JP2011192791A - Laminated film for solar cell rear surface protective film - Google Patents
Laminated film for solar cell rear surface protective film Download PDFInfo
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- JP2011192791A JP2011192791A JP2010057631A JP2010057631A JP2011192791A JP 2011192791 A JP2011192791 A JP 2011192791A JP 2010057631 A JP2010057631 A JP 2010057631A JP 2010057631 A JP2010057631 A JP 2010057631A JP 2011192791 A JP2011192791 A JP 2011192791A
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- 230000001681 protective effect Effects 0.000 title claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229920000728 polyester Polymers 0.000 claims abstract description 29
- 239000002245 particle Substances 0.000 claims abstract description 24
- 229920010524 Syndiotactic polystyrene Polymers 0.000 claims abstract description 21
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 19
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 19
- 230000008859 change Effects 0.000 claims abstract description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 18
- -1 polyethylene terephthalate Polymers 0.000 claims description 17
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 12
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 11
- 230000007062 hydrolysis Effects 0.000 abstract description 16
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 16
- 239000004408 titanium dioxide Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 121
- 239000010410 layer Substances 0.000 description 60
- 210000004027 cell Anatomy 0.000 description 38
- 238000000034 method Methods 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 7
- 230000014759 maintenance of location Effects 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000004793 Polystyrene Substances 0.000 description 6
- 229920006267 polyester film Polymers 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 239000011247 coating layer Substances 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000032798 delamination Effects 0.000 description 4
- 238000011156 evaluation Methods 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 239000011888 foil Substances 0.000 description 3
- 238000003475 lamination Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000002845 discoloration Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000009998 heat setting Methods 0.000 description 2
- 239000012760 heat stabilizer Substances 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000002648 laminated material Substances 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- 238000001225 nuclear magnetic resonance method Methods 0.000 description 2
- 239000005033 polyvinylidene chloride Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 2
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical compound CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- KBKNKFIRGXQLDB-UHFFFAOYSA-N 2-fluoroethenylbenzene Chemical compound FC=CC1=CC=CC=C1 KBKNKFIRGXQLDB-UHFFFAOYSA-N 0.000 description 1
- CTHJQRHPNQEPAB-UHFFFAOYSA-N 2-methoxyethenylbenzene Chemical compound COC=CC1=CC=CC=C1 CTHJQRHPNQEPAB-UHFFFAOYSA-N 0.000 description 1
- NEQFBGHQPUXOFH-UHFFFAOYSA-N 4-(4-carboxyphenyl)benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C=C1 NEQFBGHQPUXOFH-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000004705 High-molecular-weight polyethylene Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- YMOONIIMQBGTDU-VOTSOKGWSA-N [(e)-2-bromoethenyl]benzene Chemical compound Br\C=C\C1=CC=CC=C1 YMOONIIMQBGTDU-VOTSOKGWSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 239000002216 antistatic agent Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 239000002981 blocking agent Substances 0.000 description 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 description 1
- CDQSJQSWAWPGKG-UHFFFAOYSA-N butane-1,1-diol Chemical compound CCCC(O)O CDQSJQSWAWPGKG-UHFFFAOYSA-N 0.000 description 1
- 239000002775 capsule Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000002009 diols Chemical class 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- KETWBQOXTBGBBN-UHFFFAOYSA-N hex-1-enylbenzene Chemical compound CCCCC=CC1=CC=CC=C1 KETWBQOXTBGBBN-UHFFFAOYSA-N 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229940097364 magnesium acetate tetrahydrate Drugs 0.000 description 1
- XKPKPGCRSHFTKM-UHFFFAOYSA-L magnesium;diacetate;tetrahydrate Chemical compound O.O.O.O.[Mg+2].CC([O-])=O.CC([O-])=O XKPKPGCRSHFTKM-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001565 modulated differential scanning calorimetry Methods 0.000 description 1
- 210000004985 myeloid-derived suppressor cell Anatomy 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- KHMYONNPZWOTKW-UHFFFAOYSA-N pent-1-enylbenzene Chemical compound CCCC=CC1=CC=CC=C1 KHMYONNPZWOTKW-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 229920001596 poly (chlorostyrenes) Polymers 0.000 description 1
- 229920001620 poly(3-methyl styrene) Polymers 0.000 description 1
- 229920001627 poly(4-methyl styrene) Polymers 0.000 description 1
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 1
- 229920001608 poly(methyl styrenes) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 239000011112 polyethylene naphthalate Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- 150000003918 triazines Chemical class 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Laminated Bodies (AREA)
- Photovoltaic Devices (AREA)
Abstract
Description
本発明は、太陽電池裏面保護膜用積層フィルムおよびそれを用いた太陽電池裏面保護膜に関し、詳しくは、優れた耐加水分解性、耐候性を備える太陽電池裏面保護膜用積層フィルムに関する。 TECHNICAL FIELD The present invention relates to a laminated film for a solar cell back surface protective film and a solar cell back surface protective film using the same, and specifically relates to a laminated film for a solar cell back surface protective film having excellent hydrolysis resistance and weather resistance.
近年、太陽光発電システムは、クリーンエネルギーを利用する発電手段の一つとして、普及が進んでいる。太陽電池モジュールは、例えば実開平６−３８２６４号公報に記載があるように、一般的には、受光側のガラス基板と裏面保護膜との間に複数の板状太陽電池素子を挟み、内部の隙間に封止樹脂を充填した構造をとる。 In recent years, a solar power generation system has been spreading as one of power generation means using clean energy. As described in, for example, Japanese Utility Model Publication No. Hei 6-38264, a solar cell module generally has a plurality of plate-like solar cell elements sandwiched between a light-receiving side glass substrate and a back surface protective film, The gap is filled with sealing resin.
また、太陽電池の裏面側の保護膜として、ポリエステルフィルムを用いることが知られている（特開２００１−１４８４９７号公報、特開２００１−２５７３７２号公報、特開２００３−６０２１８号公報）。これらのポリエステルフィルムは、長期使用における耐加水分解性が未だに不十分であることから改良が試みられ、高分子量のポリエチレンテレフタレートフィルムを用いること（特開２００２−２６３５４号公報）、オリゴマー含有量の少ないポリエチレンテレフタレートフィルムを用いること（特開２００２−１００７８８号公報、特開２００２−１３４７７０号公報、特開２００２−１３４７７１号公報）、２，６−ナフタレンジカルボン酸含有のポリエステルフィルムを用いること（特開２００７−００７８８５号公報、特開２００６−３０６９１０号公報）が提案されている。また、ポリエステルフィルムの耐加水分解性を上げる手法としてシンジオタクチックポリスチレンとの積層が提案されている（特開２００９−２３８４４８号公報）。しかし、シンジオタクチックポリスチレンフィルムは、耐加水分解性は向上するが紫外線による劣化が起こりやすく、耐候性に乏しいため、太陽電池裏面保護に用いることは困難である。 Further, it is known that a polyester film is used as a protective film on the back side of the solar cell (Japanese Patent Application Laid-Open Nos. 2001-148497, 2001-257372, and 2003-60218). These polyester films have been tried to be improved because hydrolysis resistance in long-term use is still insufficient, and high molecular weight polyethylene terephthalate films are used (Japanese Patent Laid-Open No. 2002-26354), and the oligomer content is low. Use of a polyethylene terephthalate film (Japanese Patent Laid-Open Nos. 2002-1000078, 2002-134770, 2002-134771), and a polyester film containing 2,6-naphthalenedicarboxylic acid (JP 2007) -007885 and JP-A-2006-306910 have been proposed. Further, as a technique for increasing the hydrolysis resistance of a polyester film, lamination with syndiotactic polystyrene has been proposed (Japanese Patent Laid-Open No. 2009-238448). However, the syndiotactic polystyrene film has improved hydrolysis resistance but is likely to be deteriorated by ultraviolet rays, and is poor in weather resistance. Therefore, it is difficult to use it for solar cell back surface protection.
本発明は、かかる従来技術の問題点を解消し、優れた耐候性および耐加水分解性を備えた太陽電池裏面保護膜用積層フィルムおよび太陽電池裏面保護膜を提供することを課題とする。 An object of the present invention is to solve the problems of the prior art and to provide a laminated film for a solar cell back surface protective film and a solar cell back surface protective film having excellent weather resistance and hydrolysis resistance.
すなわち本発明は、９８〜７０重量％のシンジオタクチックポリスチレンおよび２〜３０重量％の熱可塑性ポリエステルからなる厚み２０μｍ以上２００μｍ以下の層（Ａ）およびその少なくとも一方の面に設けられた平均粒径が０．１〜５．０μｍのルチル型酸化チタン粒子１０〜３０重量％および熱可塑性ポリエステル９０〜７０重量％からなる厚み５μｍ以上の層（Ｂ）から構成され、層（Ｂ）の厚みは積層フィルム総厚みの２５％以下の厚みであり、高圧水銀ランプ２００ｗ／ｍ２で８ｈｒ照射したときのイエローインデックスの変化ΔＹＩが８未満であることを特徴とする、太陽電池裏面保護膜用積層フィルムである。 That is, the present invention relates to a layer (A) having a thickness of 20 μm or more and 200 μm or less comprising 98 to 70% by weight of syndiotactic polystyrene and 2 to 30% by weight of thermoplastic polyester, and an average particle diameter provided on at least one surface thereof. Is composed of a layer (B) having a thickness of 5 μm or more comprising 10 to 30% by weight of rutile-type titanium oxide particles having a thickness of 0.1 to 5.0 μm and 90 to 70% by weight of a thermoplastic polyester. A laminated film for a solar cell back surface protective film, characterized in that it has a thickness of 25% or less of the total film thickness, and the yellow index change ΔYI is less than 8 when irradiated with a high-pressure mercury lamp 200 w / m 2 for 8 hours. is there.
本発明によれば、優れた耐候性および耐加水分解性を備えた太陽電池裏面保護膜用積層フィルムおよび太陽電池裏面保護膜を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, the laminated | multilayer film for solar cell back surface protective films provided with the outstanding weather resistance and hydrolysis resistance, and a solar cell back surface protective film can be provided.
以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
［シンジオタクチックポリスチレン］
本発明において層（Ａ）は９８〜７０重量％のシンジオタクチックポリスチレンおよび２〜３０重量％の熱可塑性ポリエステルからなる。
層（Ａ）を構成するシンジオタクチックポリスチレンは、立体化学構造がシンジオタクチック構造を有するポリスチレンであり、核磁気共鳴法（１３Ｃ−ＮＭＲ法）により測定されるタクティシティーが、ダイアッド（構成単位が２個）で７５％以上、好ましくは８５％以上、ペンタッド（構成単位が５個）で３０％以上、好ましくは５０％以上のものである。
[Syndiotactic polystyrene]
In the present invention, the layer (A) comprises 98 to 70% by weight of syndiotactic polystyrene and 2 to 30% by weight of thermoplastic polyester.
The syndiotactic polystyrene constituting the layer (A) is a polystyrene whose stereochemical structure has a syndiotactic structure, and the tacticity measured by a nuclear magnetic resonance method ( 13 C-NMR method) is dyad (constituent unit). 2) and 75% or more, preferably 85% or more, and pentad (5 structural units) is 30% or more, preferably 50% or more.
かかるシンジオタクチックポリスチレンとしては、ポリスチレン、ポリ（アルキルスチレン）として、ポリ（メチルスチレン）、ポリ（エチルスチレン）、ポリ（プロピルスチレン）、ポリ（ブチルスチレン）、ポリ（フェニルスチレン）およびポリ（ビニルスチレン）、ポリ（ハロゲン化スチレン）としてポリ（クロロスチレン）、ポリ（ブロモスチレン）およびポリ（フルオロスチレン）、ポリ（アルコキシスチレン）としてポリ（メトキシスチレン）、ポリ（エトキシスチレン）を例示することができる。
これらのうち、ポリスチレン、ポリ（ｐ−メチルスチレン）、ポリ（ｍ−メチルスチレ
ン）、ポリ（ｐ−ターシャリーブチルスチレン）が好ましい。
Such syndiotactic polystyrenes include polystyrene, poly (alkyl styrene), poly (methyl styrene), poly (ethyl styrene), poly (propyl styrene), poly (butyl styrene), poly (phenyl styrene) and poly (vinyl). Styrene), poly (chlorostyrene), poly (bromostyrene) and poly (fluorostyrene) as poly (halogenated styrene), poly (methoxystyrene), poly (ethoxystyrene) as poly (alkoxystyrene) it can.
Of these, polystyrene, poly (p-methylstyrene), poly (m-methylstyrene), and poly (p-tertiarybutylstyrene) are preferable.
シンジオタクチックポリスチレンは、ホモポリマーでも、シンジオタクティシティが前記範囲内であれば他のポリスチレンとの共重合体、２種以上のポリスチレンとの混合体のいずれであってもかまわない。
またシンジオタクチックポリスチレンの重合平均分子量は、好ましくは１００００〜５０００００、さらに好ましくは５００００〜５０００００である。重合平均分子量がこの範囲にあることで、耐熱性および機械的特性を確保しながら良好な製膜性を得ることができ好ましい。
シンジオタクチックポリスチレンの融点は、好ましくは２３０〜２８０℃、さらに好ましくは２４０〜２７５℃である。融点がこの範囲にあることで、層（Ｂ）との積層フィルムを容易に得ることができ好ましい。
The syndiotactic polystyrene may be a homopolymer or a copolymer with another polystyrene and a mixture with two or more kinds of polystyrene as long as the syndiotacticity is within the above range.
Moreover, the polymerization average molecular weight of syndiotactic polystyrene is preferably 10,000 to 500,000, and more preferably 50,000 to 500,000. It is preferable that the polymerization average molecular weight is in this range because good film forming property can be obtained while ensuring heat resistance and mechanical properties.
The melting point of syndiotactic polystyrene is preferably 230 to 280 ° C, more preferably 240 to 275 ° C. It is preferable that the melting point is in this range because a laminated film with the layer (B) can be easily obtained.
［熱可塑性ポリエステル］
本発明における熱可塑性ポリエステルとしては、熱可塑性のポリエステルを用い、好ましくは芳香族ポリエステルを用いる。この芳香族ポリエステルとして、例えば、ポリエチレンテレフタレート、ポリエチレンイソフタレート、ポリブチレンテレフタレート、ポリプロピレンテレフタレート、ポリシクロヘキサンジメチレンテレフタレート、ポリエチレンナフタレートを用いることができる。これらは、ホモポリマーであってもよく、コポリマーであってもよい。複数のポリマーのブレンド体であってもよい。
これらポリエステルの中でも、ポリエチレンテレフタレートは紫外線による黄変が少なく、フィルムとしての特性からみても好ましい。
[Thermoplastic polyester]
As the thermoplastic polyester in the present invention, a thermoplastic polyester is used, preferably an aromatic polyester. As this aromatic polyester, for example, polyethylene terephthalate, polyethylene isophthalate, polybutylene terephthalate, polypropylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate can be used. These may be homopolymers or copolymers. It may be a blend of a plurality of polymers.
Among these polyesters, polyethylene terephthalate is less yellowing due to ultraviolet rays, and is preferable from the viewpoint of film properties.
熱可塑性ポリエステルとして、ポリエチレンテレフタレートのコポリマーを用いる場合、共重合成分としては、例えばイソフタル酸、２，６―ナフタレンジカルボン酸、４，４′―ジフェニルジカルボン酸といった芳香族ジカルボン酸成分、１，４―ブタンジオール、１，４―シクロヘキサンジメタノール、１，６―ヘキサンジオールといったジオール成分を例示することができる。共重合成分の割合は、結果としてポリエチレンテレフタレートのコポリマーの融点が、例えば２４５〜２８０℃、好ましくは２５０〜２８０℃の範囲になる割合である。コポリマー融点が２４５℃未満になると耐熱性が低下し、２８０℃を越えると生産性が低下して好ましくない。 When a polyethylene terephthalate copolymer is used as the thermoplastic polyester, examples of the copolymer component include aromatic dicarboxylic acid components such as isophthalic acid, 2,6-naphthalenedicarboxylic acid, and 4,4′-diphenyldicarboxylic acid, and 1,4- Examples of the diol component include butanediol, 1,4-cyclohexanedimethanol, and 1,6-hexanediol. The proportion of the copolymer component is such that the resulting melting point of the polyethylene terephthalate copolymer is in the range of, for example, 245 to 280 ° C, preferably 250 to 280 ° C. When the copolymer melting point is less than 245 ° C., the heat resistance is lowered, and when it exceeds 280 ° C., the productivity is lowered, which is not preferable.
熱可塑性ポリエステルのポリエステルの固有粘度は、好ましくは０．６８ｄｌ／ｇ以上、さらに好ましくは０．７０〜０．９５ｄｌ／ｇである。固有粘度が０．６８ｄｌ／ｇ未満ではフィルムの重量平均分子量を４７０００〜６５０００の範囲に調整することが困難であり、また、フィルムがデラミネーションを起こしやすく好ましくない。０．９５ｄｌ／ｇより高いと溶融粘度が高いため溶融押出しが困難になり、また重合時間が長く不経済であり好ましくない。 The intrinsic viscosity of the polyester of the thermoplastic polyester is preferably 0.68 dl / g or more, and more preferably 0.70 to 0.95 dl / g. If the intrinsic viscosity is less than 0.68 dl / g, it is difficult to adjust the weight average molecular weight of the film to a range of 47000 to 65000, and the film tends to cause delamination, which is not preferable. When it is higher than 0.95 dl / g, melt extrusion is difficult because of high melt viscosity, and the polymerization time is long and uneconomical.
［ルチル型酸化チタン粒子］
酸化チタンの結晶形態には、ルチル型とアナターゼ型がある。本発明の太陽電池裏面保護膜用積層フィルムにおいては、ルチル型酸化チタンの粒子を用いる。このルチル型酸化チタン粒子を用いることで、フィルムの紫外線劣化を抑制し、光線を長時間照射したときのフィルム変色や機械的強度の低下を少なくすることができる。
本発明におけるルチル型酸化チタン粒子の平均粒径は、０．１〜５．０μｍ、好ましくは０．１〜３．０μｍである。０．１μｍ未満であると分散性が悪くなり、粒子の凝集が起こるため、均一なフィルムを得ることができない。他方、５．０μｍを超えるとフィルムの延伸性が悪くなる。
[Rutyl-type titanium oxide particles]
Crystal forms of titanium oxide include a rutile type and an anatase type. In the laminated film for solar cell back surface protective film of the present invention, particles of rutile type titanium oxide are used. By using the rutile-type titanium oxide particles, it is possible to suppress UV deterioration of the film and reduce film discoloration and mechanical strength reduction when irradiated with light for a long time.
The average particle size of the rutile-type titanium oxide particles in the present invention is 0.1 to 5.0 μm, preferably 0.1 to 3.0 μm. If the thickness is less than 0.1 μm, the dispersibility deteriorates and the particles are aggregated, so that a uniform film cannot be obtained. On the other hand, when it exceeds 5.0 μm, the stretchability of the film is deteriorated.
［層（Ａ）の組成］
層（Ａ）は、９８〜７０重量％のシンジオタクチックポリスチレンおよび２〜３０重量％の熱可塑性ポリエステル、好ましくは９０〜８０重量％のシンジオタクチックポリスチレンおよび１０〜２０重量％の熱可塑性ポリエステルから構成される。熱可塑性ポリエステルの含有量が２重量％未満であると層（Ｂ）との密着性が不十分で層剥離が起きやすくなる。また、熱可塑性ポリエステルの含有量が３０重量％を超えると、耐加水分解性に劣る。
[Composition of layer (A)]
Layer (A) is composed of 98-70% by weight syndiotactic polystyrene and 2-30% by weight thermoplastic polyester, preferably 90-80% by weight syndiotactic polystyrene and 10-20% by weight thermoplastic polyester. Composed. When the content of the thermoplastic polyester is less than 2% by weight, the adhesion with the layer (B) is insufficient, and delamination tends to occur. Moreover, when content of thermoplastic polyester exceeds 30 weight%, it is inferior to hydrolysis resistance.
層（Ａ）は、ルチル型酸化チタン粒子を含有することが好ましい。その場合、層（Ａ）のシンジオタクチックポリスチレン１００重量％あたり、ルチル型酸化チタン粒子を好ましくは０．４〜３重量％、さらに好ましくは１．０〜２．０重量％含有する。この範囲で含有することで、層（Ａ）と層（Ｂ）との良好な密着性を得ることができ、積層界面から層間剥離が発生することをさらに抑制することができ、耐加水分解性に優れ、強伸度保持率を高く維持することができ、他の積層材との接着性に優れた積層フィルムを得ることができる。 The layer (A) preferably contains rutile type titanium oxide particles. In that case, the rutile type titanium oxide particles are preferably contained in an amount of 0.4 to 3% by weight, more preferably 1.0 to 2.0% by weight, per 100% by weight of the syndiotactic polystyrene in the layer (A). By containing in this range, it is possible to obtain good adhesion between the layer (A) and the layer (B), it is possible to further suppress the occurrence of delamination from the lamination interface, and hydrolysis resistance It is possible to obtain a laminated film that is excellent in strength, can maintain a high tensile elongation retention rate, and has excellent adhesion to other laminated materials.
［層（Ｂ）の組成］
層（Ｂ）は、ルチル型酸化チタン粒子１０〜３０重量％および熱可塑性ポリエステル９０〜７０重量％からなる。層（Ｂ）は、ルチル型酸化チタン粒子を１０〜３０重量％、好ましくは１４〜２５重量％含有する。ルチル型酸化チタン粒子が１０重量％未満であるとフィルムの十分な耐候性を得ることができず、紫外線による劣化が起こり易い。他方、３０重量％を超えると層（Ａ）との密着性に乏しくなり積層界面から層間剥離が生じるだけでなく、積層フィルムの耐加水分解性が低下して、早く劣化する。
[Composition of layer (B)]
The layer (B) consists of 10 to 30% by weight of rutile titanium oxide particles and 90 to 70% by weight of thermoplastic polyester. The layer (B) contains 10 to 30% by weight, preferably 14 to 25% by weight of rutile-type titanium oxide particles. If the rutile-type titanium oxide particles are less than 10% by weight, sufficient weather resistance of the film cannot be obtained, and deterioration due to ultraviolet rays tends to occur. On the other hand, when it exceeds 30% by weight, not only the adhesion to the layer (A) becomes poor and delamination occurs from the lamination interface, but also the hydrolysis resistance of the laminated film is lowered and deteriorates quickly.
［層構成］
本発明の太陽電池裏面保護膜用積層フィルムは、耐候性、耐加水分解性および他積層材との接着性を鼎立させるために、層（Ａ）およびその少なくとも一方の面に設けられた層（Ｂ）から構成される。
本発明の太陽電池裏面保護膜用積層フィルムを太陽電池裏面保護膜として用いるときには、シンジオタクチックポリスチレンの耐候性を向上させるとともに太陽電池を紫外線から保護する観点から、層（Ｂ）が太陽電池モジュールの外側になるように配置する。
層（Ｂ）の厚みは、５μｍ以上であり、かつ積層フィルム総厚みの２５％以下の厚みである。層（Ｂ）の厚みが５μｍ未満であるとフィルムに十分な耐候性が得られず紫外線によるフィルム変色が大きくなる。また、積層フィルム総厚みの２５％を超えると、フィルムの耐加水分解性に劣り伸度保持率が低下し劣化が速くなる。
[Layer structure]
The laminated film for a solar cell back surface protective film of the present invention has a layer (A) and a layer (A) provided on at least one surface thereof in order to elevate weather resistance, hydrolysis resistance and adhesion to other laminated materials ( B).
When the laminated film for a solar cell back surface protective film of the present invention is used as a solar cell back surface protective film, the layer (B) is a solar cell module from the viewpoint of improving the weather resistance of syndiotactic polystyrene and protecting the solar cell from ultraviolet rays. Arrange so that it is outside
The thickness of the layer (B) is 5 μm or more and 25% or less of the total thickness of the laminated film. When the thickness of the layer (B) is less than 5 μm, sufficient weather resistance cannot be obtained for the film, and film discoloration due to ultraviolet rays increases. Moreover, when it exceeds 25% of laminated film total thickness, it will be inferior to the hydrolysis resistance of a film, elongation retention will fall, and deterioration will become quick.
［耐候性］
本発明の太陽電池裏面保護膜用積層フィルムは、層（Ｂ）側からの紫外線照射前後において、層（Ｂ）のイエローインデックスの変化ΔＹＩが８未満、好ましくは５未満である耐候性を備える。ΔＹＩが８以上であると、耐候性の不足により太陽電池裏面保護膜用フィルムとして太陽電池を保護することができない。
このΔＹＩは、高圧水銀ランプを用い２００Ｗ／ｍ２の照射強度で８時間フィルムに紫外線照射する前後でのフィルムのＹＩ値の変化量であり、日本電色工業製自動色差計（ＳＥ−Σ９０型）を用いて測定した、紫外線照射前後のフィルムのＹＩ値から、下記式で算出される。
ΔＹＩ＝照射後のＹＩ値−照射前のＹＩ値
[Weatherability]
The laminated film for a solar cell back surface protective film of the present invention has weather resistance such that the yellow index change ΔYI of the layer (B) is less than 8, preferably less than 5, before and after the ultraviolet irradiation from the layer (B) side. When ΔYI is 8 or more, the solar cell cannot be protected as a film for protecting the back surface of the solar cell due to insufficient weather resistance.
This ΔYI is the amount of change in the YI value of the film before and after irradiating the film with ultraviolet rays at an irradiation intensity of 200 W / m 2 for 8 hours using a high-pressure mercury lamp, and is an automatic color difference meter (SE-Σ90 type manufactured by Nippon Denshoku Industries Co., Ltd.). ), And the YI value of the film before and after UV irradiation was measured by the following formula.
ΔYI = YI value after irradiation−YI value before irradiation
［耐加水分解性］
本発明の太陽電池裏面保護膜用積層フィルムは、長期間屋外に暴露され使用されることから高温・高湿度環境で長期間加水分解による伸度低下が小さいことが好ましく、具体的には温度１２１℃、湿度１００％ＲＨの環境下において２００時間エージング後の伸度保持率が８０％以上であれば、当該用途で十分な耐久性を備えていると言うことができる。
[Hydrolysis resistance]
The laminated film for a solar cell back surface protective film of the present invention is preferably exposed to the outdoors for a long period of time, so that the decrease in elongation due to hydrolysis for a long period of time in a high temperature / high humidity environment is preferably small. If the elongation retention after aging for 200 hours in an environment of ° C. and humidity of 100% RH is 80% or more, it can be said that it has sufficient durability for the application.
［添加剤］
層（Ａ）および／または層（Ｂ）には、本発明の目的を阻害しない範囲で、従来公知の添加剤を含有してもよい。この添加剤としては、例えば、酸化防止剤、末端封止剤、熱安定剤、紫外線吸収剤、帯電防止剤、難燃剤を挙げることができる。酸化防止剤としては、例えばヒンダードフェノール系化合物を、熱安定剤としては、例えばリン系化合物を、紫外線吸収剤としては、例えばベンゾトリアゾール系化合物、トリアジン系化合物を例示することができる。
[Additive]
The layer (A) and / or the layer (B) may contain conventionally known additives as long as the object of the present invention is not impaired. Examples of the additive include an antioxidant, a terminal blocking agent, a heat stabilizer, an ultraviolet absorber, an antistatic agent, and a flame retardant. Examples of antioxidants include hindered phenol compounds, examples of heat stabilizers include phosphorus compounds, and examples of ultraviolet absorbers include benzotriazole compounds and triazine compounds.
［製造方法］
本発明の太陽電池裏面保護膜用積層フィルムは、上述のシンジオタクチックポリスチレンと熱可塑性ポリエステルとを原料とし、これらをそれぞれ溶融状態で積層し、例えば共押出製膜法によりシート状に押出した後、テンター法、インフレーション法など公知の製膜方法を用いて製造することができる。
以下、一例としてシンジオタクチックポリスチレン、ポリエステルおよびポリエステルに酸化チタン粒子を含有させたマスターペレットを用いて、２層積層フィルム（Ａ／Ｂの構成）を製造する例を挙げて説明する。以下、ガラス転移温度をＴｇ、融点をＴｍという。
[Production method]
The laminated film for a solar cell back surface protective film of the present invention is obtained by using the above-mentioned syndiotactic polystyrene and thermoplastic polyester as raw materials, laminating them in a molten state, and extruding them into a sheet by, for example, a coextrusion film forming method. The film can be produced using a known film forming method such as a tenter method or an inflation method.
Hereinafter, as an example, syndiotactic polystyrene, polyester, and an example of producing a two-layer laminated film (A / B configuration) using master pellets containing titanium oxide particles in polyester will be described. Hereinafter, the glass transition temperature is referred to as Tg, and the melting point is referred to as Tm.
まず層（Ａ）用に調整したポリマー組成物を乾燥後、（Ｔｍａ）〜（Ｔｍａ＋７０）℃（Ｔｍａは層（Ａ）を構成するポリマーの融点を表わす）の温度範囲内で溶融する。同時に、層（Ｂ）用に調整したポリマー組成物を必要に応じて乾燥し、（Ｔｍｂ）〜（Ｔｍｂ＋７０）℃（Ｔｍｂは層（Ｂ）を構成するポリマーの融点を表わす）の温度範囲内で溶融する。溶融は各々別々の押し出し機でおこなう。続いて、フィードブロックを用いた同時多層押出し法により、未延伸積層シートを製造する。すなわち層（Ａ）を構成するポリマーの溶融物と層（Ｂ）を構成するポリマーの溶融物とを、フィードブロックを用いて層（Ａ）／層（Ｂ）となるように２層に積層し、スリットダイに展開して押出しを実施する。この時、フィードブロックで積層されたポリマーは積層された形態を維持している。 First, the polymer composition prepared for the layer (A) is dried and then melted within a temperature range of (Tma) to (Tma + 70) ° C. (Tma represents the melting point of the polymer constituting the layer (A)). At the same time, the polymer composition prepared for the layer (B) is dried if necessary, and within the temperature range of (Tmb) to (Tmb + 70) ° C. (Tmb represents the melting point of the polymer constituting the layer (B)). Melt. Melting takes place in separate extruders. Subsequently, an unstretched laminated sheet is produced by a simultaneous multilayer extrusion method using a feed block. That is, the polymer melt constituting the layer (A) and the polymer melt constituting the layer (B) are laminated into two layers using a feed block so as to be layer (A) / layer (B). Then, it is developed on a slit die and extruded. At this time, the polymer laminated by the feed block maintains the laminated form.
次に、得られた未延伸積層シートを、少なくとも１軸方向、好ましくは二軸方向に延伸する。延伸は、逐次二軸延伸でもよく、同時二軸延伸でもよい。逐次二軸延伸する場合、スリットダイより押出されたポリマーは、キャスティングドラムで冷却固化され、未延伸積層シートとなる。この未延伸積層シートを、ロール加熱、赤外線加熱等で加熱し、縦方向に延伸して縦延伸積層フィルムを得る。この延伸は２個以上のロールの周速差を利用して行うのが好ましい。延伸温度は層（Ａ）のＴｇａ（Ｔｇａは層（Ａ）を構成するポリマーのガラス転移温度を表わす）以上の温度、さらには（Ｔｇａ）〜（Ｔｇａ＋４０℃）とするのが好ましい。 Next, the obtained unstretched laminated sheet is stretched in at least a uniaxial direction, preferably in a biaxial direction. Stretching may be sequential biaxial stretching or simultaneous biaxial stretching. In the case of sequential biaxial stretching, the polymer extruded from the slit die is cooled and solidified by a casting drum to form an unstretched laminated sheet. This unstretched laminated sheet is heated by roll heating, infrared heating or the like, and stretched in the longitudinal direction to obtain a longitudinally stretched laminated film. This stretching is preferably performed by utilizing the difference in peripheral speed between two or more rolls. The stretching temperature is preferably a temperature equal to or higher than the Tga of the layer (A) (Tga represents the glass transition temperature of the polymer constituting the layer (A)), and more preferably (Tga) to (Tga + 40 ° C.).
縦延伸後のフィルムは、続いて、横延伸、熱固定、熱弛緩の処理を順次施して二軸配向フィルムとするが、これら処理はフィルムを走行させながら行う。横延伸の処理はＴｇａより高い温度から始める。そしてＴｇａより（５〜７０）℃高い温度まで昇温しながら行う。横延伸過程での昇温は連続的でも段階的（逐次的）でもよいが通常逐次的に昇温する。例えばテンターの横延伸ゾーンをフィルム走行方向に沿って複数に分け、ゾーン毎に所定温度の加熱媒体を流すことで昇温する。 Subsequently, the film after longitudinal stretching is subjected to lateral stretching, heat setting, and thermal relaxation in order to form a biaxially oriented film. These processes are performed while the film is running. The transverse stretching process starts from a temperature higher than Tga. And it is performed while raising the temperature to (5 to 70) ° C. higher than Tga. Although the temperature rise in the transverse stretching process may be continuous or stepwise (sequential), the temperature is usually raised sequentially. For example, the transverse stretching zone of the tenter is divided into a plurality along the film running direction, and the temperature is raised by flowing a heating medium having a predetermined temperature for each zone.
延伸倍率は、用途の要求特性にもよるが、縦方向、縦方向と直交する方向（以降、横方向と呼ぶ）ともに、好ましくは３．０〜４．２倍、さらに好ましくは３．２〜４．０倍である。３．０倍未満とするとフィルムの厚み斑の良好なフィルムが得られない。また、耐加水分解性に劣るフィルムとなり好ましくない。他方、４．２倍を超えると層（Ａ）と層（Ｂ）の密着力が低くなり好ましくない。 The draw ratio is preferably 3.0 to 4.2 times, more preferably 3.2, both in the longitudinal direction and the direction orthogonal to the longitudinal direction (hereinafter referred to as the transverse direction), although it depends on the required properties of the application. It is 4.0 times. If it is less than 3.0 times, a film with good thickness unevenness cannot be obtained. Moreover, it becomes a film inferior to hydrolysis resistance, and is not preferable. On the other hand, if it exceeds 4.2 times, the adhesion between the layer (A) and the layer (B) is lowered, which is not preferable.
横延伸後のフィルムは両端を把持したまま（Ｔｍａ−２０℃）〜（Ｔｍａ−８０℃）で定幅または１０％以下の幅減少下で熱処理して熱収縮率を低下させると寸法安定性が良くなる。これより高い温度で熱処理するとフィルムの平面性が悪くなり、厚み斑が大きくなり好ましくない。また、（Ｔｍａ−８０）℃より低い温度で熱処理すると熱収縮率が大きくなることがあり好ましくない。 When the film after transverse stretching is heat-treated with a constant width or a decrease in width of 10% or less while holding both ends (Tma-20 ° C) to (Tma-80 ° C), the dimensional stability is reduced. Get better. If heat treatment is performed at a temperature higher than this, the flatness of the film deteriorates, and the thickness unevenness increases, which is not preferable. Further, heat treatment at a temperature lower than (Tma-80) ° C. is not preferable because the heat shrinkage rate may increase.
二軸延伸後の積層フィルムの厚みは、好ましくは２５〜２５０μｍ、さらに好ましくは４０〜２００μｍ、特に好ましくは５０〜１２５μｍである。２５μｍ未満であると耐候性が低下して好ましくなく、他方、２５０μｍを超えると不経済なだけである。 The thickness of the laminated film after biaxial stretching is preferably 25 to 250 μm, more preferably 40 to 200 μm, and particularly preferably 50 to 125 μm. If it is less than 25 μm, the weather resistance is not preferred, and if it exceeds 250 μm, it is only uneconomical.
本発明の太陽電池裏面保護膜用積層フィルムのうえに太陽電池素子の封止樹脂を設ける場合、フィルムと封止樹脂との接着性を向上させる目的で、太陽電池モジュールの内側に接する層のうえに易接着性のコーティング層を設けてもよい。コーティング層の構成材としては、フィルムとＥＶＡの双方に優れた接着性を示す材を用いることが好ましく、この材として、例えばポリエステル樹脂やアクリル樹脂を例示することができ、これらの樹脂にさらに架橋成分を含有させることが好ましい。 When the sealing resin for the solar cell element is provided on the laminated film for the solar cell back surface protective film of the present invention, for the purpose of improving the adhesion between the film and the sealing resin, on the layer in contact with the inner side of the solar cell module. An easy-adhesive coating layer may be provided. As the constituent material of the coating layer, it is preferable to use a material exhibiting excellent adhesion to both the film and EVA, and examples of this material include polyester resins and acrylic resins, and these resins can be further crosslinked. It is preferable to contain a component.
コーティング層の塗設は、一般的な既知のコーティング方法を用いることができるが、好ましくは、延伸可能なフィルムに前述のコーティング層の構成成分を含む水性液を塗布した後、乾燥、延伸し、熱処理するインラインコーティング法で行う。このとき、フィルムの上に形成されるコーティング層の厚さは０．０１〜１μｍであることが好ましい。 The coating layer can be coated by using a general known coating method. Preferably, an aqueous liquid containing the above-mentioned coating layer components is applied to a stretchable film, followed by drying and stretching. The in-line coating method is used for heat treatment. At this time, it is preferable that the thickness of the coating layer formed on a film is 0.01-1 micrometer.
［太陽電池裏面保護膜］
本発明の太陽電池裏面保護膜用積層フィルムは、単独で太陽電池裏面保護膜として用いてもよく、また積層フィルムの２枚以上を貼り合わせて太陽電池裏面保護膜として用いてもよい。
例えば、絶縁特性を向上させる目的で別の透明ポリエステルフィルム等と貼り合わせて用いることができる。
太陽電池裏面保護膜として用いる際に、水蒸気バリア性を付与する目的で、水蒸気バリア層を積層することが好ましい。この構成の太陽電池裏面保護膜は、ＪＩＳ Ｚ０２０８−７３に従い測定される水蒸気の透過率が５ｇ／（ｍ２・２４ｈ）以下であることが好ましい。
[Solar cell back surface protective film]
The laminated film for a solar cell back surface protective film of the present invention may be used alone as a solar cell back surface protective film, or two or more laminated films may be bonded together and used as a solar cell back surface protective film.
For example, it can be used by being bonded to another transparent polyester film or the like for the purpose of improving the insulating properties.
When used as a solar cell back surface protective film, a water vapor barrier layer is preferably laminated for the purpose of imparting water vapor barrier properties. The solar cell back surface protective film having this configuration preferably has a water vapor transmission rate of 5 g / (m 2 · 24 h) or less as measured according to JIS Z0208-73.
水蒸気バリア層としては、水蒸気バリア性を有するフィルムや箔を用いることができる。フィルムとしては、ポリ塩化ビニリデンフィルム、ポリ塩化ビニリデンコートフィルム、ポリフッ化ビニリデンコートフィルム、酸化ケイ素蒸着フィルム、酸化アルミニウム蒸着フィルム、アルミニウム蒸着フィルムを例示することができ、箔としては、アルミニウム箔、銅箔を例示することができる。水蒸気バリア層は、コーティングで設けてもよく、蒸着で設けてもよい。 As the water vapor barrier layer, a film or foil having a water vapor barrier property can be used. Examples of the film include a polyvinylidene chloride film, a polyvinylidene chloride coated film, a polyvinylidene fluoride coated film, a silicon oxide deposited film, an aluminum oxide deposited film, and an aluminum deposited film, and the foil includes an aluminum foil and a copper foil. Can be illustrated. The water vapor barrier layer may be provided by coating or may be provided by vapor deposition.
以下、実施例に基づき本発明を説明する。各特性値ならびに評価法は下記の方法によって測定、評価した。 Hereinafter, the present invention will be described based on examples. Each characteristic value and evaluation method were measured and evaluated by the following methods.
（１）フィルム厚み
フィルムの試料をエレクトリックマイクロメーター（アンリツ製 Ｋ−４０２Ｂ）にて、１０点厚みを測定し、平均値をフィルムの厚みとした。
(1) Film thickness A 10-point thickness of a film sample was measured with an electric micrometer (K-402B manufactured by Anritsu), and the average value was defined as the film thickness.
（２）各層の厚み
フィルムから試料を三角形に切り出し、包埋カプセルに固定後、エポキシ樹脂にて包埋した。そして、包埋されたサンプルをミクロトーム（ＵＬＴＲＡＣＵＴ−Ｓ）で縦方向に平行な断面を５０ｎｍ厚の薄膜切片にした後、透過型電子顕微鏡を用いて、加速電圧１００ｋｖにて観察撮影し、写真から各層の厚みを測定し、平均厚みを求めた。
(2) Thickness of each layer A sample was cut into a triangle from the film, fixed in an embedded capsule, and then embedded in an epoxy resin. Then, after embedding the sample with a microtome (ULTRACUT-S) into a thin film section having a thickness of 50 nm in parallel with the microtome, the specimen was observed and photographed with a transmission electron microscope at an acceleration voltage of 100 kv. The thickness of each layer was measured and the average thickness was determined.
（３）ガラス転移点（Ｔｇ）、融点（Ｔｍ）
フィルムの試料について、示差走査熱量装置ＴＡ Ｉｎｓｔｒｕｍｅｎｔｓ製 ＭＤＳＣ Ｑ１００を用い、昇温速度２０℃／分でガラス転移および融解ピークを求めた。なお、サンプル量はフィルム原料チップの測定の場合は１０ｍｇ、フィルムの測定の場合は２０ｍｇとした。
(3) Glass transition point (Tg), melting point (Tm)
About the sample of the film, the glass transition and the melting peak were calculated | required with the temperature increase rate of 20 degree-C / min using differential scanning calorimeter TA Instruments MDSC Q100. Note that the sample amount was 10 mg in the case of measuring film raw material chips, and 20 mg in the case of measuring films.
（４）耐候性
高圧水銀ランプ（東芝製 ＴＯＳ ＣＵＲＥ ４０１）を用いて、フィルムに２００Ｗ／ｍ２の照射強度で８時間紫外線照射を行った。予め測定しておいた紫外線照射前のフィルムのＹＩ値と、紫外線照射前のフィルムのＹＩ値を用いて、ΔＹＩを下記式に従い算出し、下記の基準で耐光性を評価した。なお、イエローインデックスのＹＩ値は、日本電色工業製自動色差計（ＳＥ−Σ９０型）を用いて層（Ｂ）の面について測定した。
ΔＹＩ＝照射後のＹＩ値−照射前のＹＩ値
○：ΔＹＩが８未満
△：ΔＹＩが８以上１２未満
×：ΔＹＩが１２以上
(4) Weather resistance Using a high-pressure mercury lamp (TOS CURE 401 manufactured by Toshiba), the film was irradiated with ultraviolet rays at an irradiation intensity of 200 W / m 2 for 8 hours. ΔYI was calculated according to the following formula using the YI value of the film before ultraviolet irradiation and the YI value of the film before ultraviolet irradiation, which were measured in advance, and light resistance was evaluated according to the following criteria. The YI value of the yellow index was measured on the surface of the layer (B) using an automatic color difference meter (SE-Σ90 type) manufactured by Nippon Denshoku Industries Co., Ltd.
ΔYI = YI value after irradiation−YI value before irradiation ○: ΔYI is less than 8 Δ: ΔYI is 8 or more and less than 12 ×: ΔYI is 12 or more
（５）耐加水分解性
１２１℃−２ａｔｍ−１００％ＲＨの雰囲気にフィルムを２００時間エージングした後、ＡＳＴＭ−Ｄ６１Ｔによりフィルムの破断伸度を測定し、エージング前の破断伸度を１００％にしたときの比（保持率）で比較し下記の基準で判定した。
○：保持率が８０％を超える
△：保持率が５０以上８０％未満
×：保持率が５０％未満
(5) Hydrolysis resistance After aging the film for 200 hours in an atmosphere of 121 ° C.-2 atm-100% RH, the breaking elongation of the film was measured by ASTM-D61T, and the breaking elongation before aging was set to 100%. Comparison was made based on the ratio (retention rate) at the time, and the following criteria were used for judgment.
○: Retention rate exceeds 80% Δ: Retention rate is 50 or more and less than 80% ×: Retention rate is less than 50%
（６）ポリエステルの固有粘度（ＩＶ）
試料０．６ｇをオルソクロロフェノール５０ｍｌ中に加熱溶解した後、一旦冷却させ、遠心分離機により白色無機顔料等の無機物を取り除き、その溶液をオストワルド式粘度管を用いて３５℃の温度条件で測定した溶液粘度から算出した。
(6) Intrinsic viscosity of polyester (IV)
After 0.6 g of sample is dissolved in 50 ml of orthochlorophenol by heating, it is once cooled, and inorganic substances such as white inorganic pigment are removed by a centrifuge, and the solution is measured at 35 ° C. using an Ostwald viscosity tube. Calculated from the solution viscosity.
（参考例１）ＰＥＴ−Ａ
エステル交換反応容器にジメチルテレフタレートを１００重量部、エチレングリコールを６１重量部、酢酸マグネシウム四水塩を０．０６重量部仕込み、１５０℃に加熱して溶融し撹拌した。反応容器内温度をゆっくりと２３５℃まで昇温しながら反応を進め、生成するメタノールを反応容器外へ留出させた。メタノールの留出が終了したらトリメチルリン酸を０．０２重量部添加した。トリメチルリン酸を添加した後、三酸化アンチモンを０．０３重量部添加し、反応物を重合装置に移行した。ついで重合装置内の温度を２３５℃から２９０℃まで９０分かけて昇温し、同時に装置内の圧力を大気圧から１００Ｐａまで９０分かけて減圧した。重合装置内容物の撹拌トルクが所定の値に達したら装置内を窒素ガスで大気圧に戻して重合を終了した。重合装置下部のバルブを開いて重合装置内部を窒素ガスで加圧し、重合の完了したポリエチレンテレフタレートをストランド状にして水中に吐出した。ストランドはカッターによってチップ化した。このようにして固有粘度が０．６５ｄｌ／ｇであるポリエチレンテレフタレートのポリマーを得た。これをＰＥＴ−Ａと称する。
(Reference Example 1) PET-A
A transesterification vessel was charged with 100 parts by weight of dimethyl terephthalate, 61 parts by weight of ethylene glycol, and 0.06 part by weight of magnesium acetate tetrahydrate, heated to 150 ° C., melted and stirred. The reaction was advanced while the temperature inside the reaction vessel was slowly raised to 235 ° C., and the methanol produced was distilled out of the reaction vessel. When the distillation of methanol was completed, 0.02 part by weight of trimethyl phosphoric acid was added. After adding trimethyl phosphoric acid, 0.03 part by weight of antimony trioxide was added, and the reaction product was transferred to a polymerization apparatus. Subsequently, the temperature in the polymerization apparatus was raised from 235 ° C. to 290 ° C. over 90 minutes, and at the same time, the pressure in the apparatus was reduced from atmospheric pressure to 100 Pa over 90 minutes. When the stirring torque of the contents of the polymerization apparatus reached a predetermined value, the interior of the apparatus was returned to atmospheric pressure with nitrogen gas to complete the polymerization. The valve at the bottom of the polymerization apparatus was opened and the inside of the polymerization apparatus was pressurized with nitrogen gas, and the polymerized polyethylene terephthalate was discharged into water in the form of a strand. The strand was chipped with a cutter. In this way, a polyethylene terephthalate polymer having an intrinsic viscosity of 0.65 dl / g was obtained. This is referred to as PET-A.
（参考例２）ＰＥＴ−Ｂ
参考例１で得られたＰＥＴ−Ａを６０重量部と、テイカ株式会社製ルチル型酸化チタン粒子ＪＲ３０１（平均粒径０．３μｍ）を４０重量部とをブレンドし、二軸混練機に供給して２８０℃で溶融した。溶融混練したポリエステル組成物をストランド状にして水中に吐出し、カッターによってチップ化した。これをＰＥＴ−Ｂと称する。
(Reference Example 2) PET-B
60 parts by weight of PET-A obtained in Reference Example 1 and 40 parts by weight of Rutile type titanium oxide particles JR301 (average particle size 0.3 μm) manufactured by Teika Co., Ltd. were blended and supplied to a biaxial kneader. And melted at 280 ° C. The melt-kneaded polyester composition was made into a strand shape, discharged into water, and chipped with a cutter. This is referred to as PET-B.
（参考例３）ＰＥＴ−Ｃ
参考例１で得られたＰＥＴ−Ａを６０重量部と、堺化学工業株式会社製沈降性硫酸バリウム粒子３００Ｒ（平均粒径０．７μｍ）を４０重量部とをブレンドし、二軸混練機に供給して２８０℃で溶融した。溶融混練したポリエステル組成物をストランド状にして水中に吐出し、カッターによってチップ化した。これをＰＥＴ−Ｃと称する。
(Reference Example 3) PET-C
60 parts by weight of PET-A obtained in Reference Example 1 and 40 parts by weight of precipitated barium sulfate particles 300R (average particle size 0.7 μm) manufactured by Sakai Chemical Industry Co., Ltd. were blended into a biaxial kneader. Feed and melt at 280 ° C. The melt-kneaded polyester composition was made into a strand shape, discharged into water, and chipped with a cutter. This is referred to as PET-C.
［実施例１］
シンジオタクチックポリスチレン（出光化学株式会社製、グレード；１３０ＺＣ）、ＰＥＴ−ＡおよびＰＥＴ−Ｂをシンジオタクチックポリスチレンが９０重量％、ポリエチレンテレフタレートが１９重量％、ルチル型酸化チタン粒子が１重量％となるように混合し、回転式真空乾燥機にて１８０℃で３時間乾燥した後、押出機１に供給し２８０℃で溶融押出しした。これを層（Ａ）とする。
層（Ｂ）は、ＰＥＴ−ＡとＰＥＴ−Ｂを、ルチル型酸化チタン粒子の含有率が２０重量％となるように混合し、回転式真空乾燥機にて１８０℃で３時間乾燥した後、押出機２に供給し２８０℃で溶融押出しした。それぞれの押出機で溶融した樹脂組成物を、２層フィードブロック装置を使用して合流させ、その積層状態を保持したままスリットダイよりシート状に成形した。さらにこのシートを表面温度２５℃の冷却ドラムで冷却固化した未延伸フィルムを１２０℃にて長手方向（縦方向）に３．４倍延伸し、２５℃のロール群で冷却した。続いて、縦延伸したフィルムの両端をクリップで保持しながらテンターに導き１４０℃に加熱された雰囲気中で長手に垂直な方向（横方向）に３．７倍延伸した。その後テンター内で２２０℃に加熱された雰囲気中で熱固定を行い、横方向に３％の幅入れを行い、室温まで冷やして太陽電池裏面保護膜用積層フィルムを得た。得られた積層フィルムの層構成は表１のとおりであった。評価結果を表１に示す。
[Example 1]
Syndiotactic polystyrene (manufactured by Idemitsu Chemical Co., Ltd., grade: 130ZC), PET-A and PET-B are 90% by weight of syndiotactic polystyrene, 19% by weight of polyethylene terephthalate, and 1% by weight of rutile titanium oxide particles. The mixture was mixed and dried at 180 ° C. for 3 hours in a rotary vacuum dryer, then supplied to the extruder 1 and melt extruded at 280 ° C. This is layer (A).
Layer (B) is a mixture of PET-A and PET-B so that the content of the rutile-type titanium oxide particles is 20% by weight, and after drying at 180 ° C. for 3 hours in a rotary vacuum dryer, It supplied to the extruder 2 and melt-extruded at 280 degreeC. The resin compositions melted in the respective extruders were merged using a two-layer feed block device, and formed into a sheet shape from a slit die while maintaining the laminated state. Further, an unstretched film obtained by cooling and solidifying the sheet with a cooling drum having a surface temperature of 25 ° C. was stretched 3.4 times in the longitudinal direction (longitudinal direction) at 120 ° C., and cooled by a roll group at 25 ° C. Subsequently, while holding both ends of the longitudinally stretched film with clips, the film was drawn to a tenter and stretched 3.7 times in a direction perpendicular to the longitudinal direction (lateral direction) in an atmosphere heated to 140 ° C. Thereafter, heat setting was performed in an atmosphere heated to 220 ° C. in a tenter, a width of 3% was applied in the lateral direction, and the film was cooled to room temperature to obtain a laminated film for a solar cell back surface protective film. The layer structure of the obtained laminated film was as shown in Table 1. The evaluation results are shown in Table 1.
［実施例２〜９、比較例１〜４］
フィルムの層構成を表１に示すとおりに変更した以外は実施例１と同様にして太陽電池裏面保護膜用積層フィルムを得た。得られた積層フィルムの評価結果は表１のとおりであった。なお、比較例１は、Ｂ／Ａ／Ｂの３層構成とし、２種の溶融した樹脂組成物を３層フィードブロック装置を使用して合流させることで積層した。
[Examples 2 to 9, Comparative Examples 1 to 4]
A laminated film for a solar cell back surface protective film was obtained in the same manner as in Example 1 except that the layer configuration of the film was changed as shown in Table 1. The evaluation results of the obtained laminated film were as shown in Table 1. In addition, the comparative example 1 was made into the 3 layer structure of B / A / B, and it laminated | stacked by making 2 types of melted resin compositions merge using a 3 layer feed block apparatus.
ただし、表において、「酸化チタン」はルチル型酸化チタンを意味し、「ＰＥＴ」はポリエチレンテレフタレートを意味する。
なお、シンジオタクチックポリスチレンとして用いた１３０ＺＣ（出光化学株式会社製）は、立体化学構造がシンジオタクチック構造を有するポリスチレンであり、核磁気共鳴法（１３Ｃ−ＮＭＲ法）により測定されるタクティシティーが、ダイアッド（構成単位が２個）１００％、ペンタッド（構成単位が５個）９９％以上である。
In the table, “titanium oxide” means rutile-type titanium oxide, and “PET” means polyethylene terephthalate.
In addition, 130ZC (made by Idemitsu Chemical Co., Ltd.) used as syndiotactic polystyrene is a polystyrene whose stereochemical structure has a syndiotactic structure, and is a tacticity measured by a nuclear magnetic resonance method ( 13 C-NMR method). However, it is 100% for dyad (2 structural units) and 99% or more for pentad (5 structural units).
［比較例５］
層（Ｂ）のポリエステルを、それぞれＰＥＴ−ＡとＰＥＴ−Ｃを硫酸バリウムの含有率が２０重量％となるように混合した以外は実施例１と同様にして太陽電池裏面保護膜用積層フィルムを得た。得られた積層フィルムの層構成は表１のとおりであった。評価結果を表１に示す。
[Comparative Example 5]
A laminated film for a solar cell back surface protective film was prepared in the same manner as in Example 1 except that the polyester of layer (B) was mixed with PET-A and PET-C so that the barium sulfate content was 20% by weight. Obtained. The layer structure of the obtained laminated film was as shown in Table 1. The evaluation results are shown in Table 1.
［比較例６］
フィルムの層構成を表１に示すとおりに変更した以外は実施例１と同様にして太陽電池裏面保護膜用積層フィルムを得た。得られたフィルムは層間の密着力に乏しく、手で容易に層（Ａ）と層（Ｂ）との間で剥離できる状態であった。
[Comparative Example 6]
A laminated film for a solar cell back surface protective film was obtained in the same manner as in Example 1 except that the layer configuration of the film was changed as shown in Table 1. The obtained film had poor adhesion between the layers, and was easily peelable between the layer (A) and the layer (B) by hand.
本発明の太陽電池裏面保護膜用積層ポリエステルフィルムは、太陽電池裏面保護膜として有用である。 The laminated polyester film for solar cell back surface protective film of the present invention is useful as a solar cell back surface protective film.
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