WO2018180483A1 - Composition de résine, feuille, matériau d'étanchéité de pile solaire, module de pile solaire, et procédé de production de feuille pour matériau d'étanchéité de pile solaire - Google Patents

Composition de résine, feuille, matériau d'étanchéité de pile solaire, module de pile solaire, et procédé de production de feuille pour matériau d'étanchéité de pile solaire Download PDF

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WO2018180483A1
WO2018180483A1 PCT/JP2018/009877 JP2018009877W WO2018180483A1 WO 2018180483 A1 WO2018180483 A1 WO 2018180483A1 JP 2018009877 W JP2018009877 W JP 2018009877W WO 2018180483 A1 WO2018180483 A1 WO 2018180483A1
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solar cell
sheet
copolymer
ethylene
propylene
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PCT/JP2018/009877
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English (en)
Japanese (ja)
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洸哉 吉本
野田　公憲
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三井化学株式会社
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Priority to JP2019509219A priority Critical patent/JP6898426B2/ja
Publication of WO2018180483A1 publication Critical patent/WO2018180483A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • 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 resin composition and a sheet, and particularly to a resin composition and a sheet suitable for a solar cell encapsulant.
  • Solar cells are attracting attention as an energy source that is clean and has no risk of exhaustion.
  • 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.
  • a solar cell module generally protects both sides of a solar cell element such as silicon, gallium-arsenic, copper-indium-selenium with a solar cell encapsulant, and the encapsulant is composed of an upper transparent protective material and a lower substrate protective material. Protected and packaged. For this reason, as a solar cell sealing material, high transparency is calculated
  • Patent Document 1 discusses the use of a resin composition containing an ethylene / ⁇ -olefin copolymer as a solar cell sealing material.
  • a resin composition containing an ethylene / ⁇ -olefin copolymer as a solar cell sealing material.
  • an ethylene / 1-butene copolymer and an ethylene / 1-octene copolymer are described.
  • Patent Document 1 a low-density ethylene / ⁇ -olefin copolymer is used to improve transparency.
  • Patent Document 2 discusses the use of a resin composition containing an ethylene / ⁇ -olefin copolymer and an ethylene-functional group-containing monomer copolymer as a solar cell encapsulant.
  • a resin composition containing an ethylene / ⁇ -olefin copolymer and an ethylene-functional group-containing monomer copolymer as a solar cell encapsulant.
  • an ethylene / propylene / 1-hexene terpolymer is described.
  • an object of the present invention is to provide a resin composition capable of suitably obtaining a solar cell encapsulant having high transparency, excellent impact resistance (low density), and high strength, and the composition
  • the present invention relates to a film or sheet containing an ethylene / propylene / ⁇ -olefin copolymer [X] that satisfies the following requirement (x-1).
  • (X-1) an ⁇ -olefin having 74 to 92 mol% of the structural unit (i) derived from ethylene, 5 to 16 mol% of the structural unit (ii) derived from propylene, and having 5 to 20 carbon atoms.
  • the derived structural unit (iii) is contained in an amount of 3 to 10 mol% [provided that the total of the structural units (i), (ii) and (iii) is 100 mol%. ].
  • the film or sheet containing the ethylene / propylene / ⁇ -olefin copolymer [X] of the present invention has high transparency, excellent heat-resistant mechanical strength, and good flexibility, a solar cell encapsulant, And the solar cell module containing this solar cell sealing material can be obtained suitably.
  • the resin composition of the present invention contains an ethylene / propylene / ⁇ -olefin copolymer [X] that satisfies specific requirements.
  • the resin composition preferably contains the copolymer [X] and the organic peroxide [Y] in specific amounts.
  • (X-1) 74 to 92 mol%, preferably 76 to 90 mol% of the structural unit (i) derived from ethylene, and 5 to 16 mol%, preferably 7 to 16 mol of the structural unit (ii) derived from propylene.
  • the ethylene / propylene / ⁇ -olefin copolymer [X] includes a structural unit derived from ethylene, a structural unit derived from propylene, and a structural unit derived from an ⁇ -olefin having 5 to 20 carbon atoms. By including in a range, a film or sheet having high transparency, excellent mechanical strength, and good flexibility can be obtained.
  • Examples of the ⁇ -olefin having 5 to 20 carbon atoms constituting the ethylene / propylene / ⁇ -olefin copolymer [X] according to the present invention include 1-pentene, 3-methyl-1-butene, 1-hexene, 4 -Methyl-1-pentene, 3-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicosene and the like. Of these, 1-hexene, 4-methyl-1-pentene and 1-octene are preferred.
  • the type of ⁇ -olefin constituting the copolymer [X] according to the present invention is clear depending on the type of ⁇ -olefin used in the production of the copolymer [X].
  • the ⁇ -olefin content can be quantified using the method described in the Examples.
  • the ethylene / propylene / ⁇ -olefin copolymer [X] according to the present invention preferably has the following requirements (x-2) and (x-3).
  • the lower limit of the density of the (x-2) according to the density present invention copolymer [X] is, 850kg / m 3, preferably 855kg / m 3.
  • the upper limit of the density is 900 kg / m 3 , preferably 895 kg / m 3 , more preferably 890 kg / m 3 .
  • the density of the copolymer [X] is a value measured at 23 ° C. according to ASTM D1505. The density value can be adjusted by selecting the type and content of the comonomer in the copolymer [X].
  • the MFR of the copolymer [X] according to the present invention has a melt flow rate (MFR, ASTM D1238) at 190 ° C. and a load of 2.16 kg, preferably 0.1 to 50 g / 10 min, more preferably 0. .1 to 40 g / 10 min, more preferably 0.1 to 30 g / 10 min.
  • the ethylene / propylene / ⁇ -olefin copolymer [X] according to the present invention preferably further has the following requirement (x-4) and requirement (x-5).
  • the copolymer [X] according to the present invention has a molecular weight distribution (Mw / Mn) represented by a ratio of the weight average molecular weight (Mw) and the number average molecular weight (Mn), preferably 3.0 or less, More preferably, it is 2.5 or less.
  • Mw and Mn are EPR converted values measured by gel permeation chromatography (GPC). The EPR conversion is as described in the examples.
  • the copolymer [X] having Mw / Mn in the above range is preferable in terms of blocking resistance.
  • the weight average molecular weight (Mw) (EPR conversion) of the copolymer [X] is not particularly limited as long as the effect of the present invention is exhibited, but is preferably 10,000 or more, more preferably 20000 or more, and further preferably 30000 or more.
  • the ethylene / propylene / ⁇ -olefin copolymer [X] according to the present invention more preferably has the following requirement (x-6).
  • Unsaturated bond amount Unsaturated bonds that can be included in the copolymer [X] include the following vinyl type double bonds, vinylidene type double bonds, disubstituted olefin type double bonds and A trisubstituted olefin type double bond is mentioned. The content of these unsaturated bonds can be determined by 1 H-NMR.
  • the copolymer [X] has a vinyl type double bond (vinyl group) and a vinylidene type double bond (vinylidene group) per 1000 carbon atoms determined by 1 H-NMR measurement.
  • a double bond is also referred to as a molecular terminal double bond), a disubstituted olefin type double bond, and a trisubstituted olefin type double bond (in the present invention, these double bonds are also referred to as internal molecular double bonds).
  • the total content of is usually less than 0.40, preferably less than 0.38, and more preferably less than 0.35.
  • the content of the molecular terminal double bond and the internal double bond in the copolymer [X] is in the above range, the generation of fish eyes during film / sheet formation can be reduced, and the yield is high.
  • the copolymer [X] a sheet having excellent mechanical strength or a sheet for solar cell encapsulating material can be suitably obtained.
  • the copolymer [X] having Mw in the above range has a good balance between film / sheet moldability and mechanical strength.
  • High transparency and good film / sheet moldability can be obtained by using the copolymer [X] having a density and Mw within the above ranges.
  • ⁇ Method for producing ethylene / propylene / ⁇ -olefin copolymer [X] is not limited as long as it has the above-described properties.
  • copolymer [X] is obtained by copolymerizing ethylene, propylene and an ⁇ -olefin having 5 to 20 carbon atoms in the presence of an olefin polymerization catalyst containing catalyst components [A] and [B]. Can be manufactured.
  • the catalyst component [A] is a metallocene compound represented by the general formula [I].
  • M is a transition metal
  • p represents the valence of the transition metal
  • X may be the same or different, and each independently represents a hydrogen atom, a halogen atom or a hydrocarbon group
  • R 1 and R 2 are each independently a ⁇ -electron conjugated ligand coordinated to M.
  • transition metal represented by M examples include Zr, Ti, Hf, V, Nb, Ta, and Cr. Preferred transition metals are Zr, Ti, or Hf, and more preferred transition metals are Zr or Hf. is there.
  • Examples of the ⁇ -electron conjugated ligand represented by R 1 and R 2 include a ⁇ -cyclopentadienyl structure, ⁇ -benzene structure, ⁇ -cycloheptatrienyl structure, and ⁇ -cyclooctatetraene structure.
  • a particularly preferred ligand is a ligand having a ⁇ -cyclopentadienyl structure.
  • Examples of the ligand having an ⁇ -cyclopentadienyl structure include a cyclopentadienyl group, an indenyl group, a hydrogenated indenyl group, and a fluorenyl group.
  • These groups are further substituted with halogen atoms; hydrocarbon groups such as alkyl, aryl and aralkyl; oxygen atom-containing groups such as alkoxy groups and aryloxy groups; hydrocarbon-containing silyl groups such as trialkylsilyl groups, and the like. May be.
  • Examples of the catalyst component [A] include bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, but are not limited to the above compounds. Such a catalyst component [A] is preferably used as a catalyst for olefin polymerization together with the catalyst component [B].
  • the catalyst component [B] is selected from (b-1) an organoaluminum oxy compound, (b-2) a compound that reacts with the catalyst component [A] to form an ion pair, and (b-3) an organoaluminum compound. At least one compound.
  • the catalyst component [B] [1] Only organoaluminum oxy compound (b-1), [2] Organoaluminum oxy compound (b-1) and organoaluminum compound (b-3), [3] Compound (b-2) and organoaluminum compound (b-3), [4] It is preferably used in any embodiment of the organoaluminum oxy compound (b-1) and the compound (b-2).
  • Organic aluminum oxy compound (b-1) As the organoaluminum oxy compound (b-1), a conventionally known aluminoxane can be used as it is. Specifically, the compound represented by general formula [II] and / or general formula [III] is mentioned.
  • R is a hydrocarbon group having 1 to 10 carbon atoms, and n is an integer of 2 or more.
  • methylaluminoxane in which R is a methyl group and n is 3 or more, preferably 10 or more, is suitably used.
  • the organoaluminum oxy compound in which R is a methyl group may be hereinafter referred to as “methylaluminoxane”.
  • organoaluminum oxy compound (b-1) it is also preferable to use a methylaluminoxane analogue that dissolves in a saturated hydrocarbon, and examples thereof include a modified methylaluminoxane represented by the general formula [IV].
  • R is a hydrocarbon group having 2 to 20 carbon atoms, and m and n are integers of 2 or more.
  • the modified methylaluminoxane represented by the formula [IV] is prepared using, for example, trimethylaluminum and an alkylaluminum other than trimethylaluminum, and prepared using a trimethylaluminum and triisobutylaluminum from a manufacturer such as Tosoh Finechem, Those in which R is an isobutyl group are commercially produced under trade names such as MMAO and TMAO.
  • organoaluminum oxy compound (b-1) a benzene insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 may be used, which contains boron represented by the general formula [V].
  • An organoaluminum oxy compound may be used.
  • R c is a hydrocarbon group having 1 to 10 carbon atoms
  • R d may be the same or different from each other, and is a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. It is a group.
  • the organoaluminum oxy compound (b-1) may be used alone or in combination of two or more. Note that a slight amount of organoaluminum compound may be mixed in the organoaluminum oxy compound (b-1).
  • JP-A-1-501950 discloses a compound (b-2) that reacts with the catalyst component [A] to form an ion pair (hereinafter sometimes abbreviated as “ionic compound (b-2)”).
  • ionic compound (b-2) Lewis acids described in JP-A-1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc.
  • Ionic compounds, borane compounds and carborane compounds examples of the ionic compound (b-2) include heteropoly compounds and isopoly compounds.
  • the ionic compound (b-2) is preferably a compound represented by the general formula [VI].
  • examples of R e + include H + , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, and ferrocenium cation having a transition metal.
  • R f to R i may be the same as or different from each other, and are organic groups, preferably aryl groups.
  • carbenium cation examples include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.
  • ammonium cations include trialkylammonium cations, triethylammonium cations, tri (n-propyl) ammonium cations, triisopropylammonium cations, tri (n-butyl) ammonium cations, triisobutylammonium cations, and the like, N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexylammonium Examples thereof include dialkylammonium cations such as cations.
  • phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.
  • R e + a carbenium cation and an ammonium cation are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.
  • ionic compound (b-2) which is a carbenium salt examples include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoro).
  • Examples thereof include methylphenyl) borate, tris (4-methylphenyl) carbenium tetrakis (pentafluorophenyl) borate, and tris (3,5-dimethylphenyl) carbeniumtetrakis (pentafluorophenyl) borate.
  • ionic compound (b-2) that is an ammonium salt examples include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, and dialkylammonium salts.
  • ionic compound (b-2) which is a trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p -Tolyl) borate, trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate , Tripropylammonium tetrakis (2,4-dimethylphenyl) borate, tri (n-butyl) ammonium tetra
  • ionic compound (b-2) that is an N, N-dialkylanilinium salt include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N- Diethylanilinium tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis ( Pentafluorophenyl)
  • dialkylammonium salt examples include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.
  • an ionic compound disclosed by the present applicant Japanese Patent Laid-Open No. 2004-516766 can also be used without limitation.
  • the ionic compound (b-2) may be used alone or in combination of two or more.
  • Organoaluminum compound (b-3) examples include an organoaluminum compound represented by the general formula [VII] and a complex alkylated product of a group 1 metal of the periodic table represented by the general formula [VIII] and aluminum. It is done.
  • organoaluminum compound represented by the formula [VII] include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum and trioctylaluminum; triisopropylaluminum, triisobutyl Tri-branched alkyl aluminums such as aluminum, tri-sec-butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricyclohexylaluminum, tricyclooctylaluminum, etc.
  • tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum and trioctylaluminum
  • Tricycloalkylaluminum Triarylaluminum such as triphenylaluminum and tolylylaluminum; diisopropylaluminum hydra Id, dialkylaluminum hydride such as diisobutylaluminum hydride; formula (iC 4 H 9) x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, is z ⁇ 2x ) Alkenyl aluminum such as isoprenyl aluminum, etc .; Alkyl aluminum alkoxide such as isobutylaluminum methoxide and isobutylaluminum ethoxide; Dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; formula R a 2.5 Al (OR b) partially alkoxylated alkyl aluminum having an average composition represented by 0.5
  • Dialkylaluminum halides alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; partially halogenated alkylaluminums such as alkylaluminum dihalides such as ethylaluminum dichloride; diethylaluminum hydride Dialkylaluminum hydrides such as dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as alkylaluminum dihydrides such as aluminum dihydride, propylaluminum dihydride; partially alkoxylated such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide and the like A halogenated alkylaluminum is mentioned.
  • M 2 is Li, Na or K
  • R a is a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms. Examples of such a compound include LiAl (C 2 H 5 ) 4 and LiAl (C 7 H 15 ) 4 .
  • a compound similar to the compound represented by the general formula [VII] can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom.
  • organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom.
  • Specific examples of such a compound include (C 2 H 5 ) 2 AlN (C 2 H 5 ) Al (C 2 H 5 ) 2 .
  • organoaluminum compound (b-3) trimethylaluminum and triisobutylaluminum are preferably used from the viewpoint of easy availability.
  • the organoaluminum compound (b-3) may be used alone or in combination of two or more.
  • the copolymer [X] can be suitably produced by copolymerizing ethylene, propylene and an ⁇ -olefin having 5 to 20 carbon atoms in the presence of the above-mentioned olefin polymerization catalyst.
  • the copolymerization is not particularly limited, but it is preferably performed by solution polymerization in the presence of an olefin polymerization catalyst at a temperature of 50 to 180 ° C. in the presence of a solvent.
  • the method of using each component and the order of addition are arbitrarily selected.
  • a method of adding the catalyst component [A] and the catalyst component [B] to the polymerization vessel in an arbitrary order can be exemplified.
  • two or more of each catalyst component may be contacted previously.
  • the catalyst component [A] is usually 10 ⁇ 9 to 1 liter of reaction volume. It can be used in an amount of 10 ⁇ 1 mol, preferably 10 ⁇ 8 to 10 ⁇ 2 mol.
  • the component (b-1) has a molar ratio [(b-1) / M] of the component (b-1) to all transition metal atoms (M) in the component [A] of usually 1 to 10,000, preferably 10 It can be used in an amount of ⁇ 5000.
  • Component (b-2) has a molar ratio [(b-2) / M] of component (b-2) to all transition metal atoms (M) in component [A], usually 0.5 to 50, The amount can be preferably 1 to 20.
  • Component (b-3) can be used in an amount of usually 0 to 5 mmol, preferably about 0 to 2 mmol, per liter of polymerization volume.
  • the charged molar ratio of ethylene, propylene and ⁇ -olefin may be appropriately selected according to the characteristics of the target copolymer [X], and is not particularly limited.
  • Solution polymerization preferably employed in the production of the copolymer [X] is a general term for a method of performing polymerization in a state where the polymer is dissolved in a hydrocarbon solvent inert to the copolymerization reaction.
  • the polymerization temperature in the solution polymerization is usually 50 to 180 ° C., preferably 70 to 150 ° C., more preferably 90 to 130 ° C.
  • the polymerization temperature is preferably in the above range from the viewpoint of polymerization activity and heat removal from the polymerization heat. Specifically, it is preferable from the viewpoint of productivity when it is at least the lower limit of the above range; it is preferable from the viewpoint of blocking resistance that it is difficult to form a branch in the polymer when it is not more than the upper limit of the above range.
  • the polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 8 MPa gauge pressure, and the copolymerization can be carried out by any of batch, semi-continuous and continuous methods.
  • the reaction time (average residence time when the copolymerization reaction is carried out in a continuous manner) varies depending on conditions such as the catalyst concentration and polymerization temperature, and can be appropriately selected, but is usually 1 minute to 3 hours, preferably 10 minutes to 2.5 hours.
  • Polymerization can be performed in two or more stages with different reaction conditions.
  • the molecular weight of the obtained copolymer [X] can also be adjusted by changing the hydrogen concentration or polymerization temperature in the polymerization system. Furthermore, it can also adjust with the quantity of the catalyst component [B] to be used. When hydrogen is added to the polymerization system, the amount is suitably about 0.001 to 5,000 NL per 1 kg of the produced copolymer [X]. Further, the density of the obtained copolymer [X] can be adjusted by the feed amount of propylene and ⁇ -olefin.
  • the solvent used in the solution polymerization is usually an inert hydrocarbon solvent, preferably a saturated hydrocarbon having a boiling point of 50 to 200 ° C. under normal pressure.
  • an inert hydrocarbon solvent preferably a saturated hydrocarbon having a boiling point of 50 to 200 ° C. under normal pressure.
  • Specific examples include aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, and kerosene; and alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane.
  • aromatic hydrocarbons such as benzene, toluene and xylene
  • halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane are also included in the category of “inert hydrocarbon solvents” and their use is not limited.
  • the copolymer [X] obtained by the polymerization reaction and other components added as desired may be melted by any method, kneaded, granulated, etc. preferable.
  • the resin composition according to the present invention is a composition containing the ethylene / propylene / ⁇ -olefin copolymer [X], and preferably contains a specific amount of the organic peroxide [Y].
  • the organic peroxide [Y] used in the present invention is a film or sheet made of the copolymer [X], or a solar cell encapsulant sheet, and a crosslinking reaction during solar cell module laminate molding. Used as a radical initiator.
  • a film or sheet having high transparency, excellent heat resistance, high mechanical strength, and good flexibility by crosslinking the copolymer [X] with an organic peroxide [Y] or a sheet for solar cell encapsulant Preferably obtained.
  • the organic peroxide [Y] is not particularly limited as long as it can crosslink the copolymer [X].
  • the organic peroxide (Y) having a half-life temperature of 1 minute of the organic peroxide (Y) in the range of 100 to 190 ° C. is preferable from the balance of the crosslinking rate at the time of module lamination molding. More preferably, the 1-minute half-life temperature is 100 to 180 ° C.
  • the one-minute half-life temperature of the organic peroxide [Y] is less than 100 ° C.
  • gel is generated in the sheet for solar cell encapsulant obtained from the resin composition at the time of extrusion sheet molding, and the torque of the extruder increases.
  • sheet forming may be difficult. Even if a sheet is obtained, unevenness may occur on the surface of the sheet due to the gel generated in the extruder, and the appearance may deteriorate.
  • a voltage is applied, cracks are generated around the gel within the sheet, and the dielectric breakdown resistance is reduced. Furthermore, moisture permeation at the gel object interface is likely to occur and moisture permeability is reduced.
  • the amount of the organic peroxide [Y] is usually 0.1 to 3 parts by weight, preferably 0.2 to 3 parts by weight, and more preferably 0.2 parts by weight with respect to 100 parts by weight of the copolymer [X]. ⁇ 2.5 parts by weight.
  • the organic peroxide [Y] is less than 0.1 part by weight, the crosslinking characteristics at the time of laminate molding of the solar cell module become insufficient, and the heat resistance and the glass adhesiveness are lowered.
  • the organic peroxide [Y] is more than 3 parts by weight, gelation occurs when a sheet or a solar cell encapsulant sheet is obtained from the resin composition with an extruder or the like, and the torque of the extruder is increased. Molding may be difficult.
  • the organic peroxide [Y] described above preferably has a one-minute half-life temperature in the range of 100 to 180 ° C.
  • dilauroyl peroxide 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, dibenzoyl peroxide, cyclohexanone peroxide, di-t-butyl perphthalate, t- Butyl hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-amylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate , T-butylperoxyisobutyrate, t-butylperoxymaleic acid, 1,1-di (t-amylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-amylper) Oxy) cyclohexane, t-amyl peroxy isononanoate, t-amyl peroxy normal octo
  • dilauroyl peroxide 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t-butylperoxyisopropyl carbonate, t-butylperoxybenzoate, t-butylperoxyacetate
  • examples thereof include t-butyl peroxyisononanoate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxybenzoate and the like.
  • the organic peroxide [Y] may be used singly or in appropriate combination of two or more.
  • the resin composition of the present invention contains an ethylenically unsaturated silane compound (C), which has good crosslinkability and excellent heat resistance, or a sheet for solar cell encapsulant. It is preferable from the point which can be obtained.
  • ethylenically unsaturated silane compound (C) conventionally known compounds can be used, and there is no particular limitation. Specifically, vinyltriethoxysilane, vinyltrimethoxysilane, vinyltris ( ⁇ -methoxyethoxysilane), ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -methacryloxypropyltrimethoxysilane Etc. can be used.
  • Preferred examples include ⁇ -glycidoxypropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane, which have good adhesion.
  • the ethylenically unsaturated silane compound (C) may be used alone or in a suitable mixture of two or more.
  • the resin composition of the present invention comprises 0.1 to 3 parts by weight of organic peroxide [Y] and 0.1 to 3 parts of ethylenically unsaturated silane compound (C) with respect to 100 parts by weight of copolymer [X].
  • a preferred embodiment contains 5 parts by weight. More preferably, the organic peroxide [Y] is 0.2 to 3 parts by weight and the ethylenically unsaturated silane compound (C) is 0.1 to 4 parts by weight with respect to 100 parts by weight of the copolymer [X]. More preferably, the organic peroxide [Y] is 0.2 to 2.5 parts by weight and the ethylenically unsaturated silane compound (C) is 0 with respect to 100 parts by weight of the copolymer [X].
  • the resin composition in the above range has good adhesion to glass and a good balance between the cost and performance of the resin composition. Further, when the sheet is formed, the surface of the sheet is not uneven due to the gel material generated in the extruder, and the appearance is improved. Moreover, even when a voltage is applied, no cracks occur and the dielectric breakdown resistance is improved. Furthermore, moisture permeability is less likely to occur. In addition, adhesion and adhesion to the glass, thin film electrode, and back sheet are also improved when the solar cell module is laminated.
  • the organic peroxide [Y] When the organic peroxide [Y] is less than 0.1 parts by weight, the crosslinking characteristics at the time of laminate molding of the solar cell module become insufficient, and the heat resistance and the glass adhesiveness are lowered.
  • the organic peroxide [Y] When the organic peroxide [Y] is more than 3 parts by weight, gelation occurs when a sheet or a solar cell encapsulant sheet is obtained from the resin composition with an extruder or the like, and the torque of the extruder is increased. Molding may be difficult. Even if a sheet is obtained, the gel material generated in the extruder may cause unevenness on the surface of the sheet, which may deteriorate the appearance. In addition, when a voltage is applied, cracks are generated around the gel within the sheet, and the dielectric breakdown resistance is reduced.
  • the resin composition of the present invention preferably contains at least one additive selected from an ultraviolet absorber (D), a light stabilizer (E) and a heat resistance stabilizer (F).
  • the amount of the additive is preferably 0.005 to 5 parts by weight with respect to 100 parts by weight of the copolymer [X].
  • the amount of the additive is within the above range, the effect of improving the resistance to high temperature and humidity, heat cycle resistance, weather resistance stability and heat stability is sufficiently ensured, and the transparency of the resin composition is ensured. And glass, a back sheet, a thin film electrode, and a decrease in adhesiveness with aluminum can be prevented, which is preferable.
  • ultraviolet absorber (D) examples include 2-hydroxy-4-normal-octyloxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2--2-dihydroxy-4-methoxybenzophenone, 2-hydroxy- Benzophenone series such as 4-methoxy-4-carboxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2- (2-hydroxy-3,5-di-t-butylphenyl) benzotriazole, 2- (2 Benzotrializoles such as -hydroxy-5-methylphenyl) benzotriazole and salicylic acid esters such as phenylsulcylate and p-octylphenylsulcylate are used.
  • Examples of the light stabilizer (E) 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) ) Imino ⁇ ] and other hindered amine-based and hindered piperidine-based compounds are preferably used.
  • heat stabilizer (F) examples include tris (2,4-di-tert-butylphenyl) phosphite and 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, and bis (2,4-di-tert -Butylphenyl) pentaerythritol diphosphite and other phosphite heat stabilizers, lactones such as the reaction product of 3-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene Heat-resistant stabilizer, 3,3 ′, 3 ′′, 5,5 ′, 5 ′′ -hexa-tert-butyl-a, a ′, a ′′-
  • phosphite heat stabilizers and hindered phenol heat stabilizers are preferred.
  • the resin composition of the present invention can appropriately contain various components other than the components detailed above in a range not impairing the object of the present invention.
  • various polyolefins other than the copolymer [X] for example, ethylene / ⁇ -olefin copolymers having a density lower than 850 kg / m 3 , styrene or ethylene block copolymers, propylene (co) polymers
  • Examples include coalescence. These are not particularly limited as long as the effects of the present invention are exerted with respect to 100 parts by weight of the copolymer [X], but are usually 0.0001 to 50 parts by weight, preferably 0.001 to 40 parts by weight. Part.
  • various rubbers other than polyolefin, various rubbers, antioxidants, plasticizers, fillers, pigments, dyes, antistatic agents, antibacterial agents, antifungal agents, flame retardants, crosslinking aids (G), dispersants, etc.
  • One kind or two or more kinds of additives selected can be appropriately contained, but are not limited thereto.
  • the blending amount is 0.01 to 5 parts by weight with respect to 100 parts by weight of the copolymer [X], so that an appropriate crosslinking structure can be obtained. It is preferable because heat resistance, mechanical properties, and adhesiveness can be improved.
  • crosslinking aid (G) conventionally known ones generally used for olefin resins can be used.
  • Such a crosslinking aid (G) is a compound having two or more double bonds in the molecule, and specifically includes t-butyl acrylate, lauryl acrylate, cetyl acrylate, stearyl acrylate, 2-methoxyethyl.
  • Monoacrylate such as acrylate, ethyl carbitol acrylate, methoxytripropylene glycol acrylate, t-butyl methacrylate, lauryl methacrylate, cetyl methacrylate, stearyl methacrylate, methoxyethylene glycol methacrylate, monomethacrylate such as methoxypolyethylene glycol methacrylate, 1,4-butane Diol diacrylate, 1,6-hexanediol diacrylate, 1,9-nonanediol diacrylate, neopentyl glycol diacrylate Diacrylate, diethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethylene glycol diacrylate, tripropylene glycol diacrylate, polypropylene glycol diacrylate, etc., 1,3-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate 1,9-nonanediol
  • the resin composition of the present invention can be produced by employing any known method. For example, a predetermined amount of copolymer [X] and, if necessary, a predetermined amount of organic peroxide [Y], an ethylenically unsaturated silane compound (C), an ultraviolet absorber (D), a light stabilizer. (E), heat stabilizer (F), etc.
  • a Henschel mixer, V-blender, ribbon blender, tumbler blender, or the like or after mixing, a single-screw extruder or a twin-screw extruder It can be produced by a method of granulating or pulverizing after melt-kneading usually at 60 to 140 ° C., preferably 80 to 120 ° C. with a kneader, Banbury mixer or the like.
  • Film or sheet comprising the resin composition according to the present invention [hereinafter sometimes referred to as “sheet”. ] Can be obtained by a known method, for example, melt extrusion molding or press molding of powders, granules and pellets obtained from the resin composition of the present invention.
  • the resin composition of the present invention a sheet comprising the resin composition, and a film or sheet obtained by crosslinking the sheet comprising the resin composition (hereinafter sometimes abbreviated as “crosslinked sheet”) are glass, back.
  • seat for solar cell sealing materials whose resin composition of this invention is a sheet form is also one of preferable embodiment of this invention.
  • seat containing the resin composition of this invention can also be used suitably for a solar cell sealing material.
  • the thickness of the layer of the film or sheet according to the present invention and the sheet for solar cell encapsulant is usually 0.01 to 2 mm, preferably 0.01 to 1.5 mm, more preferably 0.1 to 1.2 mm.
  • the thickness is 01 to 1 mm, more preferably 0.01 to 0.5 mm, more preferably 0.01 to 0.3 mm, and most preferably m 0.01 to 0.2 mm.
  • the thickness is within this range, damage to the glass, solar battery cell, 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, And since it can laminate-mold the solar cell module at low temperature, it is preferable.
  • the extrusion temperature is usually 100 to 150 ° C.
  • the productivity of the sheet decreases.
  • the extrusion temperature exceeds 150 ° C.
  • gelation may occur when a sheet is obtained from the resin composition with an extruder or the like, and the torque of the extruder may increase to make sheet molding difficult. Even if a sheet is obtained, unevenness may occur on the surface of the sheet due to the gel generated in the extruder, and the appearance may deteriorate.
  • a voltage when a voltage is applied, cracks are generated around the gel within the sheet, and the dielectric breakdown resistance is reduced. Furthermore, moisture permeability at the gel object interface is likely to occur, and moisture permeability is reduced.
  • the surface of the sheet can be embossed, and the surface of this layer can be decorated by embossing to prevent blocking between the sealing sheets or between the sealing sheet and other sheets.
  • the embossing is preferable because it becomes a cushion for the solar cell element or the like at the time of laminating and prevents the breakage.
  • the sheet can be used as a solar cell encapsulant in a single wafer form cut to fit the solar cell module size or a roll form that can be cut to fit the size just before producing the solar cell module. .
  • the solar cell encapsulant which is a preferred embodiment of the present invention may have at least one layer composed of the solar cell encapsulant sheet of the present invention. Therefore, the number of layers of the solar cell encapsulant sheet of the present invention may be one, or two or more. From the viewpoint of simplifying the structure and reducing the cost, and from the viewpoint of effectively utilizing light by minimizing interface reflection between layers, a single layer is preferable.
  • the solar cell encapsulant which is a preferred embodiment of the present invention may be composed of only a layer composed of the sheet for solar cell encapsulant of the present invention, and contains the sheet for solar cell encapsulant of the present invention.
  • a layer other than the layer hereinafter also referred to as “other layer” may be included.
  • a hard coat layer As examples of other layers, if classified according to the purpose, a hard coat layer, an adhesive layer, an antireflection layer, a gas barrier layer, an antifouling layer and the like for protecting the front surface or the back surface can be provided.
  • 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)
  • a layer made of a polymer, a layer made of an inorganic compound, or the like can be provided.
  • the positional relationship between the layer made of the solar cell encapsulant sheet of the present invention and the other layers is not particularly limited, and a preferable layer configuration is appropriately selected depending on the purpose of the invention. That is, the other layer may be provided between two or more layers made of the solar cell encapsulant sheet of the present invention, or may be provided in the outermost layer of the solar cell encapsulant sheet. , It may be provided at other locations. Other layers may be provided only on one side of the layer made of the solar cell encapsulant sheet of the present invention, or other layers may be provided on both sides. There is no restriction
  • melt extrusion such as cast molding machine, extrusion sheet molding machine, etc.
  • a method of obtaining a laminate by co-extrusion using a machine, or a method of obtaining a laminate by melting or heating and laminating the other layer on one previously formed layer is preferred.
  • suitable adhesives for example, maleic anhydride-modified polyolefin resin (for example, Admer (registered trademark) manufactured by Mitsui Chemicals, Inc., Modic (registered trademark) manufactured by Mitsubishi Chemical), unsaturated polyolefin, etc.
  • Acrylic adhesives such as low (non-) crystalline soft polymers, ethylene / acrylic acid ester / maleic anhydride terpolymers (for example, Bondine (registered trademark) manufactured by Sumika Sea-Dief Chemical), ethylene / Vinyl acetate copolymer or adhesive resin composition containing these) may be laminated by a dry laminating method or a heat laminating method.
  • the adhesive one having a heat resistance of usually about 120 ° C.
  • a polyester-based or polyurethane-based adhesive is exemplified as a suitable one.
  • a silane coupling treatment, a titanium coupling treatment, a corona treatment, a plasma treatment, or the like may be used.
  • the sheet for solar cell encapsulant (non-crosslinked sheet) of the present invention has an internal haze of usually 60% or less when measured with a 0.5 mm thick sample obtained by extrusion sheet molding of the resin composition of the present invention. Preferably, it is desirable to be in the range of 50% or less.
  • the solar cell encapsulant sheet (non-crosslinked sheet) of the present invention has a light transmittance (wavelength of 400 to 700 nm) measured with a 0.3 mm thick sample obtained by extrusion sheet molding of the resin composition of the present invention. Is usually in the range of 85% or more, preferably in the range of 88% to 100%, more preferably in the range of 90 to 100%.
  • the solar cell encapsulant comprising the solar cell encapsulant sheet made of the resin composition of the present invention as a part thereof is obtained, for example, by taking 1 g of the encapsulant sheet sample from the solar cell module, and boiling xylene. Soxhlet extraction is performed for 10 hours, filtered through a 30 mesh stainless steel mesh, the mesh is dried under reduced pressure at 110 ° C. for 8 hours, and calculated from the residual amount on the mesh, the gel fraction is 70 to 95%, preferably Is in the range of 70-90%. When the gel fraction is less than 70%, the heat resistance of the solar cell encapsulant is insufficient, a constant temperature and humidity test at 85 ° C.
  • the solar cell encapsulant of the present invention and the solar cell encapsulant sheet which is a preferred embodiment of the present invention have excellent characteristics as described above. Therefore, the solar cell module obtained by using such a solar cell encapsulant or solar cell encapsulant sheet can utilize the effects of the present invention, and is one of the preferred embodiments of the present invention. is there.
  • the solar cell module examples include a crystalline solar cell module in which solar cell elements usually formed of polycrystalline silicon or the like are sandwiched and stacked between solar cell encapsulant sheets, and both front and back surfaces are covered with protective sheets. . That is, a typical solar cell module includes a solar cell module protective sheet (surface protective sheet) / solar cell encapsulant sheet / solar cell element / solar cell encapsulant sheet / solar cell module protective sheet (back surface protection). Sheet).
  • the solar cell module which is one of the preferred embodiments of the present invention is not limited to the above-described configuration, and a part of each of the above layers is appropriately omitted as long as the object of the present invention is not impaired. Layers other than the above can be provided as appropriate.
  • an adhesive layer a shock absorbing layer, a coating layer, an antireflection layer, a back surface rereflection layer, a light diffusion layer, and the like can be provided, but not limited thereto.
  • the layers can be provided at appropriate positions in consideration of the purpose of providing such layers and the characteristics of such layers.
  • a solar cell in which amorphous silicon formed by chemical vapor deposition (CVD) from silane gas is formed on a glass or film substrate with a thin silicon film of several ⁇ m, and an electrode such as silver is sputtered as necessary.
  • CVD chemical vapor deposition
  • a thin film (amorphous) solar cell module in which elements are covered in the order of a solar cell encapsulant sheet and a solar cell module protective sheet (back surface protective sheet) is also a preferred embodiment of the present invention.
  • solar cell modules using silicon for solar cells hybrid type (HIT type) solar cell modules in which crystalline silicon and amorphous silicon are laminated, and multiple silicon layers having different absorption wavelength ranges are laminated.
  • conventional pin Examples include a field effect solar cell module having a structure in which the role of an amorphous silicon p-type window layer having a junction structure is replaced with an inversion layer induced by a field effect from an insulated transparent electrode.
  • a GaAs-based solar battery module using single-crystal GaAs for solar cells and a light-absorbing layer material called a chalcopyrite system made of Cu, In, Ga, Al, Se, S, etc. instead of silicon CIS or CIGS (chalcopyrite) solar cell module using I-III-VI group compound as a solar cell, CdTe-CdS solar cell using a Cd compound thin film as a solar cell, Cu 2 ZnSnS 4 (CZTS) ) Solar cell module and the like.
  • the solar cell encapsulant or solar cell encapsulant sheet of the present invention can be suitably used for all these solar cell modules.
  • the solar cell module of the present invention is excellent in hygroscopicity, it can be suitably used as a thin-film solar cell module that is vulnerable to moisture penetration.
  • the surface protective sheet preferably used in the solar cell module which is a preferred embodiment of the present invention is not particularly limited, but is located on the outermost layer of the solar cell module, so that it has weather resistance, water repellency, stain resistance, and mechanical strength.
  • the solar cell module has performance for ensuring long-term reliability in outdoor exposure.
  • Examples of the material for the surface protective sheet suitably used for the solar cell module include a resin film made of a polyester resin, a fluorine resin, an acrylic resin, a cyclic olefin (co) polymer, an ethylene-vinyl acetate copolymer, glass, and the like. Examples include substrates.
  • the resin film is a polyester resin excellent in transparency, strength, cost, etc., particularly a polyethylene terephthalate resin.
  • a fluorine resin having particularly good weather resistance is also preferably used.
  • ethylene tetrafluoride-ethylene copolymer ETFE
  • polyvinyl fluoride resin PVDF
  • PVDF polyvinylidene fluoride resin
  • TFE polytetrafluoroethylene resin
  • FEP fluorinated propylene copolymer
  • CTFE poly (trifluorotrifluoroethylene resin)
  • Polyvinylidene fluoride resin is excellent from the viewpoint of weather resistance, but tetrafluoroethylene-ethylene copolymer is excellent from the viewpoint of both weather resistance and mechanical strength.
  • a corona treatment and a plasma treatment on the surface protective sheet in order to improve the adhesiveness with a material constituting another layer such as a layer made of a solar cell encapsulant sheet. It is also possible to use a sheet that has been subjected to stretching treatment for improving mechanical strength, for example, a biaxially stretched polypropylene sheet.
  • the total light transmittance of light having a wavelength of 350 to 1400 nm is preferably 80% or more, more preferably 90% or more.
  • a glass substrate it is common to use white plate glass with little absorption in the infrared part, but even blue plate glass has little influence on the output characteristics of the solar cell module if the thickness is 3 mm or less.
  • tempered glass can be obtained by heat treatment to increase the mechanical strength of the glass substrate, but float plate glass without heat treatment may be used.
  • an antireflection coating may be provided on the light receiving surface side of the glass substrate in order to suppress reflection.
  • a reinforcing plate may be attached to increase the mechanical strength of the solar cell module or to prevent distortion and warpage due to temperature change.
  • a steel plate, a plastic plate, an FRP (glass fiber reinforced plastic) plate or the like can be preferably used.
  • the solar cell element in the solar cell module which is a preferred embodiment of the present invention is not particularly limited as long as it can generate power using the photovoltaic effect of a semiconductor.
  • silicon single crystal system, polycrystalline system, Amorphous solar cells, compound semiconductor (Group 3-5, 2-6, etc.) solar cells, wet solar cells, organic semiconductor solar cells and the like can be used.
  • a polycrystalline silicon solar cell is preferable from the viewpoint of balance between power generation performance and cost.
  • both silicon and compound semiconductors have excellent characteristics as solar cell elements, but are known to be easily damaged by external stress, impact, and the like. Since the solar cell encapsulant sheet of the present invention is excellent in flexibility, it has a great effect of absorbing stress, impact, etc. on the solar cell element and preventing damage to the solar cell element. Therefore, in the solar cell module which is a preferred embodiment of the present invention, it is desirable that the layer made of the sheet for solar cell sealing material of the present invention is directly joined to the solar cell element.
  • the solar cell encapsulant sheet has thermoplasticity, it is possible to take out the solar cell element relatively easily even after the solar cell module is once manufactured. Are better. Since the essential component of the sheet
  • the sheet for solar cell encapsulant of the present invention is prepared in advance, and the laminating temperature is usually 120 to 170 ° C. by a conventional laminating method in which the sheet is pressure-bonded at a melting temperature.
  • the laminating temperature is usually 120 to 170 ° C. by a conventional laminating method in which the sheet is pressure-bonded at a melting temperature.
  • a module having the configuration described above can be formed.
  • the solar cell encapsulant sheet has excellent cross-linking properties by containing the organic peroxide [Y], and it is not necessary to go through a two-step bonding process in forming the module. It can be completed in a short time, and the module productivity can be remarkably improved.
  • the solar cell module which is a preferred embodiment of the present invention is excellent in productivity, power generation efficiency, life and the like. For this reason, the power generation equipment using such a solar cell module is excellent in cost, power generation efficiency, life, etc., and has a high practical value.
  • the power generation equipment described above is suitable for long-term use, whether outdoors or indoors, such as being installed on the roof of a house, used as a mobile power source for outdoor activities such as camping, or used as an auxiliary power source for automobile batteries.
  • i-PSt 0.686
  • [ ⁇ ] i-EPR 7.2 ⁇ 10 ⁇ 4 M i-EPR 0.667
  • Mw / Mn The molecular weight distribution
  • the gel permeation chromatography (GPC) method was measured as follows using a gel permeation chromatograph Alliance GPC-2000 manufactured by Waters.
  • the separation column has two TSKgel GNH6-HT and two TSKgel GNH6-HTL.
  • the column size is 7.5 mm in diameter and 300 mm in length, the column temperature is 140 ° C., and the mobile phase is Using o-dichlorobenzene (Wako Pure Chemical Industries, Ltd.) and 0.025% by weight of BHT (Takeda Pharmaceutical Co., Ltd.) as an antioxidant, the sample was transferred at 1.0 ml / min.
  • the amount of sample injection was 500 ⁇ l, and a differential refractometer was used as a detector.
  • Standard polystyrene used was made by Tosoh Corporation for molecular weights of Mw ⁇ 1000 and Mw> 4 ⁇ 10 6 , and that of Pressure Chemical Co. for 1000 ⁇ Mw ⁇ 4 ⁇ 10 6 .
  • ⁇ Double bond amount (unsaturated bond amount)> The amount of double bonds was determined by 1 H-NMR measurement of an ethylene / propylene / ⁇ -olefin copolymer (manufactured by JEOL Ltd., “ECX400P type nuclear magnetic resonance apparatus”).
  • vinyl type double bond (vinyl group), vinylidene type double bond (vinylidene group), disubstituted olefin type double bond and trisubstituted olefin type double bond are observed as signals derived from the double bond.
  • the amount of double bonds was quantified from the integrated intensity of each signal.
  • the main chain methylene signal of the ethylene / ⁇ -olefin copolymer was defined as a chemical shift standard (1.2 ppm).
  • the total amount of vinyl groups and vinylidene groups is determined as the amount of molecular terminal double bonds, and the total amount of disubstituted olefin type double bonds and trisubstituted olefin type double bonds is determined as the amount of internal unsaturated bonds. (Total unsaturated bond amount) was determined as the sum of each double bond. An analysis with 0.1 / 1000 C as the limit of quantification was performed, and when a signal was confirmed even in the case of less than 0.1 / 1000 C, a calibration curve was extrapolated to calculate the double bond amount.
  • the sample was cooled to ⁇ 40 ° C. and then increased to 200 ° C. at a temperature rising rate of 10 ° C./min.
  • ⁇ MFR> MFR was measured at 190 ° C. and 2.16 kg load according to ASTM D1238.
  • ⁇ Comonomer content (composition)> A JNM GX-400 NMR measuring apparatus manufactured by JEOL Ltd. was used. A 0.35 g sample is dissolved by heating in 2.0 ml of hexachlorobutadiene. This solution is filtered through a glass filter (G2), 0.5 ml of deuterated benzene is added, and the solution is placed in an NMR tube having an inner diameter of 10 mm, and 13 C-NMR measurement is performed at 120 ° C. The number of integration is 8000 times or more. From the obtained 13 C-NMR spectrum, the ethylene content (mol%), propylene content (mol%) and ⁇ -olefin content (mol%) in the copolymer were quantified.
  • Production Examples 1 to 5 which are production examples of the ethylene / propylene / ⁇ -olefin copolymer according to the present invention are shown below.
  • the opening degree of the liquid level control valve is adjusted so that the produced hexane solution of ethylene / propylene / 1-octene copolymer maintains the amount of solution in the polymerization vessel of 20 L through the outlet provided in the side wall of the polymerization vessel. It discharged continuously while adjusting.
  • the obtained hexane solution of ethylene / propylene / 1-octene copolymer was introduced into a heater and heated to 180 ° C., and 3 mL of methanol was added every hour as a catalyst deactivator to stop the polymerization, and the pressure was reduced.
  • An ethylene / propylene / 1-octene copolymer (copolymer A) was obtained by continuously transferring to a devolatilization step and drying. The physical properties are shown in Table 1.
  • Production Examples 6 to 14 are shown below as production examples of the ethylene / propylene / ⁇ -olefin copolymer used as a comparative example of the present invention.
  • Exact (registered trademark) 5361 (manufactured by ExxonMobil Chemical Co., Ltd.) was used as the ethylene / 1-octene copolymer.
  • the physical properties are shown in Table 2-2.
  • Examples 2 and 5 and Comparative Examples 1 to 10 Except that the ethylene / propylene / 1-octene copolymer (copolymer A) described in Example 1 was changed to the copolymers described in Tables 1 and 2, the thickness was the same as in Example 1. A 0.5 mm sheet and a 0.05 mm thick film were prepared.
  • Example 4 The ethylene / propylene / 1-octene copolymer (copolymer A) described in Example 1 was replaced with the copolymer described in Table 1 in the same manner as in Example 1 except that the thickness was 0.5 mm. A sheet and a film having a thickness of 0.05 mm were prepared.

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Abstract

Le but de la présente invention consiste à obtenir : un film ou une feuille qui présente une transparence élevée, une excellente résistance aux chocs (basse densité) et une résistance élevée et qui convient pour un matériau d'étanchéité de pile solaire ; un matériau d'étanchéité de pile solaire comprenant la feuille ; et un module de pile solaire comprenant le matériau d'étanchéité de pile solaire. À cet effet, la présente invention concerne un film ou une feuille contenant un copolymère d'éthylène-propylène-α-oléfine [X] qui comprend de l'éthylène, du propylène et une α-oléfine en C5 à C20 et qui satisfait l'exigence (x-1) : un motif constitutif (i) dérivé de l'éthylène est contenu en une quantité de 74 à 92 % en mole, un motif constitutif (ii) dérivé du propylène est contenu en une quantité de 5 à 16 % en mole, et un motif constitutif (iii) dérivé d'α-oléfine en C5 à C20 est contenu en une quantité de 3 à 10 % en mole (la quantité totale des motifs constitutifs (i), (ii) et (iii) étant de 100 % en mole.)
PCT/JP2018/009877 2017-03-28 2018-03-14 Composition de résine, feuille, matériau d'étanchéité de pile solaire, module de pile solaire, et procédé de production de feuille pour matériau d'étanchéité de pile solaire WO2018180483A1 (fr)

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JP2021070793A (ja) * 2019-11-01 2021-05-06 三井化学株式会社 接着剤

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JP2021070793A (ja) * 2019-11-01 2021-05-06 三井化学株式会社 接着剤
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