowered, the crystallinity is lowered and an ethylene / ⁇ -olefin copolymer having a low density can be obtained.
  • the density of the ethylene / ⁇ -olefin copolymer is not more than the above upper limit, the crystallinity is lowered and the transparency can be increased. Furthermore, extrusion molding at low temperature becomes easy, and for example, extrusion molding can be performed at 130 ° C. or lower. For this reason, even if a cross-linking agent is kneaded into the ethylene / ⁇ -olefin copolymer, the cross-linking reaction in the extruder is prevented from progressing, the generation of gel-like foreign matters on the sealing sheet is suppressed, and the appearance of the sheet is improved. Deterioration can also be suppressed. *
  • the density of the ethylene / ⁇ -olefin copolymer is not less than the above lower limit, the crystallization speed of the ethylene / ⁇ -olefin copolymer can be increased, so that the sheet extruded from the extruder is not sticky, and cooling Peeling with a roll becomes easy and a sealing sheet can be obtained easily. Further, since stickiness is less likely to occur in the sheet, the occurrence of blocking can be suppressed, and the sheet feedability can be improved. Moreover, since it is fully bridge
  • Requirement a2 The melt flow rate (MFR) of the ethylene / ⁇ -olefin copolymer measured in accordance with ASTM D1238 and at a temperature of 190 ° C. and a load of 2.16 kg is usually 0.1 g / 10 min or more and 50 g / 10 g or less, preferably 2 g / 10 min or more and 40 g / 10 min or less, more preferably 2 g / 10 min or more and 30 g / 10 min or less, further preferably 5 g / 10 min or more and 10 g / 10 min or less. It is.
  • the MFR of the ethylene / ⁇ -olefin copolymer can be adjusted by adjusting the polymerization temperature during the polymerization reaction, the polymerization pressure, and the molar ratio between the ethylene and ⁇ -olefin monomer concentrations and the hydrogen concentration in the polymerization system. can do.
  • the MFR is 0.1 g / 10 min or more and less than 10 g / 10 min
  • a sheet can be produced by calendar molding.
  • the MFR is 0.1 g / 10 min or more and less than 10 g / 10 min
  • the flowability of the resin composition containing the ethylene / ⁇ -olefin copolymer is low. This is preferable in that the laminating apparatus can be prevented from being soiled by the resin.
  • the MFR is 2 g / 10 min or more, preferably the MFR is 10 g / 10 min or more, the fluidity of the resin composition containing the ethylene / ⁇ -olefin copolymer is improved, and the productivity at the time of sheet extrusion molding is improved. Can be improved.
  • the MFR is 50 g / 10 min or less, the molecular weight increases, and therefore, adhesion to a roll surface such as a chill roll can be suppressed. Therefore, peeling is unnecessary, and a sheet having a uniform thickness can be formed. Furthermore, since it becomes a resin composition with “koshi”, a thick sheet of 0.1 mm or more can be easily formed.
  • the crosslinking characteristic at the time of laminate molding of the solar cell module is improved, it is possible to sufficiently crosslink and suppress a decrease in heat resistance.
  • the MFR is 27 g / 10 min or less, the draw-down during sheet forming can be further suppressed, a wide sheet can be formed, the cross-linking characteristics and heat resistance are further improved, and the best sealing sheet is obtained. Can do.
  • the influence of the decomposition of the crosslinking agent is small in the melt extrusion step, so that the MFR is 0.1 g / 10 min or more and less than 10 g / 10 min, preferably A sheet can also be obtained by extrusion molding using a resin composition of 0.5 g / 10 min or more and less than 8.5 g / 10 min.
  • a resin composition having an MFR of 0.1 g / 10 min or more and less than 10 g / 10 min is used.
  • the ethylene / ⁇ -olefin copolymer preferably further satisfies the following requirement a3.
  • Requirement a3 The content ratio of the structural unit derived from ethylene contained in the ethylene / ⁇ -olefin copolymer is 80 mol% or more and 90 mol% or less, preferably 80 mol% or more and 88 mol% or less, more preferably 82 mol% or more and 88 mol%. % Or less, more preferably 82 mol% or more and 87 mol% or less.
  • the proportion of structural units derived from an ⁇ -olefin having 3 to 20 carbon atoms (hereinafter also referred to as “ ⁇ -olefin unit”) contained in the ethylene / ⁇ -olefin copolymer is 10 mol% or more and 20 mol% or less, Preferably they are 12 mol% or more and 20 mol% or less, More preferably, they are 12 mol% or more and 18 mol% or less, More preferably, they are 13 mol% or more and 18 mol% or less.
  • the resulting sealing sheet has excellent transparency. Further, extrusion molding at a low temperature can be easily performed, and for example, extrusion molding at 130 ° C. or lower is possible. Therefore, even when a cross-linking agent is kneaded into the ethylene / ⁇ -olefin copolymer, it is possible to suppress the progress of the cross-linking reaction in the extruder, and a gel-like foreign matter is generated on the sealing sheet. The appearance can be prevented from deteriorating. Moreover, since moderate softness
  • the crystallization speed of the ethylene / ⁇ -olefin copolymer becomes appropriate, so that it is extruded from the extruder.
  • the sheet is not sticky, can be easily peeled off by a cooling roll, and a sealing sheet can be obtained efficiently. Further, since no stickiness is generated on the sheet, blocking can be prevented, and the sheet feeding property is good. In addition, a decrease in heat resistance can be prevented.
  • the ethylene / ⁇ -olefin copolymer can be produced using a Ziegler compound, a vanadium compound, a metallocene compound or the like as a catalyst. Among them, it is preferable to produce using various metallocene compounds shown below as catalysts.
  • the metallocene compound for example, the metallocene compounds described in JP-A-2006-077261, JP-A-2008-231265, JP-A-2005-314680 and the like can be used. However, a metallocene compound having a structure different from the metallocene compounds described in these patent documents may be used, or two or more metallocene compounds may be used in combination.
  • the polymerization of the ethylene / ⁇ -olefin copolymer can be carried out by any of the conventionally known gas phase polymerization methods and liquid phase polymerization methods such as slurry polymerization methods and solution polymerization methods. Preferably, it is carried out by a liquid phase polymerization method such as a solution polymerization method.
  • the melt flow rate (MFR) of the ethylene / vinyl acetate copolymer is preferably 5 g / 10 min to 50 g / 10 min, more preferably 5 g / 10 min to 30 g / 10 min, and still more preferably It is 5 g / 10 min or more and 25 g / 10 min 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 MFR of the ethylene / vinyl acetate copolymer is measured under conditions of 190 ° C. and a load of 2.16 kg in accordance with ASTM D1238.
  • the content of 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 K7192: 1999. Specifically, the vinyl acetate content was determined by dissolving the sample in xylene, hydrolyzing the acetate group with an alcohol solution of potassium hydroxide, adding excess sulfuric acid or hydrochloric acid, and adding dropwise with a standard sodium hydroxide solution. It can be measured by quantification.
  • 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, 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 method for producing the ethylene / vinyl acetate copolymer is not particularly limited, and can be produced by a known method. For example, in the presence of a radical generator, at 500 to 4000 atm and 100 to 300 ° C., in the presence or absence of a solvent or a chain transfer agent, ethylene, vinyl acetate, and other copolymerization components as necessary are copolymerized. It can be produced by polymerization.
  • an ethylene / ⁇ -olefin copolymer or an ethylene / vinyl acetate copolymer may be used alone, or may be blended.
  • the total amount of ethylene / ⁇ -olefin copolymer and ethylene / vinyl acetate copolymer is 100 parts by mass.
  • the ethylene / ⁇ -olefin copolymer is preferably 50 to 99 parts by mass, the ethylene / vinyl acetate copolymer is preferably 1 to 50 parts by mass, and the ethylene / ⁇ -olefin copolymer is preferably More preferably, it is 50 to 98 parts by mass, more preferably 2 to 50 parts by mass of ethylene / vinyl acetate copolymer, and still more preferably 50 to 95 parts by mass of ethylene / ⁇ -olefin copolymer.
  • the ethylene / vinyl acetate copolymer is 5 parts by weight or more and 50 parts by weight or less, and the ethylene / ⁇ -olefin copolymer is 5 parts by mass or more 95 parts by mass or less, and particularly preferably an ethylene-vinyl acetate copolymer is less than 25 parts by mass 5 parts by mass or more.
  • the sealing sheet in this embodiment may contain a silane coupling agent.
  • the content of the silane coupling agent in the sealing sheet is preferably 0.1 parts by mass or more and 2 parts by mass or less, more preferably 0.1 parts by mass or more and 1. 8 parts by mass or less, more preferably 0.1 parts by mass or more and 1.5 parts by mass or less. It can suppress that a bubble generate
  • the adhesive strength between the sealing sheet and other members can be made better.
  • the silane coupling agent is below the above upper limit, methanol and ethanol generated by hydrolysis derived from the methoxy group and ethoxy group of the silane coupling agent are reduced, and bubbles are more reliably generated in the sealing sheet. Can be suppressed.
  • silane coupling agent examples include vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxysilane), 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 3-glycidoxypropylmethyl.
  • the sealing sheet in this embodiment may contain a crosslinking agent.
  • the crosslinking agent preferably used for the encapsulating sheet in this embodiment is an organic material having a half-life temperature of 100 to 170 ° C. for 1 minute from the balance between productivity in extrusion sheet molding and crosslinking speed in laminate molding of a solar cell module. Peroxides are preferred. When the one-minute half-life temperature of the organic peroxide is 100 ° C. or higher, sheet molding can be facilitated and the appearance of the sheet can be improved. In addition, the dielectric breakdown voltage can be prevented from being lowered, moisture permeability can be prevented from being lowered, and adhesiveness is further improved.
  • the one-minute half-life temperature of the organic peroxide is 170 ° C. or lower, it is possible to suppress a decrease in the crosslinking rate when the solar cell module is laminated, and thus it is possible to prevent a decrease in the productivity of the solar cell module. Moreover, the heat resistance of a sealing sheet and the fall of adhesiveness can also be prevented.
  • Organic peroxides having a 1 minute half-life temperature in the range of 100 to 170 ° C. include dilauroyl peroxide, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, and dibenzoylperoxide.
  • Oxide 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-amylperoxy) cyclohexane, t-amylperoxyisononanoate, t-amylperoxynormal octoate, 1 , 1-Di (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-butylpero C) Cyclohexane, t-butylperoxyisopropyl carbonate, t-butylperoxy-2-ethylhexyl carbonate, 2,5-dimethyl-2,5-di (benzoy
  • dilauroyl peroxide t-butyl peroxyisopropyl carbonate, t-butyl peroxyacetate, t-butyl peroxyisononanoate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxybenzoate It is preferable to use 1 type, or 2 or more types selected from.
  • the sealing sheet in the present embodiment has an excellent crosslinking property 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.
  • the content of the crosslinking agent in the sealing sheet is preferably 0.1 parts by mass or more and 3 parts by mass or less, more preferably 0.2 parts by mass or more and 2 parts by mass or less with respect to 100 parts by mass of the crosslinkable resin. Yes, more preferably 0.2 parts by mass or more and 1.5 parts by mass or less.
  • the content of the cross-linking agent is not less than the above lower limit value, the deterioration of the cross-linking properties of the sealing sheet is suppressed, the graft reaction of the silane coupling agent to the main chain of the cross-linkable resin is improved, and the heat resistance and adhesion Deterioration 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 suppressed more reliably. .
  • the resin composition constituting the encapsulating sheet in this embodiment may contain one or more additives selected from the group consisting of an ultraviolet absorber, a light stabilizer, and a heat stabilizer. preferable.
  • the 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 crosslinkable resin. By making it within this range, the effect of improving the resistance to constant temperature and humidity, heat cycle resistance, weather resistance stability, and heat resistance 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-4- 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; one or more selected from salicylic acid ester ultraviolet absorbers such as phenyl salicylate and p-octylphenyl salicylate may be used. it can.
  • Examples of the light stabilizer include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, 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)
  • One or more selected from hindered amine compounds such as imino ⁇ ], hindered piperidine compounds, and the like can be used.
  • heat stabilizers 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 heat stabilizers such as phyto; Lactone heat stabilizers 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 sealing sheet in this embodiment contains a crosslinking aid.
  • the content of the crosslinking aid in the sealing sheet is preferably 0.05 parts by mass or more and 5 parts by mass or less, and 0.1 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the crosslinkable resin. More preferably, it is more preferably 0.2 parts by mass or more and 2 parts by mass or less. Thereby, it can be set as a moderate crosslinked structure and can improve the heat resistance of a sealing sheet, a mechanical physical property, and adhesiveness.
  • a compound having two or more double bonds in the molecule can be used.
  • t-butyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, 2-methoxyethyl acrylate, ethyl carbitol acrylate Monoacrylates such as methoxytripropylene glycol acrylate; monomethacrylates such as t-butyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, methoxyethylene glycol methacrylate, methoxypolyethylene glycol methacrylate; 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate, Diacrylates such as ethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate
  • Triacrylate Triacrylate; trimethacrylate such as trimethylolpropane trimethacrylate and trimethylolethane trimethacrylate; tetraacrylate such as pentaerythritol tetraacrylate and tetramethylolmethane tetraacrylate; divinyl aromatic compound such as divinylbenzene and di-i-propenylbenzene; Cyanurates such as triallyl cyanurate and triallyl isocyanurate; diallyl compounds such as diallyl phthalate; triallyl compounds; oximes such as p-quinonedioxime and pp′-dibenzoylquinonedioxime; maleimides such as phenylmaleimide One kind or two or more kinds selected can be used.
  • triacrylates such as diacrylate, dimethacrylate, divinyl aromatic compound, trimethylolpropane triacrylate, tetramethylolmethane triacrylate, pentaerythritol triacrylate; trimethylolpropane trimethacrylate, trimethylolethanetri Trimethacrylates such as methacrylate; tetraacrylates such as pentaerythritol tetraacrylate and tetramethylolmethane tetraacrylate; cyanurates such as triallyl cyanurate and triallyl isocyanurate; diallyl compounds such as diallyl phthalate; triallyl compounds; p-quinonedioxime; selected from oximes such as pp'-dibenzoylquinonedioxime; maleimides such as phenylmaleimide It is preferable to use one kind or two or more kinds. Further, among these, triallyl isocyan
  • the crosslinking aid may contain a copper element resulting from the raw material or the manufacturing process, and may increase the copper element in the sealing sheet.
  • some triallyl isocyanurates contain a copper element exceeding 0.1 ppm, and when added to a sealing sheet, the copper element content may exceed 1.0 ppb.
  • the triallyl isocyanurate is preferably one having an amount of copper element of 0.01 ppm or less. The amount of elemental copper in triallyl isocyanurate can be measured by ICP emission analysis.
  • the sealing sheet in 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.
  • examples include various polyolefins other than the crosslinkable resin, styrene-based, ethylene-based block copolymers, and propylene-based polymers. These may be contained in an amount of 0.0001 to 50 parts by mass, preferably 0.001 to 40 parts by mass with respect to 100 parts by mass of the crosslinkable resin.
  • the above additives can be appropriately contained.
  • the thickness of the sealing sheet in this embodiment 0.01 mm or more and 2 mm or less are preferable, More preferably, it is 0.05 mm or more and 1.5 mm or less, More preferably, it is 0.1 mm or more and 1.2 mm or less, More preferably, it is 0.00. 2 mm or more and 1 mm or less, particularly preferably 0.3 mm or more and 0.9 mm or less, and particularly preferably 0.3 mm or more and 0.8 mm or less.
  • 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.
  • the solar cell module can be laminated at a low temperature.
  • the sealing sheet in the present embodiment may have layers such as a hard coat layer for protecting the front surface or the back surface, an adhesive layer, an antireflection layer, a gas barrier layer, and an antifouling layer. If classified by material, 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.
  • Method for producing sealing sheet Although the manufacturing method of the sealing sheet in 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 sheet molding and calendar molding are preferred.
  • a crosslinkable resin and, if necessary, one or more additives selected from a silane coupling agent, a crosslinking agent, a crosslinking aid, an ultraviolet absorber, a light stabilizer, and a heat stabilizer prepare.
  • content of a copper element is 1.0 ppb or less.
  • the content of the copper element contained in one or more selected from the crosslinkable resin and the additive is reduced.
  • the content of copper element contained in the crosslinking aid is reduced. More preferably, the content of copper element contained in triallyl isocyanurate is reduced.
  • content of the copper element in the sealing sheet in this embodiment can be 1.0 ppb or less.
  • a method of reducing the content of copper element contained in a crosslinking aid such as triallyl isocyanurate a method of removing with a ligand (EDTA etc.) that forms a chelate complex with copper, a method of removing with an ion exchange resin Etc.
  • the content of the copper element in the crosslinkable resin can be measured, for example, by wet decomposition of the crosslinkable resin, then constant volume with pure water, and ICP emission analysis using an ICP emission analyzer.
  • the content of copper element in each additive can be measured, for example, by ICP emission analysis using an ICP emission analyzer.
  • Ethylene / ⁇ -olefin copolymers and ethylene-vinyl acetate copolymers which are crosslinkable resins, are often polymerized using a high-pressure radical method, a titanium catalyst / metallocene catalyst, and rarely contain copper element.
  • a high-pressure radical method a titanium catalyst / metallocene catalyst
  • copper element when the content of copper element is large, for example, purification such as deashing operation with acid or alkali, reprecipitation operation with poor solvent, etc., to reduce the content of copper element in the crosslinkable resin. Is preferred.
  • various additives may contain the metal element resulting from the raw material and manufacturing process, and increase the quantity of the copper element in a sealing sheet.
  • various additives are purified by, for example, a deashing operation with an acid or an alkali or a reprecipitation operation with a poor solvent to reduce the content of copper element in the various additives.
  • the decalcification operation with an acid or alkali and the reprecipitation operation with a poor solvent can be generally performed according to a known method.
  • a crosslinkable resin and, if necessary, one or more additives selected from silane coupling agents, crosslinking agents, crosslinking assistants, ultraviolet absorbers, light stabilizers, and heat stabilizers Dry blend.
  • 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.
  • 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 extrusion temperature range is preferably 100 ° C or higher and 130 ° C or lower.
  • the productivity of the sealing sheet can be improved.
  • the extrusion temperature is 130 ° C. or lower, gelation is unlikely to occur when the resin composition is formed into a sheet with an extruder to obtain a sealing sheet. Therefore, an increase in the torque of the extruder can be prevented and sheet forming can be facilitated.
  • seat the fall of an external appearance can be prevented.
  • the sealing sheet in 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 in 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 structure and material of the electrode used for a solar cell module are not specifically limited, In a specific example, it has a laminated structure of a transparent conductive film and a metal film.
  • the transparent conductive film is made of SnO 2 , ITO, ZnO or the like.
  • the metal film is made of a metal such as silver, gold, copper, tin, aluminum, cadmium, zinc, mercury, chromium, molybdenum, tungsten, nickel, and vanadium. These metal films may be used alone or as a composite alloy.
  • the transparent conductive film and the metal film are formed by a method such as CVD, sputtering, or vapor deposition.
  • the metal contained in the electrode is silver, that is, when the electrode is a silver electrode, a phenomenon that silver migrates in the sealing sheet is particularly likely to occur. Therefore, when an electrode is a silver electrode, the effect of the sealing sheet in this embodiment can be acquired especially effectively.
  • the manufacturing method of the solar cell module in this embodiment is not specifically limited, For example, the following method is mentioned.
  • a plurality of solar cell elements 13 electrically connected using the interconnector 16 are sandwiched between a pair of light receiving surface side sealing sheets 11 and a back surface side sealing sheet 12, and further, these light receiving surface side sealing sheet sheets 11 and The back side sealing sheet 12 is sandwiched between the front side transparent protective member 14 and the back side protective member 15 to produce a laminate.
  • 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.
  • a sealing sheet is prepared in advance, and is bonded at a temperature at which the sealing sheet melts.
  • a temperature at which the sealing sheet melts For example, at a lamination temperature of 145 to 170 ° C. and a vacuum pressure of 10 Torr or less. Heat for 0.5-10 minutes under vacuum.
  • pressurization by atmospheric pressure is performed for about 2 to 30 minutes, and a module having the configuration as described above can be formed.
  • the encapsulating sheet has excellent cross-linking properties by containing a specific cross-linking agent, and it is not necessary to go through a two-step bonding process in forming the module, and it can be completed at a high temperature in a short time. And the productivity of the module can be greatly improved.
  • the module is produced by heating at 120 to 170 ° C. for 1 to 120 minutes. It is also possible.
  • the copper element content of triallyl isocyanurate was 0.01 ppm or less.
  • the copper element content of other additives was also 0.01 ppm or less.
  • Triallyl isocyanurate was purified before use, and the copper element content was reduced to 0.01 ppm or less.
  • extrusion molding is performed from a coat hanger type T die under the condition of a die temperature of 110 ° C., and the roll temperature is 25 ° C. Molding was performed at 0.7 m / min. The maximum thickness tmax of the sheet was 450 ⁇ m. Content of the copper element in the obtained sealing sheet was 1.0 ppb or less.
  • Ethylene / ⁇ -olefin copolymer which is a crosslinkable resin ( ⁇ -olefin: 1-butene, density: 0.870 g / cm 3 , MFR: 20 g / 10 min, content ratio of structural units derived from ethylene: 86 mol% , Ratio of structural unit derived from ⁇ -olefin: 14 mol%, synthesized according to Synthesis Example 1 described in paragraph 0178 of WO2012 / 046456.)
  • T-Butylperoxy-2 as a crosslinking agent with respect to 100 parts by mass -0.7 parts by weight of ethylhexyl carbonate, 0.4 parts by weight of 3-methacryloxypropyltrimethoxysilane as a silane coupling agent, and 0.2 parts by weight of 2-hydroxy-4-normal-octyloxybenzophenone as an ultraviolet absorber Bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate as
  • Example 1 A sealing sheet was produced in the same manner as in Example 1 except that triallyl isocyanurate (copper element content 0.63 ppm, unrefined product) was used as a crosslinking aid. Content of the copper element in the obtained sealing sheet was 7.6 ppb.
  • FIG. 2 shows an enlarged photograph of the electrode in which a decrease in resistance was observed. Aggregation called dendrites was observed between the electrodes, confirming that conduction was occurring.

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PCT/JP2015/075091 2014-09-30 2015-09-03 封止シート、太陽電池モジュールおよび封止シートの製造方法 WO2016052070A1 (ja)

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WO2024014812A1 (ko) * 2022-07-11 2024-01-18 주식회사 엘지화학 올레핀계 공중합체용 가교제 조성물, 이를 포함하는 광소자용 봉지재 조성물 및 광소자용 봉지재 필름

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