WO2014148056A1 - Sealing material sheet for solar cell modules, and solar cell module - Google Patents
Sealing material sheet for solar cell modules, and solar cell module Download PDFInfo
- Publication number
- WO2014148056A1 WO2014148056A1 PCT/JP2014/001627 JP2014001627W WO2014148056A1 WO 2014148056 A1 WO2014148056 A1 WO 2014148056A1 JP 2014001627 W JP2014001627 W JP 2014001627W WO 2014148056 A1 WO2014148056 A1 WO 2014148056A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sealing material
- solar cell
- organic peroxide
- material sheet
- cell module
- Prior art date
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- 239000003566 sealing material Substances 0.000 title claims abstract description 79
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 46
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 33
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims abstract description 30
- 239000004711 α-olefin Substances 0.000 claims abstract description 30
- 239000008393 encapsulating agent Substances 0.000 claims description 26
- 238000004132 cross linking Methods 0.000 abstract description 25
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 230000007774 longterm Effects 0.000 abstract description 9
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 abstract 2
- 239000005977 Ethylene Substances 0.000 abstract 2
- 229920005989 resin Polymers 0.000 description 21
- 239000011347 resin Substances 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 16
- -1 crosslinking aid Substances 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 239000000853 adhesive Substances 0.000 description 7
- 230000001070 adhesive effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000008961 swelling Effects 0.000 description 7
- 230000007423 decrease Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000005038 ethylene vinyl acetate Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 239000003963 antioxidant agent Substances 0.000 description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 239000003431 cross linking reagent Substances 0.000 description 3
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 3
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 3
- JXCAHDJDIAQCJO-UHFFFAOYSA-N (1-tert-butylperoxy-2-ethylhexyl) hydrogen carbonate Chemical compound CCCCC(CC)C(OC(O)=O)OOC(C)(C)C JXCAHDJDIAQCJO-UHFFFAOYSA-N 0.000 description 2
- XDLMVUHYZWKMMD-UHFFFAOYSA-N 3-trimethoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[Si](OC)(OC)CCCOC(=O)C(C)=C XDLMVUHYZWKMMD-UHFFFAOYSA-N 0.000 description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- 239000006096 absorbing agent Substances 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- BXKDSDJJOVIHMX-UHFFFAOYSA-N edrophonium chloride Chemical compound [Cl-].CC[N+](C)(C)C1=CC=CC(O)=C1 BXKDSDJJOVIHMX-UHFFFAOYSA-N 0.000 description 2
- QUAMTGJKVDWJEQ-UHFFFAOYSA-N octabenzone Chemical compound OC1=CC(OCCCCCCCC)=CC=C1C(=O)C1=CC=CC=C1 QUAMTGJKVDWJEQ-UHFFFAOYSA-N 0.000 description 2
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 239000011112 polyethylene naphthalate Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920002620 polyvinyl fluoride Polymers 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004383 yellowing Methods 0.000 description 2
- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- VBQCFYPTKHCPGI-UHFFFAOYSA-N 1,1-bis(2-methylpentan-2-ylperoxy)cyclohexane Chemical compound CCCC(C)(C)OOC1(OOC(C)(C)CCC)CCCCC1 VBQCFYPTKHCPGI-UHFFFAOYSA-N 0.000 description 1
- HSLFISVKRDQEBY-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)cyclohexane Chemical compound CC(C)(C)OOC1(OOC(C)(C)C)CCCCC1 HSLFISVKRDQEBY-UHFFFAOYSA-N 0.000 description 1
- KOMNUTZXSVSERR-UHFFFAOYSA-N 1,3,5-tris(prop-2-enyl)-1,3,5-triazinane-2,4,6-trione Chemical compound C=CCN1C(=O)N(CC=C)C(=O)N(CC=C)C1=O KOMNUTZXSVSERR-UHFFFAOYSA-N 0.000 description 1
- HQOVXPHOJANJBR-UHFFFAOYSA-N 2,2-bis(tert-butylperoxy)butane Chemical compound CC(C)(C)OOC(C)(CC)OOC(C)(C)C HQOVXPHOJANJBR-UHFFFAOYSA-N 0.000 description 1
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 description 1
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 description 1
- LEVFXWNQQSSNAC-UHFFFAOYSA-N 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexoxyphenol Chemical compound OC1=CC(OCCCCCC)=CC=C1C1=NC(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=N1 LEVFXWNQQSSNAC-UHFFFAOYSA-N 0.000 description 1
- BIISIZOQPWZPPS-UHFFFAOYSA-N 2-tert-butylperoxypropan-2-ylbenzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC=C1 BIISIZOQPWZPPS-UHFFFAOYSA-N 0.000 description 1
- WPMYUUITDBHVQZ-UHFFFAOYSA-M 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=CC(CCC([O-])=O)=CC(C(C)(C)C)=C1O WPMYUUITDBHVQZ-UHFFFAOYSA-M 0.000 description 1
- ZVVFVKJZNVSANF-UHFFFAOYSA-N 6-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]hexyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCCCCCCOC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 ZVVFVKJZNVSANF-UHFFFAOYSA-N 0.000 description 1
- 239000004641 Diallyl-phthalate Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004049 embossing Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 1
- 229920005648 ethylene methacrylic acid copolymer Polymers 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- DOEHJNBEOVLHGL-UHFFFAOYSA-N trichloro(propyl)silane Chemical compound CCC[Si](Cl)(Cl)Cl DOEHJNBEOVLHGL-UHFFFAOYSA-N 0.000 description 1
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- TUQLLQQWSNWKCF-UHFFFAOYSA-N trimethoxymethylsilane Chemical compound COC([SiH3])(OC)OC TUQLLQQWSNWKCF-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000009849 vacuum degassing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Images
Classifications
-
- 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
- C08K5/04—Oxygen-containing compounds
- C08K5/14—Peroxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/54—Silicon-containing compounds
- C08K5/541—Silicon-containing compounds containing oxygen
- C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
- C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2457/00—Electrical equipment
- B32B2457/12—Photovoltaic modules
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
-
- 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 material sheet used for sealing solar cells in a manufacturing process of a solar battery module or the like and a solar battery module using the sealing material sheet.
- a general crystalline silicon solar cell module is composed of a front glass, a back sheet, a solar cell (photoelectric conversion cell), and a sealing material.
- the solar cell disposed between the front glass and the back sheet is a sealing material. It has a completely sealed structure.
- a material constituting such a solar cell is required to have high weather resistance that can withstand long-term use.
- the sealing material is a material for adhering and holding the front glass, the back sheet, and the solar battery cell, and therefore requires high adhesion over a long period of time, and is also disposed on the light receiving surface side of the solar battery cell. There is also a need for transparency not to be lost.
- an ethylene-vinyl acetate copolymer having appropriate adhesion and transparency has been generally used as a main resin, but in recent years, the use of an ethylene- ⁇ olefin copolymer has also been proposed. It has come to be. This is presumably because the ethylene-vinyl acetate copolymer contained a problem of corroding the solar cell member and reducing power generation when used for a long time.
- This ethylene- ⁇ -olefin copolymer is added with a crosslinking agent, crosslinking aid, silane coupling agent, light stabilizer, and UV absorber for the purpose of providing long-term durability and adhesion to glass and backsheet. In many cases, compositions such as those described in Patent Documents 1, 2, and 3 have been proposed.
- the composition as shown in the prior art is not yet satisfactory as the reliability of the sealing material for solar cells intended for long-term use.
- the present invention is intended to solve the above-described problems of the prior art, and has a high adhesiveness and crosslinking density, and a highly reliable encapsulant sheet for solar cell modules and a solar cell module that does not cause the problem of swelling. The purpose is to provide.
- a solar cell module encapsulant sheet includes an ethylene- ⁇ -olefin copolymer, an organic peroxide, and a silane coupling agent, and includes the following conditions (1) and (2) is satisfied.
- the density of the ethylene- ⁇ -olefin copolymer may be 0.86 g / cm 3 or more and 0.90 g / cm 3 or less.
- the solar cell module which concerns on the other aspect of this invention is a solar cell, the sealing material layer which seals the said photovoltaic cell, the surface protection member which protects the surface side of the said sealing material layer, And a back surface protection member for protecting the back surface side of the sealing material layer, wherein the sealing material layer is formed by the solar cell module sealing material sheet.
- the solar cell module encapsulant sheet of the present invention can stably form an encapsulant layer having excellent adhesion and high crosslink density, has no problem of swelling, and has high reliability in long-term use. Modules can be manufactured. Moreover, since the solar cell module of this invention uses the said sealing material sheet for solar cell modules, it is highly reliable in long-term use.
- the encapsulant sheet of the present invention contains an ethylene- ⁇ olefin copolymer, an organic peroxide, and a silane coupling agent.
- the resin base material forming the sealing material sheet of the present invention preferably uses an ethylene- ⁇ -olefin copolymer as a main component.
- the ethylene- ⁇ olefin copolymer is more advantageous than the ethylene-vinyl acetate copolymer in that it has high transparency and does not generate acetic acid.
- the phrase “having the ethylene- ⁇ -olefin copolymer as a main component” means that the ethylene- ⁇ -olefin copolymer is 95% by mass or more based on the total amount of the resin base material.
- the sealing material sheet of the present invention may contain other resins in addition to the ethylene- ⁇ -olefin copolymer.
- other resins include ionomers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, polyvinyl fluoride, polyvinyl chloride, and copolymers thereof.
- the proportion of the ethylene- ⁇ -olefin copolymer in the resin substrate of the encapsulant sheet of the present invention is preferably 95% by mass or more, more preferably 97% by mass or more, and particularly preferably 100% by mass.
- Organic peroxide acts as a crosslinking agent that initiates a crosslinking reaction of the ethylene- ⁇ -olefin copolymer.
- organic peroxides include 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexyl monocarbonate, 1,1-di (t-hexylperoxy) cyclohexane, and n-butyl.
- the silane coupling agent has an effect of improving adhesion between a sealing material formed of a resin base material containing an ethylene- ⁇ -olefin copolymer, and a surface protection member and a back surface protection member for protecting the front surface and the back surface. is there.
- Examples of the silane coupling agent include ⁇ -methacryloxypropyltrimethoxysilane, trimethoxypropylsilane, trimethoxymethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, trichloropropylsilane, triethoxyphenylsilane, and the like.
- the organic peroxide and the silane coupling agent in the sealing material sheet of the present invention are contained so as to satisfy the following condition (1) and condition (2).
- (1) 5.4 ⁇ (A ⁇ B) /C ⁇ 10.1 (2) 6.0 ⁇ 10 ⁇ 3 ⁇ A ⁇ (D / E) ⁇ 1.0 ⁇ 10 ⁇ 2
- A is the amount of theoretical oxy radicals generated from one molecule of organic peroxide
- B is the molar amount of organic peroxide
- C is the molar amount of silane coupling agent
- D is ethylene- ⁇
- E is the molecular weight of the organic peroxide.
- the theoretical oxy radical amount A generated from one molecule of the organic peroxide under the condition (1) is an amount represented by the following formula (1-1).
- the sealing material sheet of the present invention the ratio of the product of the theoretical oxy radical amount A generated from one molecule of the organic peroxide and the molar amount B of the organic peroxide to the molar amount C of the silane coupling agent (A The value of xB) / C is preferably 5.4 or more and 10.1 or less.
- the ratio (A ⁇ B) / C is 5.4 or more, the crosslinking reaction of the ethylene- ⁇ -olefin copolymer is likely to proceed sufficiently, and high heat resistance can be obtained. If ratio (A * B) / C is 10.1 or less, the outstanding adhesiveness will be obtained and peeling with a sealing material layer, a surface protection member, and a back surface protection member can be suppressed.
- the value of A ⁇ (D / E) is preferably 6.0 ⁇ 10 ⁇ 3 or more and 1.0 ⁇ 10 ⁇ 2 or less.
- a ⁇ (D / E) is 6.0 ⁇ 10 ⁇ 3 or more, the cross-linking reaction of the ethylene- ⁇ -olefin copolymer proceeds sufficiently and high heat resistance can be obtained. If the value of A ⁇ (D / E) is 1.0 ⁇ 10 ⁇ 2 or less, the problem of blistering derived from organic peroxide reaction residues and unreacted substances in the encapsulant sheet can be prevented. . Moreover, the stability at the time of the shaping
- Condition (1) represents that the value obtained by dividing the theoretical number of radicals (A ⁇ B) generated during radical crosslinking by the number of silane coupling agents (C) is within a certain range. This is because when the number of radicals (A ⁇ B) increases (decreases), the crosslinking reaction increases (decreases), and when the number of silane coupling agents (C) increases (decreases), the crosslinking reaction decreases. This finding is shown as condition (1). When the crosslinking reaction is too low, deterioration resistance against yellowing of the resin is lowered, and when the crosslinking reaction is too high, the adhesiveness is lowered. Therefore, it was found that the range of the condition (1) is optimal.
- the silane coupling agent has a radical deactivation effect.
- Condition (2) represents the theoretical radical number ratio with respect to the ethylene- ⁇ -olefin copolymer. It is found that the crosslinking reaction increases (decreases) when the radical number ratio increases (decreases), and this knowledge is shown as condition (2). When the cross-linking reaction is too low, the deterioration resistance against the yellowing of the resin is lowered, and when the cross-linking reaction is too high, the adhesiveness is lowered, so that the condition (2) is found to be optimal. It is. And it discovered that the range which satisfy
- the density of the ethylene- ⁇ -olefin copolymer used in the sealing material sheet of the present invention is preferably 0.86 g / cm 3 or more and 0.90 g / cm 3 or less.
- the density can be adjusted by changing the ⁇ -olefin content, the polymerization temperature, the catalyst amount, etc. during the polymerization of the ethylene- ⁇ -olefin copolymer.
- the measurement of the density of the ethylene- ⁇ -olefin copolymer is based on JIS-K6922-2: 2010.
- the sealing material sheet of this invention may contain the crosslinking adjuvant which accelerates
- the crosslinking aid include triallyl isocyanurate, diallyl phthalate, triallyl cyanurate and the like.
- stabilizers such as a ultraviolet absorber and antioxidant, may contain in the sealing material sheet of this invention from a viewpoint of the light resistance and heat stability of the sealing material layer formed.
- ultraviolet absorbers used for improving light resistance include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5.
- Antioxidants used for improving thermal stability include 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (2,4-di-tert-butylphenyl) phosphite, 2,4-bis- (n-octylthio) Examples include -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
- the encapsulant sheet of the present invention can be produced by a known production method except that the organic peroxide and the silane coupling agent are contained so as to satisfy the conditions (1) and (2).
- the resin base material is mixed with an organic peroxide, a silane coupling agent, and other additives that are added as necessary, and the resin is heated and melted.
- a method having a film forming step of forming a film by a co-extrusion method is
- the surface of the heat-melted resin sheet is brought into close contact with a roll (made of metal or rubber) having a concavo-convex pattern, so that the surface of the roll is placed on one or both sides of the resin sheet.
- the uneven pattern may be transferred.
- the embossing for blocking prevention can be given to a sealing material sheet.
- the sealing material sheet of the present invention contains the organic peroxide and the silane coupling agent so as to satisfy the conditions (1) and (2), it is excellent in high crosslinking density. It is possible to stably form a sealing material layer having adhesiveness and no swelling and having high reliability. Therefore, the reliability in the long-term use of the solar cell module using this sealing material sheet becomes high.
- the solar battery cell 3 is a cell having a function of converting light incident on the light receiving surface into electricity by a photoelectric effect.
- a plurality (two in FIG. 1) of solar cells 3 are connected by electrodes (not shown) in the solar cell module 5.
- the number of the photovoltaic cells 3 is not specifically limited. Examples of the material of the solar battery cell 3 include crystalline silicon. Among these, polycrystalline silicon is particularly preferable from the viewpoint of manufacturing simplicity and cost.
- the sealing material layer 2 is a layer that embeds and seals the solar cells 3 and is formed of the sealing material sheet of the present invention.
- the thickness of the sealing material layer 2 is preferably 0.2 to 0.8 mm.
- Examples of the surface protection member 1 include glass, polyethylene terephthalate, polyethylene naphthalate, tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), and the like. Glass is preferably used in terms of transparency, weather resistance, and flame retardancy. Further, other materials having high durability, weather resistance, and transparency may be used. Further, in order to impart durability and weather resistance to these materials, a hard coat layer, a UV absorption layer, a water vapor barrier layer, or the like may be laminated.
- the back surface protection member 4 examples include glass, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polycarbonate, ETFE, PCTFE, polyvinyl fluoride, ethylene-vinyl acetate copolymer (EVA), aluminum foil, and laminates thereof. Can be mentioned. Other materials having high durability and weather resistance may be used. Moreover, you may laminate
- the manufacturing method of the solar cell module 5 is demonstrated as an example of the manufacturing method of the solar cell module of this invention.
- the manufacturing method of the solar cell module of the present invention is not limited to the following method.
- the back surface protection member 4, the sealing material sheet 6, the solar cell 3, the sealing material sheet 6, and the surface protection member 1 are laminated
- vacuum lamination is performed by heating and pressurizing the laminate in a vacuum state, the solar cells 3 are embedded in the upper and lower two sealing material sheets 6, and the resin base material of the sealing material sheet 6 is crosslinked and cured to be bonded.
- the sealing material layer 2 is formed by integrating. Thereby, the solar cell module 5 is obtained.
- the two encapsulant sheets 6 are the encapsulant sheets of the present invention, both of which may be the same composition encapsulant sheet or different composition encapsulant sheets, but uniformly It is preferable that the encapsulant sheet has the same composition from the viewpoint that a good quality module can be easily obtained by forming a crosslinked structure.
- the encapsulant sheet 6 according to the present invention includes an ethylene- ⁇ olefin copolymer resin, an organic peroxide, and a silane coupling agent.
- the organic peroxide acts as a crosslinking agent for initiating the crosslinking reaction of the ethylene- ⁇ -olefin copolymer resin
- the silane coupling agent is composed of the ethylene- ⁇ -olefin copolymer resin, the surface protection member 1 and the back surface protection member 4. It has the effect of improving adhesion.
- the laminate is placed in a laminator that can be evacuated on the upper lid side and the laminate chamber, respectively, and evacuated for 90 seconds on both the upper lid side and the laminate chamber while maintaining the temperature in the laminate chamber at 150 ° C.
- Temporary pressure bonding was performed while degassing the inside of the laminate (vacuum degassing and temporary pressure bonding).
- the temperature in the laminate chamber was set to 150 ° C.
- the vacuum state on the laminator upper lid side was released, and the laminate was subjected to thermocompression bonding at atmospheric pressure for 10 minutes (main pressure bonding) to obtain a solar cell module.
- Example 2 A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.0 part by mass and the addition amount of the silane coupling agent was 0.2 part by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
- Example 3 A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.8 parts by mass and the addition amount of the silane coupling agent was 0.3 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
- Example 1 A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.2 parts by mass and the addition amount of the silane coupling agent was 0.5 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
- Comparative Example 2 A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.8 parts by mass and the addition amount of the silane coupling agent was 0.1 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
- Example 3 A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.4 parts by mass and the addition amount of the silane coupling agent was 0.4 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
- Comparative Example 4 A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.6 parts by mass and the addition amount of the silane coupling agent was 0.3 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1. [Evaluation methods] About the solar cell module of an Example and a comparative example, the crosslinking density of a sealing material layer, the adhesive strength between a back surface protection member / sealing material layer, and the swelling after throwing into a high temperature environment were evaluated.
- Table 1 it is indicated by a circle, and when it is less than 20 N / 10 mm, it is determined to be unacceptable. (About evaluation of swelling) The appearance was observed after being left for 96 hours in a high temperature and high humidity environment (temperature 121 ° C., humidity 100% saturation) in a pressure cooker tester (PCT). Table 1 shows the evaluation results of the swelling. When the blister cannot be confirmed visually, it is accepted, and in Table 1, it is indicated by a circle, and when the blister is confirmed, it is rejected. In Table 1, it is indicated by a cross.
- SYMBOLS 1 Surface protection member, 2 ... Sealing material layer, 3 ... Solar cell, 4 ... Back surface protection member, 5 ... Solar cell module, 6 ... Sealing material sheet
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Abstract
The purpose of the present invention is to provide: a sealing material sheet for solar cell modules, which is capable of stably forming a sealing material layer that has excellent adhesion and high crosslinking density, and which enables the production of a solar cell module that has high reliability for long-term use; and a solar cell module which uses this sealing material sheet for solar cell modules. A sealing material sheet (6) for solar cell modules contains an ethylene/α-olefin copolymer, an organic peroxide and a silane coupling agent, and satisfies condition (1) 5.4 ≤ (A × B)/C ≤ 10.1 and condition (2) 6.0 × 10-3 ≤ A × (D/E) ≤ 1.0 × 10-2. In this connection, A is the theoretical amount of oxy radicals generated from one molecule of the organic peroxide; B is the molar quantity of the organic peroxide; C is the molar quantity of the silane coupling agent; D is the content (parts by mass) of the organic peroxide relative to 100 parts by mass of the ethylene/α-olefin copolymer; and E is the molecular weight of the organic peroxide. A solar cell module (5) uses this sealing material sheet (6).
Description
本発明は、太陽電池モジュール等の製造工程で太陽電池セルを封止するために使用される封止材シート及び当該封止材シートを用いた太陽電池モジュールに関する。
The present invention relates to a sealing material sheet used for sealing solar cells in a manufacturing process of a solar battery module or the like and a solar battery module using the sealing material sheet.
太陽光を利用するクリーンな発電技術として、太陽電池が近年注目を集めている。太陽電池には、結晶シリコン、非晶シリコン、化合物半導体、有機色素等、多様な方式が存在する。中でも、結晶シリコン系太陽電池は耐候性、耐久性に優れ、比較的高い光電変換効率を有しているため、最も普及が進んでいる。
一般的な結晶シリコン太陽電池モジュールは、前面ガラス、バックシート、太陽電池セル（光電変換セル）、封止材からなり、前面ガラスとバックシートの間に配置される太陽電池セルが封止材で完全に封止された構造となっている。
このような太陽電池を構成する材料には、長期使用に耐え得る高い耐候性が求められている。中でも封止材は、前面ガラス、バックシート及び太陽電池セルを接着保持する材料であるため、長期間にわたる高い密着性が必要であり、また、太陽電池セルの受光面側にも配置されるため、透明性が失われないことも求められている。 In recent years, solar cells have attracted attention as a clean power generation technology that uses sunlight. There are various types of solar cells, such as crystalline silicon, amorphous silicon, compound semiconductors, and organic dyes. Among these, crystalline silicon solar cells are most popular because they are excellent in weather resistance and durability and have a relatively high photoelectric conversion efficiency.
A general crystalline silicon solar cell module is composed of a front glass, a back sheet, a solar cell (photoelectric conversion cell), and a sealing material. The solar cell disposed between the front glass and the back sheet is a sealing material. It has a completely sealed structure.
A material constituting such a solar cell is required to have high weather resistance that can withstand long-term use. Among them, the sealing material is a material for adhering and holding the front glass, the back sheet, and the solar battery cell, and therefore requires high adhesion over a long period of time, and is also disposed on the light receiving surface side of the solar battery cell. There is also a need for transparency not to be lost.
一般的な結晶シリコン太陽電池モジュールは、前面ガラス、バックシート、太陽電池セル（光電変換セル）、封止材からなり、前面ガラスとバックシートの間に配置される太陽電池セルが封止材で完全に封止された構造となっている。
このような太陽電池を構成する材料には、長期使用に耐え得る高い耐候性が求められている。中でも封止材は、前面ガラス、バックシート及び太陽電池セルを接着保持する材料であるため、長期間にわたる高い密着性が必要であり、また、太陽電池セルの受光面側にも配置されるため、透明性が失われないことも求められている。 In recent years, solar cells have attracted attention as a clean power generation technology that uses sunlight. There are various types of solar cells, such as crystalline silicon, amorphous silicon, compound semiconductors, and organic dyes. Among these, crystalline silicon solar cells are most popular because they are excellent in weather resistance and durability and have a relatively high photoelectric conversion efficiency.
A general crystalline silicon solar cell module is composed of a front glass, a back sheet, a solar cell (photoelectric conversion cell), and a sealing material. The solar cell disposed between the front glass and the back sheet is a sealing material. It has a completely sealed structure.
A material constituting such a solar cell is required to have high weather resistance that can withstand long-term use. Among them, the sealing material is a material for adhering and holding the front glass, the back sheet, and the solar battery cell, and therefore requires high adhesion over a long period of time, and is also disposed on the light receiving surface side of the solar battery cell. There is also a need for transparency not to be lost.
封止材としては、一般的に、適切な密着性と透明性を有するエチレン－酢酸ビニル共重合体がメイン樹脂として用いられてきたが、近年、エチレン－αオレフィン共重合体の使用も提案されるようになってきた。これはエチレン－酢酸ビニル共重合体は、長期にわたって使用すると太陽電池部材を腐食し、発電低下を起こす問題を含んでいたためだと考えられる。
このエチレン－αオレフィン共重合体には、長期耐久性とガラスやバックシートとの密着性を付与する目的で、架橋剤、架橋助剤、シランカップリング剤、光安定剤、紫外線吸収剤を添加することが多く、特許文献１，２，３に記載されるような組成が提案されている。 As a sealing material, an ethylene-vinyl acetate copolymer having appropriate adhesion and transparency has been generally used as a main resin, but in recent years, the use of an ethylene-α olefin copolymer has also been proposed. It has come to be. This is presumably because the ethylene-vinyl acetate copolymer contained a problem of corroding the solar cell member and reducing power generation when used for a long time.
This ethylene-α-olefin copolymer is added with a crosslinking agent, crosslinking aid, silane coupling agent, light stabilizer, and UV absorber for the purpose of providing long-term durability and adhesion to glass and backsheet. In many cases, compositions such as those described in Patent Documents 1, 2, and 3 have been proposed.
このエチレン－αオレフィン共重合体には、長期耐久性とガラスやバックシートとの密着性を付与する目的で、架橋剤、架橋助剤、シランカップリング剤、光安定剤、紫外線吸収剤を添加することが多く、特許文献１，２，３に記載されるような組成が提案されている。 As a sealing material, an ethylene-vinyl acetate copolymer having appropriate adhesion and transparency has been generally used as a main resin, but in recent years, the use of an ethylene-α olefin copolymer has also been proposed. It has come to be. This is presumably because the ethylene-vinyl acetate copolymer contained a problem of corroding the solar cell member and reducing power generation when used for a long time.
This ethylene-α-olefin copolymer is added with a crosslinking agent, crosslinking aid, silane coupling agent, light stabilizer, and UV absorber for the purpose of providing long-term durability and adhesion to glass and backsheet. In many cases, compositions such as those described in
しかしながら、従来技術に示されるような組成では、長期使用を目的とする太陽電池用の封止材の信頼性としては、まだ満足できるものではない。
本発明は上記のような従来技術の課題を解決しようとするものであり、密着性や架橋密度が高い、膨れの問題が生じない高信頼性の太陽電池モジュール用封止材シート及び太陽電池モジュールを提供することを目的とする。 However, the composition as shown in the prior art is not yet satisfactory as the reliability of the sealing material for solar cells intended for long-term use.
The present invention is intended to solve the above-described problems of the prior art, and has a high adhesiveness and crosslinking density, and a highly reliable encapsulant sheet for solar cell modules and a solar cell module that does not cause the problem of swelling. The purpose is to provide.
本発明は上記のような従来技術の課題を解決しようとするものであり、密着性や架橋密度が高い、膨れの問題が生じない高信頼性の太陽電池モジュール用封止材シート及び太陽電池モジュールを提供することを目的とする。 However, the composition as shown in the prior art is not yet satisfactory as the reliability of the sealing material for solar cells intended for long-term use.
The present invention is intended to solve the above-described problems of the prior art, and has a high adhesiveness and crosslinking density, and a highly reliable encapsulant sheet for solar cell modules and a solar cell module that does not cause the problem of swelling. The purpose is to provide.
前記目的を達成するため、本発明の一態様に係る太陽電池モジュール用封止材シートは、エチレン－αオレフィン共重合体、有機過酸化物及びシランカップリング剤を含み、下記条件（１）及び（２）を満たすことを特徴とする。
（１）５．４≦（Ａ×Ｂ）／Ｃ≦１０．１
（２）６．０×１０－３≦Ａ×（Ｄ／Ｅ）≦１．０×１０－２
（ただし、Ａは前記有機過酸化物１分子から発生する理論オキシラジカル量であり、Ｂは前記有機過酸化物のモル量であり、Ｃは前記シランカップリング剤のモル量であり、Ｄは前記エチレン－αオレフィン共重合体１００質量部に対する前記有機過酸化物の含有量（質量部）であり、Ｅは前記有機過酸化物の分子量である。）
この太陽電池モジュール用封止材シートにおいては、前記エチレン－αオレフィン共重合体の密度を０．８６ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下としてもよい。
また、本発明の他の態様に係る太陽電池モジュールは、太陽電池セルと、前記太陽電池セルを封止する封止材層と、前記封止材層の表面側を保護する表面保護部材と、前記封止材層の裏面側を保護する裏面保護部材と、を有し、前記封止材層が、前記太陽電池モジュール用封止材シートにより形成されていることを特徴とする。 In order to achieve the above object, a solar cell module encapsulant sheet according to an aspect of the present invention includes an ethylene-α-olefin copolymer, an organic peroxide, and a silane coupling agent, and includes the following conditions (1) and (2) is satisfied.
(1) 5.4 ≦ (A × B) /C≦10.1
(2) 6.0 × 10 −3 ≦ A × (D / E) ≦ 1.0 × 10 −2
(However, A is the theoretical oxy radical amount generated from one molecule of the organic peroxide, B is the molar amount of the organic peroxide, C is the molar amount of the silane coupling agent, and D is (The content (parts by mass) of the organic peroxide relative to 100 parts by mass of the ethylene-α-olefin copolymer, and E is the molecular weight of the organic peroxide.)
In this solar cell module encapsulant sheet, the density of the ethylene-α-olefin copolymer may be 0.86 g / cm 3 or more and 0.90 g / cm 3 or less.
Moreover, the solar cell module which concerns on the other aspect of this invention is a solar cell, the sealing material layer which seals the said photovoltaic cell, the surface protection member which protects the surface side of the said sealing material layer, And a back surface protection member for protecting the back surface side of the sealing material layer, wherein the sealing material layer is formed by the solar cell module sealing material sheet.
（１）５．４≦（Ａ×Ｂ）／Ｃ≦１０．１
（２）６．０×１０－３≦Ａ×（Ｄ／Ｅ）≦１．０×１０－２
（ただし、Ａは前記有機過酸化物１分子から発生する理論オキシラジカル量であり、Ｂは前記有機過酸化物のモル量であり、Ｃは前記シランカップリング剤のモル量であり、Ｄは前記エチレン－αオレフィン共重合体１００質量部に対する前記有機過酸化物の含有量（質量部）であり、Ｅは前記有機過酸化物の分子量である。）
この太陽電池モジュール用封止材シートにおいては、前記エチレン－αオレフィン共重合体の密度を０．８６ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下としてもよい。
また、本発明の他の態様に係る太陽電池モジュールは、太陽電池セルと、前記太陽電池セルを封止する封止材層と、前記封止材層の表面側を保護する表面保護部材と、前記封止材層の裏面側を保護する裏面保護部材と、を有し、前記封止材層が、前記太陽電池モジュール用封止材シートにより形成されていることを特徴とする。 In order to achieve the above object, a solar cell module encapsulant sheet according to an aspect of the present invention includes an ethylene-α-olefin copolymer, an organic peroxide, and a silane coupling agent, and includes the following conditions (1) and (2) is satisfied.
(1) 5.4 ≦ (A × B) /C≦10.1
(2) 6.0 × 10 −3 ≦ A × (D / E) ≦ 1.0 × 10 −2
(However, A is the theoretical oxy radical amount generated from one molecule of the organic peroxide, B is the molar amount of the organic peroxide, C is the molar amount of the silane coupling agent, and D is (The content (parts by mass) of the organic peroxide relative to 100 parts by mass of the ethylene-α-olefin copolymer, and E is the molecular weight of the organic peroxide.)
In this solar cell module encapsulant sheet, the density of the ethylene-α-olefin copolymer may be 0.86 g / cm 3 or more and 0.90 g / cm 3 or less.
Moreover, the solar cell module which concerns on the other aspect of this invention is a solar cell, the sealing material layer which seals the said photovoltaic cell, the surface protection member which protects the surface side of the said sealing material layer, And a back surface protection member for protecting the back surface side of the sealing material layer, wherein the sealing material layer is formed by the solar cell module sealing material sheet.
本発明の太陽電池モジュール用封止材シートは、優れた密着性と高い架橋密度を有する封止材層を安定して形成でき、膨れの問題が生じず長期使用において高い信頼性を有する太陽電池モジュールを製造できる。また、本発明の太陽電池モジュールは、前記太陽電池モジュール用封止材シートを用いているため、長期使用において信頼性が高い。
The solar cell module encapsulant sheet of the present invention can stably form an encapsulant layer having excellent adhesion and high crosslink density, has no problem of swelling, and has high reliability in long-term use. Modules can be manufactured. Moreover, since the solar cell module of this invention uses the said sealing material sheet for solar cell modules, it is highly reliable in long-term use.
＜太陽電池モジュール用封止材シートについて＞
以下、本発明の太陽電池モジュール用封止材シート（以下、「封止材シート」という。）の実施形態の一例について詳細に説明する。本発明の封止材シートは、エチレン－αオレフィン共重合体、有機過酸化物及びシランカップリング剤を含む。
本発明の封止材シートを形成する樹脂基材は、エチレン－αオレフィン共重合体を主成分として使用することが好ましい。エチレン－αオレフィン共重合体は、高い透明性を有し、酢酸が発生しない点でエチレン－酢酸ビニル共重合体よりも有利である。エチレン－αオレフィン共重合体を主成分とするとは、樹脂基材の総量に対して、エチレン－αオレフィン共重合体を９５質量％以上とすることを意味する。 <About the sealing sheet for solar cell modules>
Hereinafter, an example of an embodiment of a sealing material sheet for solar cell modules of the present invention (hereinafter referred to as “sealing material sheet”) will be described in detail. The encapsulant sheet of the present invention contains an ethylene-α olefin copolymer, an organic peroxide, and a silane coupling agent.
The resin base material forming the sealing material sheet of the present invention preferably uses an ethylene-α-olefin copolymer as a main component. The ethylene-α olefin copolymer is more advantageous than the ethylene-vinyl acetate copolymer in that it has high transparency and does not generate acetic acid. The phrase “having the ethylene-α-olefin copolymer as a main component” means that the ethylene-α-olefin copolymer is 95% by mass or more based on the total amount of the resin base material.
以下、本発明の太陽電池モジュール用封止材シート（以下、「封止材シート」という。）の実施形態の一例について詳細に説明する。本発明の封止材シートは、エチレン－αオレフィン共重合体、有機過酸化物及びシランカップリング剤を含む。
本発明の封止材シートを形成する樹脂基材は、エチレン－αオレフィン共重合体を主成分として使用することが好ましい。エチレン－αオレフィン共重合体は、高い透明性を有し、酢酸が発生しない点でエチレン－酢酸ビニル共重合体よりも有利である。エチレン－αオレフィン共重合体を主成分とするとは、樹脂基材の総量に対して、エチレン－αオレフィン共重合体を９５質量％以上とすることを意味する。 <About the sealing sheet for solar cell modules>
Hereinafter, an example of an embodiment of a sealing material sheet for solar cell modules of the present invention (hereinafter referred to as “sealing material sheet”) will be described in detail. The encapsulant sheet of the present invention contains an ethylene-α olefin copolymer, an organic peroxide, and a silane coupling agent.
The resin base material forming the sealing material sheet of the present invention preferably uses an ethylene-α-olefin copolymer as a main component. The ethylene-α olefin copolymer is more advantageous than the ethylene-vinyl acetate copolymer in that it has high transparency and does not generate acetic acid. The phrase “having the ethylene-α-olefin copolymer as a main component” means that the ethylene-α-olefin copolymer is 95% by mass or more based on the total amount of the resin base material.
本発明の封止材シートには、エチレン－αオレフィン共重合体に加えて他の樹脂が含有されていてもよい。他の樹脂としては、アイオノマー、エチレン－メタクリル酸共重合体、エチレン－アクリル酸共重合体、ポリフッ化ビニル、ポリ塩化ビニル、またはこれらの共重合体等が挙げられる。本発明の封止材シートの樹脂基材中のエチレン－αオレフィン共重合体の割合は、９５質量％以上が好ましく、９７質量％以上がより好ましく、１００質量％が特に好ましい。
The sealing material sheet of the present invention may contain other resins in addition to the ethylene-α-olefin copolymer. Examples of other resins include ionomers, ethylene-methacrylic acid copolymers, ethylene-acrylic acid copolymers, polyvinyl fluoride, polyvinyl chloride, and copolymers thereof. The proportion of the ethylene-α-olefin copolymer in the resin substrate of the encapsulant sheet of the present invention is preferably 95% by mass or more, more preferably 97% by mass or more, and particularly preferably 100% by mass.
有機過酸化物は、エチレン－αオレフィン共重合体の架橋反応を開始させる架橋剤として作用する。有機過酸化物としては、１，１－ジ（ｔ－ブチルパーオキシ）シクロヘキサン、ｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート、１，１－ジ（ｔ－ヘキシルパーオキシ）シクロヘキサン、ｎ－ブチル－４，４－ジ－（ｔ－ブチルパーオキシ）バレレート、ｔ－ブチルパーオキシ－３，５，５－トリメチルヘキサノエート、２，５－ジメチル－２，５－ジ（ｔ－ブチルパーオキシ）ヘキサン、ｔ－ブチルクミルパーオキシド、２，２－ジ－（ｔ－ブチルパーオキシ）ブタン等が挙げられる。
Organic peroxide acts as a crosslinking agent that initiates a crosslinking reaction of the ethylene-α-olefin copolymer. Examples of organic peroxides include 1,1-di (t-butylperoxy) cyclohexane, t-butylperoxy-2-ethylhexyl monocarbonate, 1,1-di (t-hexylperoxy) cyclohexane, and n-butyl. -4,4-di- (t-butylperoxy) valerate, t-butylperoxy-3,5,5-trimethylhexanoate, 2,5-dimethyl-2,5-di (t-butylperoxy) ) Hexane, t-butylcumyl peroxide, 2,2-di- (t-butylperoxy) butane and the like.
シランカップリング剤は、エチレン－αオレフィン共重合体を含む樹脂基材により形成される封止材と、その表面及び裏面を保護する表面保護部材及び裏面保護部材との密着性を向上させる作用がある。
シランカップリング剤としては、γ－メタクリロキシプロピルトリメトキシシラン、トリメトキシプロピルシラン、トリメトキシメチルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、トリクロロプロピルシラン、トリエトキシフェニルシラン等が挙げられる。 The silane coupling agent has an effect of improving adhesion between a sealing material formed of a resin base material containing an ethylene-α-olefin copolymer, and a surface protection member and a back surface protection member for protecting the front surface and the back surface. is there.
Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, trimethoxypropylsilane, trimethoxymethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, trichloropropylsilane, triethoxyphenylsilane, and the like.
シランカップリング剤としては、γ－メタクリロキシプロピルトリメトキシシラン、トリメトキシプロピルシラン、トリメトキシメチルシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、トリクロロプロピルシラン、トリエトキシフェニルシラン等が挙げられる。 The silane coupling agent has an effect of improving adhesion between a sealing material formed of a resin base material containing an ethylene-α-olefin copolymer, and a surface protection member and a back surface protection member for protecting the front surface and the back surface. is there.
Examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, trimethoxypropylsilane, trimethoxymethylsilane, vinyltrimethoxysilane, vinyltriethoxysilane, trichloropropylsilane, triethoxyphenylsilane, and the like.
本発明の封止材シートにおける有機過酸化物及びシランカップリング剤は、下記条件（１）及び条件（２）を満たすように含有される。
（１）５．４≦（Ａ×Ｂ）／Ｃ≦１０．１
（２）６．０×１０－３≦Ａ×（Ｄ／Ｅ）≦１．０×１０－２
（ただし、Ａは有機過酸化物１分子から発生する理論オキシラジカル量であり、Ｂは有機過酸化物のモル量であり、Ｃはシランカップリング剤のモル量であり、Ｄはエチレン－αオレフィン共重合体１００質量部に対する有機過酸化物の含有量（質量部）であり、Ｅは有機過酸化物の分子量である。）
条件（１）における有機過酸化物１分子から発生する理論オキシラジカル量Ａとは、下式（１－１）で表される量である。
Ａ＝ａ×２ ・・・（１－１）
（ただし、式（１－１）中のａは有機過酸化物中の過酸化結合の数である。）
本発明の封止材シートにおいては、有機過酸化物１分子から発生する理論オキシラジカル量Ａと有機過酸化物のモル量Ｂとの積と、シランカップリング剤のモル量Ｃの比（Ａ×Ｂ）／Ｃの値が５．４以上１０．１以下であることが好ましい。 The organic peroxide and the silane coupling agent in the sealing material sheet of the present invention are contained so as to satisfy the following condition (1) and condition (2).
(1) 5.4 ≦ (A × B) /C≦10.1
(2) 6.0 × 10 −3 ≦ A × (D / E) ≦ 1.0 × 10 −2
(Where A is the amount of theoretical oxy radicals generated from one molecule of organic peroxide, B is the molar amount of organic peroxide, C is the molar amount of silane coupling agent, and D is ethylene-α (The content (parts by mass) of the organic peroxide with respect to 100 parts by mass of the olefin copolymer, and E is the molecular weight of the organic peroxide.)
The theoretical oxy radical amount A generated from one molecule of the organic peroxide under the condition (1) is an amount represented by the following formula (1-1).
A = a × 2 (1-1)
(Where a in Formula (1-1) is the number of peroxide bonds in the organic peroxide)
In the sealing material sheet of the present invention, the ratio of the product of the theoretical oxy radical amount A generated from one molecule of the organic peroxide and the molar amount B of the organic peroxide to the molar amount C of the silane coupling agent (A The value of xB) / C is preferably 5.4 or more and 10.1 or less.
（１）５．４≦（Ａ×Ｂ）／Ｃ≦１０．１
（２）６．０×１０－３≦Ａ×（Ｄ／Ｅ）≦１．０×１０－２
（ただし、Ａは有機過酸化物１分子から発生する理論オキシラジカル量であり、Ｂは有機過酸化物のモル量であり、Ｃはシランカップリング剤のモル量であり、Ｄはエチレン－αオレフィン共重合体１００質量部に対する有機過酸化物の含有量（質量部）であり、Ｅは有機過酸化物の分子量である。）
条件（１）における有機過酸化物１分子から発生する理論オキシラジカル量Ａとは、下式（１－１）で表される量である。
Ａ＝ａ×２ ・・・（１－１）
（ただし、式（１－１）中のａは有機過酸化物中の過酸化結合の数である。）
本発明の封止材シートにおいては、有機過酸化物１分子から発生する理論オキシラジカル量Ａと有機過酸化物のモル量Ｂとの積と、シランカップリング剤のモル量Ｃの比（Ａ×Ｂ）／Ｃの値が５．４以上１０．１以下であることが好ましい。 The organic peroxide and the silane coupling agent in the sealing material sheet of the present invention are contained so as to satisfy the following condition (1) and condition (2).
(1) 5.4 ≦ (A × B) /C≦10.1
(2) 6.0 × 10 −3 ≦ A × (D / E) ≦ 1.0 × 10 −2
(Where A is the amount of theoretical oxy radicals generated from one molecule of organic peroxide, B is the molar amount of organic peroxide, C is the molar amount of silane coupling agent, and D is ethylene-α (The content (parts by mass) of the organic peroxide with respect to 100 parts by mass of the olefin copolymer, and E is the molecular weight of the organic peroxide.)
The theoretical oxy radical amount A generated from one molecule of the organic peroxide under the condition (1) is an amount represented by the following formula (1-1).
A = a × 2 (1-1)
(Where a in Formula (1-1) is the number of peroxide bonds in the organic peroxide)
In the sealing material sheet of the present invention, the ratio of the product of the theoretical oxy radical amount A generated from one molecule of the organic peroxide and the molar amount B of the organic peroxide to the molar amount C of the silane coupling agent (A The value of xB) / C is preferably 5.4 or more and 10.1 or less.
比（Ａ×Ｂ）／Ｃが５．４以上であれば、エチレン－αオレフィン共重合体の架橋反応が充分に進行しやすく、高い耐熱性を得ることができる。比（Ａ×Ｂ）／Ｃが１０．１以下であれば、優れた密着性が得られ、封止材層と、表面保護部材及び裏面保護部材との剥離を抑制できる。
また、封止材シートにおいては、前記Ａ×（Ｄ／Ｅ）の値が６．０×１０－３以上１．０×１０－２以下であることが好ましい。前記Ａ×（Ｄ／Ｅ）の値が６．０×１０－３以上であれば、エチレン－αオレフィン共重合体の架橋反応が充分に進行し、高い耐熱性を得ることができる。前記Ａ×（Ｄ／Ｅ）の値が１．０×１０－２以下であれば、封止材シート中の有機過酸化物反応残渣や未反応物に由来する膨れの問題を防ぐことができる。また、封止材シートの成形加工時の安定性も高くなる。 When the ratio (A × B) / C is 5.4 or more, the crosslinking reaction of the ethylene-α-olefin copolymer is likely to proceed sufficiently, and high heat resistance can be obtained. If ratio (A * B) / C is 10.1 or less, the outstanding adhesiveness will be obtained and peeling with a sealing material layer, a surface protection member, and a back surface protection member can be suppressed.
In the encapsulant sheet, the value of A × (D / E) is preferably 6.0 × 10 −3 or more and 1.0 × 10 −2 or less. If the value of A × (D / E) is 6.0 × 10 −3 or more, the cross-linking reaction of the ethylene-α-olefin copolymer proceeds sufficiently and high heat resistance can be obtained. If the value of A × (D / E) is 1.0 × 10 −2 or less, the problem of blistering derived from organic peroxide reaction residues and unreacted substances in the encapsulant sheet can be prevented. . Moreover, the stability at the time of the shaping | molding process of a sealing material sheet becomes high.
また、封止材シートにおいては、前記Ａ×（Ｄ／Ｅ）の値が６．０×１０－３以上１．０×１０－２以下であることが好ましい。前記Ａ×（Ｄ／Ｅ）の値が６．０×１０－３以上であれば、エチレン－αオレフィン共重合体の架橋反応が充分に進行し、高い耐熱性を得ることができる。前記Ａ×（Ｄ／Ｅ）の値が１．０×１０－２以下であれば、封止材シート中の有機過酸化物反応残渣や未反応物に由来する膨れの問題を防ぐことができる。また、封止材シートの成形加工時の安定性も高くなる。 When the ratio (A × B) / C is 5.4 or more, the crosslinking reaction of the ethylene-α-olefin copolymer is likely to proceed sufficiently, and high heat resistance can be obtained. If ratio (A * B) / C is 10.1 or less, the outstanding adhesiveness will be obtained and peeling with a sealing material layer, a surface protection member, and a back surface protection member can be suppressed.
In the encapsulant sheet, the value of A × (D / E) is preferably 6.0 × 10 −3 or more and 1.0 × 10 −2 or less. If the value of A × (D / E) is 6.0 × 10 −3 or more, the cross-linking reaction of the ethylene-α-olefin copolymer proceeds sufficiently and high heat resistance can be obtained. If the value of A × (D / E) is 1.0 × 10 −2 or less, the problem of blistering derived from organic peroxide reaction residues and unreacted substances in the encapsulant sheet can be prevented. . Moreover, the stability at the time of the shaping | molding process of a sealing material sheet becomes high.
条件（１）は、ラジカル架橋時に発生する理論上のラジカル個数（Ａ×Ｂ）をシランカップリング剤の個数（Ｃ）で除した値が一定の範囲内にあることを表す。これは、ラジカルの数（Ａ×Ｂ）が増加（減少）すると架橋反応が高く（低く）なること、かつ、シランカップリング剤の数（Ｃ）が増加（減少）すると逆に架橋反応が低く（高く）なることを見出し、この知見を条件（１）として示したものである。架橋反応が低すぎると、樹脂の黄変などに対する劣化耐性が低下し、架橋反応が高すぎると、密着性が低下することから、この条件（１）の範囲が最適であることを見出した。なお、シランカップリング剤は、ラジカルの失活効果を有するものである。
Condition (1) represents that the value obtained by dividing the theoretical number of radicals (A × B) generated during radical crosslinking by the number of silane coupling agents (C) is within a certain range. This is because when the number of radicals (A × B) increases (decreases), the crosslinking reaction increases (decreases), and when the number of silane coupling agents (C) increases (decreases), the crosslinking reaction decreases. This finding is shown as condition (1). When the crosslinking reaction is too low, deterioration resistance against yellowing of the resin is lowered, and when the crosslinking reaction is too high, the adhesiveness is lowered. Therefore, it was found that the range of the condition (1) is optimal. The silane coupling agent has a radical deactivation effect.
条件（２）は、エチレン－αオレフィン共重合体に対する理論上のラジカル個数比を表したものである。ラジカル個数比が増加（減少）すると架橋反応が高く（低く）なることを見出し、この知見を条件（２）として示したものである。架橋反応が低すぎると、樹脂の黄変などに対する劣化耐性が低下し、架橋反応が高すぎると、密着性が低下することから、この条件（２）の範囲が最適であることを見出したものである。
そして、この条件（１）、（２）の両方を満たす範囲が、良好な封止材を得ることができる範囲であることを見出したものであり、すなわち、添加量のバランス（ラジカル発生量）に着目したものである。 Condition (2) represents the theoretical radical number ratio with respect to the ethylene-α-olefin copolymer. It is found that the crosslinking reaction increases (decreases) when the radical number ratio increases (decreases), and this knowledge is shown as condition (2). When the cross-linking reaction is too low, the deterioration resistance against the yellowing of the resin is lowered, and when the cross-linking reaction is too high, the adhesiveness is lowered, so that the condition (2) is found to be optimal. It is.
And it discovered that the range which satisfy | fills both of these conditions (1) and (2) is a range which can obtain a favorable sealing material, ie, the balance of addition amount (radical generation amount). Is focused on.
そして、この条件（１）、（２）の両方を満たす範囲が、良好な封止材を得ることができる範囲であることを見出したものであり、すなわち、添加量のバランス（ラジカル発生量）に着目したものである。 Condition (2) represents the theoretical radical number ratio with respect to the ethylene-α-olefin copolymer. It is found that the crosslinking reaction increases (decreases) when the radical number ratio increases (decreases), and this knowledge is shown as condition (2). When the cross-linking reaction is too low, the deterioration resistance against the yellowing of the resin is lowered, and when the cross-linking reaction is too high, the adhesiveness is lowered, so that the condition (2) is found to be optimal. It is.
And it discovered that the range which satisfy | fills both of these conditions (1) and (2) is a range which can obtain a favorable sealing material, ie, the balance of addition amount (radical generation amount). Is focused on.
本発明の封止材シートに用いられるエチレン－αオレフィン共重合体の密度は、０．８６ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下であることが好ましい。密度が０．８６ｇ／ｃｍ３以上であれば、封止材シートのブロッキングを抑制しやすい。密度が０．９０ｇ／ｃｍ３以下であれば、高い透明性を得られる。また、シート加工時の安定性も増す。密度は、エチレン－αオレフィン共重合体の重合時のα－オレフィン含有量や重合温度、触媒量などを変えることにより調節できる。なお、エチレン－αオレフィン共重合体の密度の測定は、ＪＩＳ－Ｋ６９２２－２：２０１０に準拠する。
The density of the ethylene-α-olefin copolymer used in the sealing material sheet of the present invention is preferably 0.86 g / cm 3 or more and 0.90 g / cm 3 or less. When the density is 0.86 g / cm 3 or more, it is easy to suppress blocking of the encapsulant sheet. If the density is 0.90 g / cm 3 or less, high transparency can be obtained. In addition, stability during sheet processing is increased. The density can be adjusted by changing the α-olefin content, the polymerization temperature, the catalyst amount, etc. during the polymerization of the ethylene-α-olefin copolymer. The measurement of the density of the ethylene-α-olefin copolymer is based on JIS-K6922-2: 2010.
また、本発明の封止材シートには、前記有機過酸化物及びシランカップリング剤の他に、架橋反応を促進する架橋助剤が含有されていてもよい。架橋助剤としては、トリアリルイソシアヌレート、ジアリルフタレート、トリアリルシアヌレート等が挙げられる。
また、本発明の封止材シートには、形成される封止材層の耐光性及び熱安定性の観点から、紫外線吸収剤、酸化防止剤等の安定化剤が含有されていてもよい。
耐光性の向上のために用いられる紫外線吸収剤としては、２－（５－メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（３－ｔ－ブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノール、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノン等が挙げられる。 Moreover, the sealing material sheet of this invention may contain the crosslinking adjuvant which accelerates | stimulates a crosslinking reaction other than the said organic peroxide and a silane coupling agent. Examples of the crosslinking aid include triallyl isocyanurate, diallyl phthalate, triallyl cyanurate and the like.
Moreover, stabilizers, such as a ultraviolet absorber and antioxidant, may contain in the sealing material sheet of this invention from a viewpoint of the light resistance and heat stability of the sealing material layer formed.
Examples of ultraviolet absorbers used for improving light resistance include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5. -Chlorobenzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-dihydroxybenzophenone, 2-hydroxy-4 -N-octyloxybenzophenone and the like.
また、本発明の封止材シートには、形成される封止材層の耐光性及び熱安定性の観点から、紫外線吸収剤、酸化防止剤等の安定化剤が含有されていてもよい。
耐光性の向上のために用いられる紫外線吸収剤としては、２－（５－メチル－２－ヒドロキシフェニル）ベンゾトリアゾール、２－（３－ｔ－ブチル－５－メチル－２－ヒドロキシフェニル）－５－クロロベンゾトリアゾール、２－（４，６－ジフェニル－１，３，５－トリアジン－２－イル）－５－［（ヘキシル）オキシ］－フェノール、２，４－ジヒドロキシベンゾフェノン、２－ヒドロキシ－４－ｎ－オクチルオキシベンゾフェノン等が挙げられる。 Moreover, the sealing material sheet of this invention may contain the crosslinking adjuvant which accelerates | stimulates a crosslinking reaction other than the said organic peroxide and a silane coupling agent. Examples of the crosslinking aid include triallyl isocyanurate, diallyl phthalate, triallyl cyanurate and the like.
Moreover, stabilizers, such as a ultraviolet absorber and antioxidant, may contain in the sealing material sheet of this invention from a viewpoint of the light resistance and heat stability of the sealing material layer formed.
Examples of ultraviolet absorbers used for improving light resistance include 2- (5-methyl-2-hydroxyphenyl) benzotriazole and 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5. -Chlorobenzotriazole, 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-[(hexyl) oxy] -phenol, 2,4-dihydroxybenzophenone, 2-hydroxy-4 -N-octyloxybenzophenone and the like.
熱安定性の向上のために用いられる酸化防止剤としては、１，６－ヘキサンジオール－ビス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、ペンタエリスリチル－テトラキス［３－（３，５－ジ－ｔ－ブチル－４－ヒドロキシフェニル）プロピオネート］、トリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト、２，４－ビス－（ｎ－オクチルチオ）－６－（４－ヒドロキシ－３，５－ジ－ｔ－ブチルアニリノ）－１，３，５－トリアジン、ビス（２，２，６，６－テトラメチル－４－ピペリジル）セバケート等が挙げられる。
Antioxidants used for improving thermal stability include 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], pentaerythrityl- Tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], tris (2,4-di-tert-butylphenyl) phosphite, 2,4-bis- (n-octylthio) Examples include -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like.
（封止材シートの製造方法について）
本発明の封止材シートは、有機過酸化物及びシランカップリング剤を前記条件（１）及び条件（２）を満たすように含有させる以外は、公知の製造方法で製造できる。例えば、前記樹脂基材に、有機過酸化物及びシランカップリング剤、並びに必要に応じて添加する他の添加剤を混合して加熱溶融させた樹脂を、直線状スリットを有するＴダイ等を用いて共押し出し法により製膜する製膜工程を有する方法が挙げられる。
また、前記製膜工程においては、熱溶融した状態の樹脂シートの表面を、凹凸パターンが施されているロール（金属またはゴム製）に密着させることで、該樹脂シート片面もしくは両面に該ロールの凹凸パターンを転写させてもよい。これにより、ブロッキング防止のためのエンボス加工を封止材シートに施すことができる。 (About the manufacturing method of a sealing material sheet)
The encapsulant sheet of the present invention can be produced by a known production method except that the organic peroxide and the silane coupling agent are contained so as to satisfy the conditions (1) and (2). For example, the resin base material is mixed with an organic peroxide, a silane coupling agent, and other additives that are added as necessary, and the resin is heated and melted. And a method having a film forming step of forming a film by a co-extrusion method.
Further, in the film forming step, the surface of the heat-melted resin sheet is brought into close contact with a roll (made of metal or rubber) having a concavo-convex pattern, so that the surface of the roll is placed on one or both sides of the resin sheet. The uneven pattern may be transferred. Thereby, the embossing for blocking prevention can be given to a sealing material sheet.
本発明の封止材シートは、有機過酸化物及びシランカップリング剤を前記条件（１）及び条件（２）を満たすように含有させる以外は、公知の製造方法で製造できる。例えば、前記樹脂基材に、有機過酸化物及びシランカップリング剤、並びに必要に応じて添加する他の添加剤を混合して加熱溶融させた樹脂を、直線状スリットを有するＴダイ等を用いて共押し出し法により製膜する製膜工程を有する方法が挙げられる。
また、前記製膜工程においては、熱溶融した状態の樹脂シートの表面を、凹凸パターンが施されているロール（金属またはゴム製）に密着させることで、該樹脂シート片面もしくは両面に該ロールの凹凸パターンを転写させてもよい。これにより、ブロッキング防止のためのエンボス加工を封止材シートに施すことができる。 (About the manufacturing method of a sealing material sheet)
The encapsulant sheet of the present invention can be produced by a known production method except that the organic peroxide and the silane coupling agent are contained so as to satisfy the conditions (1) and (2). For example, the resin base material is mixed with an organic peroxide, a silane coupling agent, and other additives that are added as necessary, and the resin is heated and melted. And a method having a film forming step of forming a film by a co-extrusion method.
Further, in the film forming step, the surface of the heat-melted resin sheet is brought into close contact with a roll (made of metal or rubber) having a concavo-convex pattern, so that the surface of the roll is placed on one or both sides of the resin sheet. The uneven pattern may be transferred. Thereby, the embossing for blocking prevention can be given to a sealing material sheet.
従来の封止材シートを用いた太陽電池モジュールでは、封止材シートの組成によっては充分な密着性と架橋密度が得られないことや、膨れが生じることがある。本発明者等がこの点について詳細に検討したところ、密着性を高める目的で封止材シートにシランカップリング剤を含有させた場合に、密着性が向上する一方で、該封止材シートにより形成される封止材層の架橋密度が低下していることが判明した。また、架橋密度を上げるために、有機過酸化物を多量に添加すると、封止材シート中の有機過酸化物反応残渣や未反応物に由来する膨れの問題が生じていることも判明した。
In a conventional solar cell module using a sealing material sheet, depending on the composition of the sealing material sheet, sufficient adhesion and crosslinking density may not be obtained, and swelling may occur. When the present inventors examined in detail about this point, when the silane coupling agent was contained in the sealing material sheet for the purpose of improving the adhesiveness, the adhesiveness was improved, but the sealing material sheet It was found that the crosslink density of the encapsulant layer formed was reduced. It has also been found that when a large amount of organic peroxide is added to increase the crosslinking density, there is a problem of blistering derived from organic peroxide reaction residues and unreacted substances in the encapsulant sheet.
そして、有機過酸化物とシランカップリング剤を前記条件（１）及び条件（２）を満たすように含有させることで、密着性を向上させるとともに、封止材層の架橋密度の低下を抑制でき、膨れも生じないことを見出した。
このように、本発明の封止材シートは、前記条件（１）及び条件（２）を満たすように有機過酸化物とシランカップリング剤が含有されているため、高い架橋密度で、優れた密着性を有し、膨れの無い、高い信頼性を兼ね備えた封止材層を安定して形成できる。そのため、該封止材シートを用いた太陽電池モジュールの長期使用における信頼性が高くなる。 And by containing an organic peroxide and a silane coupling agent so that the said conditions (1) and conditions (2) may be satisfied, while improving adhesiveness, the fall of the crosslinking density of a sealing material layer can be suppressed. They found that no blistering occurred.
Thus, since the sealing material sheet of the present invention contains the organic peroxide and the silane coupling agent so as to satisfy the conditions (1) and (2), it is excellent in high crosslinking density. It is possible to stably form a sealing material layer having adhesiveness and no swelling and having high reliability. Therefore, the reliability in the long-term use of the solar cell module using this sealing material sheet becomes high.
このように、本発明の封止材シートは、前記条件（１）及び条件（２）を満たすように有機過酸化物とシランカップリング剤が含有されているため、高い架橋密度で、優れた密着性を有し、膨れの無い、高い信頼性を兼ね備えた封止材層を安定して形成できる。そのため、該封止材シートを用いた太陽電池モジュールの長期使用における信頼性が高くなる。 And by containing an organic peroxide and a silane coupling agent so that the said conditions (1) and conditions (2) may be satisfied, while improving adhesiveness, the fall of the crosslinking density of a sealing material layer can be suppressed. They found that no blistering occurred.
Thus, since the sealing material sheet of the present invention contains the organic peroxide and the silane coupling agent so as to satisfy the conditions (1) and (2), it is excellent in high crosslinking density. It is possible to stably form a sealing material layer having adhesiveness and no swelling and having high reliability. Therefore, the reliability in the long-term use of the solar cell module using this sealing material sheet becomes high.
＜太陽電池モジュールについて＞
以下、本発明の太陽電池モジュールの実施形態の一例について、図面を参照しながら詳細に説明する。
図１の太陽電池モジュール５は、太陽電池セル３と、太陽電池セル３を封止する封止材層２と、封止材層２の表面側を保護する表面保護部材１と、封止材層２の裏面側を保護する裏面保護部材４と、を有し、封止材層２が、前述した本発明の封止材シートにより形成されているモジュールである。
（太陽電池セルについて）
太陽電池セル３は、受光面に入射した光を光電効果により電気に変換する機能を有するセルである。太陽電池セル３は、太陽電池モジュール５内において複数個（図１では２つ）が電極（図示省略）によって接続されている。なお、太陽電池セル３の数は特に限定されない。
太陽電池セル３の材料としては、例えば、結晶系シリコンが挙げられる。なかでも、製造の簡便さとコスト面から、多結晶シリコンが特に好ましい。 <About solar cell module>
Hereinafter, an example of an embodiment of a solar cell module of the present invention will be described in detail with reference to the drawings.
1 includes asolar battery cell 3, a sealing material layer 2 that seals the solar battery cell 3, a surface protection member 1 that protects the surface side of the sealing material layer 2, and a sealing material. The back surface protection member 4 which protects the back surface side of the layer 2, and the sealing material layer 2 is a module formed with the sealing material sheet of this invention mentioned above.
(About solar cells)
Thesolar battery cell 3 is a cell having a function of converting light incident on the light receiving surface into electricity by a photoelectric effect. A plurality (two in FIG. 1) of solar cells 3 are connected by electrodes (not shown) in the solar cell module 5. In addition, the number of the photovoltaic cells 3 is not specifically limited.
Examples of the material of thesolar battery cell 3 include crystalline silicon. Among these, polycrystalline silicon is particularly preferable from the viewpoint of manufacturing simplicity and cost.
以下、本発明の太陽電池モジュールの実施形態の一例について、図面を参照しながら詳細に説明する。
図１の太陽電池モジュール５は、太陽電池セル３と、太陽電池セル３を封止する封止材層２と、封止材層２の表面側を保護する表面保護部材１と、封止材層２の裏面側を保護する裏面保護部材４と、を有し、封止材層２が、前述した本発明の封止材シートにより形成されているモジュールである。
（太陽電池セルについて）
太陽電池セル３は、受光面に入射した光を光電効果により電気に変換する機能を有するセルである。太陽電池セル３は、太陽電池モジュール５内において複数個（図１では２つ）が電極（図示省略）によって接続されている。なお、太陽電池セル３の数は特に限定されない。
太陽電池セル３の材料としては、例えば、結晶系シリコンが挙げられる。なかでも、製造の簡便さとコスト面から、多結晶シリコンが特に好ましい。 <About solar cell module>
Hereinafter, an example of an embodiment of a solar cell module of the present invention will be described in detail with reference to the drawings.
1 includes a
(About solar cells)
The
Examples of the material of the
（封止材層について）
封止材層２は、太陽電池セル３を包埋させて封止する層であり、本発明の封止材シートにより形成される。封止材層２の厚さは、０．２～０．８ｍｍが好ましい。
（表面保護部材について）
表面保護部材１としては、ガラス、ポリエチレンテレフタレート、ポリエチレンナフタレート、テトラフルオロエチレン－エチレン共重合体（ＥＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）等が挙げられる。透明性、耐候性、難燃性の点からガラスが好ましく用いられる。また、耐久性や耐候性、透明性の高い他の材料を用いても構わない。また、これら材料に耐久性や耐候性を付与するために、ハードコート層、ＵＶ吸収層、水蒸気バリア層等を積層しても構わない。 (About the sealing material layer)
The sealingmaterial layer 2 is a layer that embeds and seals the solar cells 3 and is formed of the sealing material sheet of the present invention. The thickness of the sealing material layer 2 is preferably 0.2 to 0.8 mm.
(About surface protection members)
Examples of thesurface protection member 1 include glass, polyethylene terephthalate, polyethylene naphthalate, tetrafluoroethylene-ethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), and the like. Glass is preferably used in terms of transparency, weather resistance, and flame retardancy. Further, other materials having high durability, weather resistance, and transparency may be used. Further, in order to impart durability and weather resistance to these materials, a hard coat layer, a UV absorption layer, a water vapor barrier layer, or the like may be laminated.
封止材層２は、太陽電池セル３を包埋させて封止する層であり、本発明の封止材シートにより形成される。封止材層２の厚さは、０．２～０．８ｍｍが好ましい。
（表面保護部材について）
表面保護部材１としては、ガラス、ポリエチレンテレフタレート、ポリエチレンナフタレート、テトラフルオロエチレン－エチレン共重合体（ＥＴＦＥ）、ポリクロロトリフルオロエチレン（ＰＣＴＦＥ）等が挙げられる。透明性、耐候性、難燃性の点からガラスが好ましく用いられる。また、耐久性や耐候性、透明性の高い他の材料を用いても構わない。また、これら材料に耐久性や耐候性を付与するために、ハードコート層、ＵＶ吸収層、水蒸気バリア層等を積層しても構わない。 (About the sealing material layer)
The sealing
(About surface protection members)
Examples of the
（裏面保護部材について）
裏面保護部材４としては、ガラス、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリメチルメタクリレート、ポリカーボネート、ＥＴＦＥ、ＰＣＴＦＥ、ポリビニルフロライド、エチレン－酢酸ビニル共重合体（ＥＶＡ）、アルミ箔及び、これらの積層体が挙げられる。耐久性や耐候性の高い他の材料を用いても構わない。また、水蒸気や酸素バリア性を付与するバリア層を積層しても構わない。 (About the back protection member)
Examples of the backsurface protection member 4 include glass, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate, polycarbonate, ETFE, PCTFE, polyvinyl fluoride, ethylene-vinyl acetate copolymer (EVA), aluminum foil, and laminates thereof. Can be mentioned. Other materials having high durability and weather resistance may be used. Moreover, you may laminate | stack the barrier layer which provides water vapor | steam and oxygen barrier property.
裏面保護部材４としては、ガラス、ポリエチレンテレフタレート、ポリエチレンナフタレート、ポリメチルメタクリレート、ポリカーボネート、ＥＴＦＥ、ＰＣＴＦＥ、ポリビニルフロライド、エチレン－酢酸ビニル共重合体（ＥＶＡ）、アルミ箔及び、これらの積層体が挙げられる。耐久性や耐候性の高い他の材料を用いても構わない。また、水蒸気や酸素バリア性を付与するバリア層を積層しても構わない。 (About the back protection member)
Examples of the back
（太陽電池モジュールの製造方法について）
以下、本発明の太陽電池モジュールの製造方法の一例として、太陽電池モジュール５の製造方法を説明する。ただし、本発明の太陽電池モジュールの製造方法は以下の方法には限定されない。
図２に示すように、裏面保護部材４、封止材シート６、太陽電池セル３、封止材シート６、表面保護部材１をこの順に積層して積層体とする。次いで、積層体を真空状態で加熱加圧する真空ラミネートを行い、上下２枚の封止材シート６内に太陽電池セル３を埋没させ、封止材シート６の樹脂基材を架橋硬化させて接着一体化することで封止材層２を形成させる。これにより、太陽電池モジュール５が得られる。２枚の封止材シート６は本発明の封止材シートであり、両者は同じ組成の封止材シートであってもよく、異なる組成の封止材シートであってもよいが、均一に架橋構造が形成されることで良好な品質のモジュールが得られやすい点から、同じ組成の封止材シートであることが好ましい。 (About solar cell module manufacturing method)
Hereinafter, the manufacturing method of thesolar cell module 5 is demonstrated as an example of the manufacturing method of the solar cell module of this invention. However, the manufacturing method of the solar cell module of the present invention is not limited to the following method.
As shown in FIG. 2, the backsurface protection member 4, the sealing material sheet 6, the solar cell 3, the sealing material sheet 6, and the surface protection member 1 are laminated | stacked in this order to make a laminated body. Next, vacuum lamination is performed by heating and pressurizing the laminate in a vacuum state, the solar cells 3 are embedded in the upper and lower two sealing material sheets 6, and the resin base material of the sealing material sheet 6 is crosslinked and cured to be bonded. The sealing material layer 2 is formed by integrating. Thereby, the solar cell module 5 is obtained. The two encapsulant sheets 6 are the encapsulant sheets of the present invention, both of which may be the same composition encapsulant sheet or different composition encapsulant sheets, but uniformly It is preferable that the encapsulant sheet has the same composition from the viewpoint that a good quality module can be easily obtained by forming a crosslinked structure.
以下、本発明の太陽電池モジュールの製造方法の一例として、太陽電池モジュール５の製造方法を説明する。ただし、本発明の太陽電池モジュールの製造方法は以下の方法には限定されない。
図２に示すように、裏面保護部材４、封止材シート６、太陽電池セル３、封止材シート６、表面保護部材１をこの順に積層して積層体とする。次いで、積層体を真空状態で加熱加圧する真空ラミネートを行い、上下２枚の封止材シート６内に太陽電池セル３を埋没させ、封止材シート６の樹脂基材を架橋硬化させて接着一体化することで封止材層２を形成させる。これにより、太陽電池モジュール５が得られる。２枚の封止材シート６は本発明の封止材シートであり、両者は同じ組成の封止材シートであってもよく、異なる組成の封止材シートであってもよいが、均一に架橋構造が形成されることで良好な品質のモジュールが得られやすい点から、同じ組成の封止材シートであることが好ましい。 (About solar cell module manufacturing method)
Hereinafter, the manufacturing method of the
As shown in FIG. 2, the back
以上説明した太陽電池モジュールは、本発明の封止材シートを用いているため、高い架橋密度で、かつ優れた密着性を有する封止材層が安定して形成されており、長期使用において高い信頼性を有している。
本発明に係る封止材シート６は、エチレン－αオレフィン共重合樹脂、有機過酸化物及びシランカップリング剤を含む。有機過酸化物はエチレン－αオレフィン共重合樹脂の架橋反応を開始させる架橋剤として作用し、シランカップリング剤は、エチレン－αオレフィン共重合樹脂と、表面保護部材１、裏面保護部材４との密着性を向上させる作用がある。 Since the solar cell module described above uses the encapsulant sheet of the present invention, an encapsulant layer having high crosslink density and excellent adhesion is stably formed, and is high in long-term use. It has reliability.
Theencapsulant sheet 6 according to the present invention includes an ethylene-α olefin copolymer resin, an organic peroxide, and a silane coupling agent. The organic peroxide acts as a crosslinking agent for initiating the crosslinking reaction of the ethylene-α-olefin copolymer resin, and the silane coupling agent is composed of the ethylene-α-olefin copolymer resin, the surface protection member 1 and the back surface protection member 4. It has the effect of improving adhesion.
本発明に係る封止材シート６は、エチレン－αオレフィン共重合樹脂、有機過酸化物及びシランカップリング剤を含む。有機過酸化物はエチレン－αオレフィン共重合樹脂の架橋反応を開始させる架橋剤として作用し、シランカップリング剤は、エチレン－αオレフィン共重合樹脂と、表面保護部材１、裏面保護部材４との密着性を向上させる作用がある。 Since the solar cell module described above uses the encapsulant sheet of the present invention, an encapsulant layer having high crosslink density and excellent adhesion is stably formed, and is high in long-term use. It has reliability.
The
以下、実施例及び比較例を示して本発明を詳細に説明する。ただし、本発明は以下の記載によっては限定されない。
本実施例で使用した原料を以下に示す。
・（樹脂）密度０．８８ｇ／ｃｍ３のエチレン－αオレフィン共重合樹脂
・（有機過酸化物）ｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート
・（シランカップリング剤）γ－メタクリロキシプロピルトリメトキシシラン
・（酸化防止剤）トリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト
［実施例１］
樹脂１００質量部に対し、有機過酸化物を１．２質量部、シランカップリング剤を０．３質量部、酸化防止剤を０．１質量部配合した樹脂材料を用いて、Ｔダイ法により厚み０．４ｍｍの封止材シートを作製した。
得られた封止材シートにおいては、（Ａ×Ｂ）／Ｃ＝８．１であり、Ａ×（Ｄ／Ｅ）＝９．７×１０－３であった。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
The raw materials used in this example are shown below.
・ (Resin) Ethylene-α-olefin copolymer resin with a density of 0.88 g / cm 3・ (Organic peroxide) t-Butylperoxy-2-ethylhexyl monocarbonate ・ (Silane coupling agent) γ-methacryloxypropyltri Methoxysilane (antioxidant) tris (2,4-di-t-butylphenyl) phosphite [Example 1]
Using a resin material in which 1.2 parts by weight of organic peroxide, 0.3 parts by weight of silane coupling agent, and 0.1 parts by weight of antioxidant are blended with respect to 100 parts by weight of resin, T-die method A sealing material sheet having a thickness of 0.4 mm was produced.
In the obtained sealing material sheet, (A × B) /C=8.1 and A × (D / E) = 9.7 × 10 −3 .
本実施例で使用した原料を以下に示す。
・（樹脂）密度０．８８ｇ／ｃｍ３のエチレン－αオレフィン共重合樹脂
・（有機過酸化物）ｔ－ブチルパーオキシ－２－エチルヘキシルモノカーボネート
・（シランカップリング剤）γ－メタクリロキシプロピルトリメトキシシラン
・（酸化防止剤）トリス（２，４－ジ－ｔ－ブチルフェニル）フォスファイト
［実施例１］
樹脂１００質量部に対し、有機過酸化物を１．２質量部、シランカップリング剤を０．３質量部、酸化防止剤を０．１質量部配合した樹脂材料を用いて、Ｔダイ法により厚み０．４ｍｍの封止材シートを作製した。
得られた封止材シートにおいては、（Ａ×Ｂ）／Ｃ＝８．１であり、Ａ×（Ｄ／Ｅ）＝９．７×１０－３であった。 Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the present invention is not limited by the following description.
The raw materials used in this example are shown below.
・ (Resin) Ethylene-α-olefin copolymer resin with a density of 0.88 g / cm 3・ (Organic peroxide) t-Butylperoxy-2-ethylhexyl monocarbonate ・ (Silane coupling agent) γ-methacryloxypropyltri Methoxysilane (antioxidant) tris (2,4-di-t-butylphenyl) phosphite [Example 1]
Using a resin material in which 1.2 parts by weight of organic peroxide, 0.3 parts by weight of silane coupling agent, and 0.1 parts by weight of antioxidant are blended with respect to 100 parts by weight of resin, T-die method A sealing material sheet having a thickness of 0.4 mm was produced.
In the obtained sealing material sheet, (A × B) /C=8.1 and A × (D / E) = 9.7 × 10 −3 .
次いで、得られた封止材シートと、表面保護部材として厚さ３ｍｍの白板ガラス、太陽電池セルとして多結晶シリコンセル、及び裏面保護部材としてポリエチレンテレフタレートとを用いて、それらを図２に例示したように表面保護部材、封止材シート、太陽電池セル、封止材シート及び裏面保護部材の順に積層した積層体を形成した。その後、上蓋側とラミネート室内でそれぞれ真空引き可能なラミネーター内に前記積層体を配置し、ラミネート室内の温度を１５０℃に維持しながら上蓋側とラミネート室内の両方で９０秒間真空引きを行い、前記積層体内部を脱気しながら仮圧着した（真空脱気・仮圧着）。前記仮圧着完了後、ラミネート室内の温度を１５０℃にし、ラミネーター上蓋側の真空状態を解除して、該積層体を大気圧により１０分間熱圧着させ（本圧着）、太陽電池モジュールを得た。
Then, using the obtained sealing material sheet, white plate glass having a thickness of 3 mm as a surface protection member, a polycrystalline silicon cell as a solar battery cell, and polyethylene terephthalate as a back surface protection member, they are illustrated in FIG. Thus, the laminated body which laminated | stacked in order of the surface protection member, the sealing material sheet, the photovoltaic cell, the sealing material sheet, and the back surface protection member was formed. Thereafter, the laminate is placed in a laminator that can be evacuated on the upper lid side and the laminate chamber, respectively, and evacuated for 90 seconds on both the upper lid side and the laminate chamber while maintaining the temperature in the laminate chamber at 150 ° C., Temporary pressure bonding was performed while degassing the inside of the laminate (vacuum degassing and temporary pressure bonding). After completion of the temporary pressure bonding, the temperature in the laminate chamber was set to 150 ° C., the vacuum state on the laminator upper lid side was released, and the laminate was subjected to thermocompression bonding at atmospheric pressure for 10 minutes (main pressure bonding) to obtain a solar cell module.
［実施例２］
有機過酸化物の添加量が１．０質量部、シランカップリング剤の添加量が０．２質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［実施例３］
有機過酸化物の添加量が０．８質量部、シランカップリング剤の添加量が０．３質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例１］
有機過酸化物の添加量が１．２質量部、シランカップリング剤の添加量が０．５質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例２］
有機過酸化物の添加量が０．８質量部、シランカップリング剤の添加量が０．１質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例３］
有機過酸化物の添加量が１．４質量部、シランカップリング剤の添加量が０．４質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例４］
有機過酸化物の添加量が０．６質量部、シランカップリング剤の添加量が０．３質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［評価方法］
実施例及び比較例の太陽電池モジュールについて、封止材層の架橋密度と、裏面保護部材／封止材層間の接着強度と、高温環境に投入した後の膨れの評価を行った。 [Example 2]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.0 part by mass and the addition amount of the silane coupling agent was 0.2 part by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Example 3]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.8 parts by mass and the addition amount of the silane coupling agent was 0.3 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 1]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.2 parts by mass and the addition amount of the silane coupling agent was 0.5 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 2]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.8 parts by mass and the addition amount of the silane coupling agent was 0.1 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 3]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.4 parts by mass and the addition amount of the silane coupling agent was 0.4 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 4]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.6 parts by mass and the addition amount of the silane coupling agent was 0.3 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Evaluation methods]
About the solar cell module of an Example and a comparative example, the crosslinking density of a sealing material layer, the adhesive strength between a back surface protection member / sealing material layer, and the swelling after throwing into a high temperature environment were evaluated.
有機過酸化物の添加量が１．０質量部、シランカップリング剤の添加量が０．２質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［実施例３］
有機過酸化物の添加量が０．８質量部、シランカップリング剤の添加量が０．３質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例１］
有機過酸化物の添加量が１．２質量部、シランカップリング剤の添加量が０．５質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例２］
有機過酸化物の添加量が０．８質量部、シランカップリング剤の添加量が０．１質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例３］
有機過酸化物の添加量が１．４質量部、シランカップリング剤の添加量が０．４質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［比較例４］
有機過酸化物の添加量が０．６質量部、シランカップリング剤の添加量が０．３質量部である点以外は、実施例１と同様にして封止材シートを作製した。その後、実施例１と同様にして太陽電池モジュールを作製した。
［評価方法］
実施例及び比較例の太陽電池モジュールについて、封止材層の架橋密度と、裏面保護部材／封止材層間の接着強度と、高温環境に投入した後の膨れの評価を行った。 [Example 2]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.0 part by mass and the addition amount of the silane coupling agent was 0.2 part by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Example 3]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.8 parts by mass and the addition amount of the silane coupling agent was 0.3 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 1]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.2 parts by mass and the addition amount of the silane coupling agent was 0.5 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 2]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.8 parts by mass and the addition amount of the silane coupling agent was 0.1 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 3]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 1.4 parts by mass and the addition amount of the silane coupling agent was 0.4 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Comparative Example 4]
A sealing material sheet was produced in the same manner as in Example 1 except that the addition amount of the organic peroxide was 0.6 parts by mass and the addition amount of the silane coupling agent was 0.3 parts by mass. Thereafter, a solar cell module was produced in the same manner as in Example 1.
[Evaluation methods]
About the solar cell module of an Example and a comparative example, the crosslinking density of a sealing material layer, the adhesive strength between a back surface protection member / sealing material layer, and the swelling after throwing into a high temperature environment were evaluated.
（架橋密度の評価について）
各実施例及び比較例で作製した太陽電池モジュールから封止材層を引き剥がし、そのうち１ｇをキシレン１００ｍＬに浸漬して、１１０℃で１２時間溶融させた後、非溶融成分の質量を測定し、下式の質量比を算出することにより架橋密度（単位：％）を求めた。結果を表１に示す。架橋密度が７０％以上である場合は合格とし、表１においては○印で示してあり、７０％未満である場合は不合格とし、表１においては×印で示してある。
架橋密度＝［非溶融成分の質量（ｇ）／溶融前の質量（１ｇ）］×１００ (Evaluation of crosslink density)
After peeling off the encapsulant layer from the solar cell modules produced in each Example and Comparative Example, 1 g of them was immersed in 100 mL of xylene and melted at 110 ° C. for 12 hours, and then the mass of the non-molten component was measured. The crosslinking density (unit:%) was determined by calculating the mass ratio of the following formula. The results are shown in Table 1. When the crosslink density is 70% or more, it is accepted, and in Table 1, it is indicated by ◯, when it is less than 70%, it is rejected, and in Table 1, it is indicated by X.
Crosslink density = [mass of non-molten component (g) / mass before melting (1 g)] × 100
各実施例及び比較例で作製した太陽電池モジュールから封止材層を引き剥がし、そのうち１ｇをキシレン１００ｍＬに浸漬して、１１０℃で１２時間溶融させた後、非溶融成分の質量を測定し、下式の質量比を算出することにより架橋密度（単位：％）を求めた。結果を表１に示す。架橋密度が７０％以上である場合は合格とし、表１においては○印で示してあり、７０％未満である場合は不合格とし、表１においては×印で示してある。
架橋密度＝［非溶融成分の質量（ｇ）／溶融前の質量（１ｇ）］×１００ (Evaluation of crosslink density)
After peeling off the encapsulant layer from the solar cell modules produced in each Example and Comparative Example, 1 g of them was immersed in 100 mL of xylene and melted at 110 ° C. for 12 hours, and then the mass of the non-molten component was measured. The crosslinking density (unit:%) was determined by calculating the mass ratio of the following formula. The results are shown in Table 1. When the crosslink density is 70% or more, it is accepted, and in Table 1, it is indicated by ◯, when it is less than 70%, it is rejected, and in Table 1, it is indicated by X.
Crosslink density = [mass of non-molten component (g) / mass before melting (1 g)] × 100
（接着強度の評価について）
ポリエチレンテレフタレートと封止材層の界面に、剥離のきっかけとしてカッターナイフで切り込みを入れ、ポリエチレンテレフタレートを接着強度測定機のチャックに固定し、１８０°の角度で裏面保護部材／封止材層間の接着強度（単位：Ｎ／１０ｍｍ）を測定した。接着強度測定機としては、株式会社ＯＲＩＥＮＴＥＣ製のＴＥＮＳＩＬＯＮ（ＲＴＣ－１２５０）を用いた。測定条件は、１０ｍｍ幅の接着強度測定とし、剥離速度は３００ｍｍ／分とした。
結果を表１に示す。接着強度が２０Ｎ／１０ｍｍ以上である場合は合格とし、表１においては○印で示してあり、２０Ｎ／１０ｍｍ未満である場合は不合格とし、表１においては×印で示してある。
（膨れの評価について）
プレッシャークッカーテスト器（ＰＣＴ）においての高温高湿環境下（温度１２１℃、湿度１００％飽和）に９６時間放置した後に、外観を観察した。膨れの評価結果を表１に示す。目視で膨れが確認できない場合は合格とし、表１においては○印で示してあり、膨れが確認できた場合は不合格とし、表１においては×印で示してある。 (About evaluation of adhesive strength)
Cut the polyethylene terephthalate / encapsulant layer at the interface with a cutter knife as a trigger for peeling, fix the polyethylene terephthalate to the chuck of the adhesive strength measuring machine, and bond the backside protective member / encapsulant layer at an angle of 180 ° The strength (unit: N / 10 mm) was measured. A TENSILON (RTC-1250) manufactured by ORIENTEC Co., Ltd. was used as an adhesive strength measuring machine. The measurement conditions were an adhesive strength measurement with a width of 10 mm, and the peeling rate was 300 mm / min.
The results are shown in Table 1. When the adhesive strength is 20 N / 10 mm or more, it is determined to be acceptable. In Table 1, it is indicated by a circle, and when it is less than 20 N / 10 mm, it is determined to be unacceptable.
(About evaluation of swelling)
The appearance was observed after being left for 96 hours in a high temperature and high humidity environment (temperature 121 ° C., humidity 100% saturation) in a pressure cooker tester (PCT). Table 1 shows the evaluation results of the swelling. When the blister cannot be confirmed visually, it is accepted, and in Table 1, it is indicated by a circle, and when the blister is confirmed, it is rejected. In Table 1, it is indicated by a cross.
ポリエチレンテレフタレートと封止材層の界面に、剥離のきっかけとしてカッターナイフで切り込みを入れ、ポリエチレンテレフタレートを接着強度測定機のチャックに固定し、１８０°の角度で裏面保護部材／封止材層間の接着強度（単位：Ｎ／１０ｍｍ）を測定した。接着強度測定機としては、株式会社ＯＲＩＥＮＴＥＣ製のＴＥＮＳＩＬＯＮ（ＲＴＣ－１２５０）を用いた。測定条件は、１０ｍｍ幅の接着強度測定とし、剥離速度は３００ｍｍ／分とした。
結果を表１に示す。接着強度が２０Ｎ／１０ｍｍ以上である場合は合格とし、表１においては○印で示してあり、２０Ｎ／１０ｍｍ未満である場合は不合格とし、表１においては×印で示してある。
（膨れの評価について）
プレッシャークッカーテスト器（ＰＣＴ）においての高温高湿環境下（温度１２１℃、湿度１００％飽和）に９６時間放置した後に、外観を観察した。膨れの評価結果を表１に示す。目視で膨れが確認できない場合は合格とし、表１においては○印で示してあり、膨れが確認できた場合は不合格とし、表１においては×印で示してある。 (About evaluation of adhesive strength)
Cut the polyethylene terephthalate / encapsulant layer at the interface with a cutter knife as a trigger for peeling, fix the polyethylene terephthalate to the chuck of the adhesive strength measuring machine, and bond the backside protective member / encapsulant layer at an angle of 180 ° The strength (unit: N / 10 mm) was measured. A TENSILON (RTC-1250) manufactured by ORIENTEC Co., Ltd. was used as an adhesive strength measuring machine. The measurement conditions were an adhesive strength measurement with a width of 10 mm, and the peeling rate was 300 mm / min.
The results are shown in Table 1. When the adhesive strength is 20 N / 10 mm or more, it is determined to be acceptable. In Table 1, it is indicated by a circle, and when it is less than 20 N / 10 mm, it is determined to be unacceptable.
(About evaluation of swelling)
The appearance was observed after being left for 96 hours in a high temperature and high humidity environment (temperature 121 ° C., humidity 100% saturation) in a pressure cooker tester (PCT). Table 1 shows the evaluation results of the swelling. When the blister cannot be confirmed visually, it is accepted, and in Table 1, it is indicated by a circle, and when the blister is confirmed, it is rejected. In Table 1, it is indicated by a cross.
表１に示すように、前記条件（１）及び条件（２）を満たすように有機過酸化物とシランカップリング剤が含有された封止材シートを用いた実施例１～４では、架橋密度が高く、かつ接着強度に優れ、長期使用における信頼性に優れた太陽電池モジュールを作製することができた。
As shown in Table 1, in Examples 1 to 4 using a sealing material sheet containing an organic peroxide and a silane coupling agent so as to satisfy the conditions (1) and (2), the crosslinking density It was possible to produce a solar cell module having a high reliability, excellent adhesive strength, and excellent reliability in long-term use.
１・・・表面保護部材、２・・・封止材層、３・・・太陽電池セル、４・・・裏面保護部材、５・・・太陽電池モジュール、６・・・封止材シート
DESCRIPTION OF SYMBOLS 1 ... Surface protection member, 2 ... Sealing material layer, 3 ... Solar cell, 4 ... Back surface protection member, 5 ... Solar cell module, 6 ... Sealing material sheet
Claims (3)
- エチレン－αオレフィン共重合体、有機過酸化物及びシランカップリング剤を含み、下記条件（１）及び（２）を満たすことを特徴とする太陽電池モジュール用封止材シート。
（１）５．４≦（Ａ×Ｂ）／Ｃ≦１０．１
（２）６．０×１０－３≦Ａ×（Ｄ／Ｅ）≦１．０×１０－２
（ただし、Ａは前記有機過酸化物１分子から発生する理論オキシラジカル量であり、Ｂは前記有機過酸化物のモル量であり、Ｃは前記シランカップリング剤のモル量であり、Ｄは前記エチレン－αオレフィン共重合体１００質量部に対する前記有機過酸化物の含有量（質量部）であり、Ｅは前記有機過酸化物の分子量である。） A sealing material sheet for a solar cell module comprising an ethylene-α-olefin copolymer, an organic peroxide, and a silane coupling agent, wherein the following conditions (1) and (2) are satisfied.
(1) 5.4 ≦ (A × B) /C≦10.1
(2) 6.0 × 10 −3 ≦ A × (D / E) ≦ 1.0 × 10 −2
(However, A is the theoretical oxy radical amount generated from one molecule of the organic peroxide, B is the molar amount of the organic peroxide, C is the molar amount of the silane coupling agent, and D is (The content (parts by mass) of the organic peroxide relative to 100 parts by mass of the ethylene-α-olefin copolymer, and E is the molecular weight of the organic peroxide.) - 前記エチレン－αオレフィン共重合体の密度が０．８６ｇ／ｃｍ３以上０．９０ｇ／ｃｍ３以下である請求項１に記載の太陽電池モジュール用封止材シート。 2. The solar cell module sealing material sheet according to claim 1, wherein a density of the ethylene-α-olefin copolymer is 0.86 g / cm 3 or more and 0.90 g / cm 3 or less.
- 太陽電池セルと、前記太陽電池セルを封止する封止材層と、前記封止材層の表面側を保護する表面保護部材と、前記封止材層の裏面側を保護する裏面保護部材と、を有し、前記封止材層が、請求項１又は２に記載の太陽電池モジュール用封止材シートにより形成されている太陽電池モジュール。 A solar battery cell, a sealing material layer that seals the solar battery cell, a surface protection member that protects the front surface side of the sealing material layer, and a back surface protection member that protects the back surface side of the sealing material layer; A solar cell module in which the encapsulant layer is formed by the encapsulant sheet for solar cell modules according to claim 1 or 2.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013058626A JP2014183294A (en) | 2013-03-21 | 2013-03-21 | Seal-material sheet for solar battery module use, and solar battery module |
| JP2013-058626 | 2013-03-21 |
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| Publication Number | Publication Date |
|---|---|
| WO2014148056A1 true WO2014148056A1 (en) | 2014-09-25 |
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|---|---|---|---|
| PCT/JP2014/001627 WO2014148056A1 (en) | 2013-03-21 | 2014-03-20 | Sealing material sheet for solar cell modules, and solar cell module |
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| JP (1) | JP2014183294A (en) |
| TW (1) | TW201441289A (en) |
| WO (1) | WO2014148056A1 (en) |
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| CN108075005A (en) * | 2017-11-29 | 2018-05-25 | 北京昶远科技有限公司 | It is a kind of for high-weatherability light flexible photovoltaic module of high altitude long time solar energy unmanned plane and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011012246A (en) * | 2009-06-01 | 2011-01-20 | Mitsui Chemicals Inc | Resin composition, solar cell sealing material and solar cell module using the same |
| WO2011108434A1 (en) * | 2010-03-04 | 2011-09-09 | 凸版印刷株式会社 | Sealing material sheet for solar cell module, and solar cell module |
| WO2013024599A1 (en) * | 2011-08-18 | 2013-02-21 | 三井化学株式会社 | Solar cell sealing material, method for manufacturing solar cell sealing material, and solar cell module |
-
2013
- 2013-03-21 JP JP2013058626A patent/JP2014183294A/en active Pending
-
2014
- 2014-03-20 WO PCT/JP2014/001627 patent/WO2014148056A1/en active Application Filing
- 2014-03-21 TW TW103110723A patent/TW201441289A/en unknown
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011012246A (en) * | 2009-06-01 | 2011-01-20 | Mitsui Chemicals Inc | Resin composition, solar cell sealing material and solar cell module using the same |
| WO2011108434A1 (en) * | 2010-03-04 | 2011-09-09 | 凸版印刷株式会社 | Sealing material sheet for solar cell module, and solar cell module |
| WO2013024599A1 (en) * | 2011-08-18 | 2013-02-21 | 三井化学株式会社 | Solar cell sealing material, method for manufacturing solar cell sealing material, and solar cell module |
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| TW201441289A (en) | 2014-11-01 |
| JP2014183294A (en) | 2014-09-29 |
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