CN101878537B - 太阳能电池用密封膜和使用其的太阳能电池 - Google Patents
太阳能电池用密封膜和使用其的太阳能电池 Download PDFInfo
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- CN101878537B CN101878537B CN2008801184518A CN200880118451A CN101878537B CN 101878537 B CN101878537 B CN 101878537B CN 2008801184518 A CN2008801184518 A CN 2008801184518A CN 200880118451 A CN200880118451 A CN 200880118451A CN 101878537 B CN101878537 B CN 101878537B
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- sealing film
- solar cell
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- vinyl acetate
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- 238000007789 sealing Methods 0.000 title claims abstract description 93
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 43
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 35
- 150000001412 amines Chemical class 0.000 claims abstract description 32
- 239000004611 light stabiliser Substances 0.000 claims abstract description 30
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012964 benzotriazole Substances 0.000 claims abstract description 26
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims abstract description 24
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 17
- -1 2,2′-methylene Chemical group 0.000 claims description 23
- 239000006096 absorbing agent Substances 0.000 claims description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 claims description 4
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 4
- OCWYEMOEOGEQAN-UHFFFAOYSA-N bumetrizole Chemical compound CC(C)(C)C1=CC(C)=CC(N2N=C3C=C(Cl)C=CC3=N2)=C1O OCWYEMOEOGEQAN-UHFFFAOYSA-N 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 2
- 230000006750 UV protection Effects 0.000 abstract description 14
- DQXBYHZEEUGOBF-UHFFFAOYSA-N but-3-enoic acid;ethene Chemical compound C=C.OC(=O)CC=C DQXBYHZEEUGOBF-UHFFFAOYSA-N 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- 239000011521 glass Substances 0.000 description 12
- 238000004132 cross linking Methods 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- 238000010248 power generation Methods 0.000 description 7
- 239000001273 butane Substances 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 238000002834 transmittance Methods 0.000 description 5
- XITRBUPOXXBIJN-UHFFFAOYSA-N bis(2,2,6,6-tetramethylpiperidin-4-yl) decanedioate Chemical group C1C(C)(C)NC(C)(C)CC1OC(=O)CCCCCCCCC(=O)OC1CC(C)(C)NC(C)(C)C1 XITRBUPOXXBIJN-UHFFFAOYSA-N 0.000 description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000004383 yellowing Methods 0.000 description 4
- VQMHSKWEJGIXGA-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-6-dodecyl-4-methylphenol Chemical compound CCCCCCCCCCCCC1=CC(C)=CC(N2N=C3C=CC=CC3=N2)=C1O VQMHSKWEJGIXGA-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000006087 Silane Coupling Agent Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
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- 239000000126 substance Substances 0.000 description 3
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MUXOBHXGJLMRAB-UHFFFAOYSA-N Dimethyl succinate Chemical compound COC(=O)CCC(=O)OC MUXOBHXGJLMRAB-UHFFFAOYSA-N 0.000 description 2
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
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- 238000007796 conventional method Methods 0.000 description 2
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- 238000007872 degassing Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-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
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 2
- 150000002978 peroxides Chemical class 0.000 description 2
- 150000002989 phenols Chemical class 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920000139 polyethylene terephthalate Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
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- 230000002195 synergetic effect Effects 0.000 description 2
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 description 2
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- NALFRYPTRXKZPN-UHFFFAOYSA-N 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane Chemical compound CC1CC(C)(C)CC(OOC(C)(C)C)(OOC(C)(C)C)C1 NALFRYPTRXKZPN-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
- UBRWPVTUQDJKCC-UHFFFAOYSA-N 1,3-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=CC(C(C)(C)OOC(C)(C)C)=C1 UBRWPVTUQDJKCC-UHFFFAOYSA-N 0.000 description 1
- GWQOYRSARAWVTC-UHFFFAOYSA-N 1,4-bis(2-tert-butylperoxypropan-2-yl)benzene Chemical compound CC(C)(C)OOC(C)(C)C1=CC=C(C(C)(C)OOC(C)(C)C)C=C1 GWQOYRSARAWVTC-UHFFFAOYSA-N 0.000 description 1
- UICXTANXZJJIBC-UHFFFAOYSA-N 1-(1-hydroperoxycyclohexyl)peroxycyclohexan-1-ol Chemical compound C1CCCCC1(O)OOC1(OO)CCCCC1 UICXTANXZJJIBC-UHFFFAOYSA-N 0.000 description 1
- OTCWVYFQGYOYJO-UHFFFAOYSA-N 1-o-methyl 10-o-(1,2,2,6,6-pentamethylpiperidin-4-yl) decanedioate Chemical compound COC(=O)CCCCCCCCC(=O)OC1CC(C)(C)N(C)C(C)(C)C1 OTCWVYFQGYOYJO-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
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- BCIOQYMTCPEOKK-UHFFFAOYSA-N 2-(2,2,3,3-tetramethylpiperidin-1-yl)ethanol Chemical compound CC1(C)CCCN(CCO)C1(C)C BCIOQYMTCPEOKK-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明提供具有优异的抗紫外线性能的太阳能电池用密封膜。一种太阳能电池用密封膜,其特征在于:含有乙烯乙酸乙烯酯共聚物、有机过氧化物、苯并三唑系紫外线吸收剂和受阻胺系光稳定剂;相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述苯并三唑系紫外线吸收剂的含量为0.01~0.3质量份;相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述受阻胺系光稳定剂的含量为0.01~2质量份。
Description
技术领域
本发明涉及以乙烯乙酸乙烯酯共聚物为主成分的太阳能电池用密封膜,以及使用该密封膜的太阳能电池,特别是涉及抗紫外线性能优异的太阳能电池用密封膜和太阳能电池。
背景技术
近年来,从资源的有效利用和防止环境污染等方面出发,把太阳光直接转换为电能的太阳能电池受到注目,并正在推进开发。
太阳能电池通常如图1所示,按如下方法制造:按由玻璃基板等构成的受光面侧透明保护部件11、受光面侧密封膜13A、硅发电元件等太阳能电池用单元14、背面侧密封膜13B和背面侧保护部件(后罩)12的顺序层叠,在进行了减压而脱气后,加热加压使受光面侧密封膜13A与背面侧密封膜13B发生交联固化而粘合一体化。现有的太阳能电池为了得到高的电力输出而将多个太阳能电池用单元14连接使用。因此,为了确保太阳能电池用单元14间的绝缘性,而使用具有绝缘性的密封膜13A、13B来密封太阳能电池用单元。
作为用于受光面侧和背面侧的密封膜,由于廉价且具有高透明性而优选使用乙烯乙酸乙烯酯共聚物(EVA)薄膜(专利文献1)。另外,为了提高膜强度、耐久性,在前述密封膜中除乙烯乙酸乙烯酯共聚物以外还使用有机过氧化物等交联剂来提高交联密度。
对于上述太阳能电池,从提高发电效率的观点来看,强烈需要将入射到太阳能电池中的光尽可能高效地聚集到太阳能电池用单元中。因此,理想的是,密封膜具有尽可能高的透明性、对入射的太阳光无吸收无反射、使绝大部分的太阳光透过。
然而,太阳能电池在长期受到光照时,紫外线会导致乙烯乙酸乙烯酯共聚物劣化,密封膜会发生黄变、粘合性降低等劣化。密封膜黄变不仅会降低太阳能电池的发电性能,还会降低美观性。
于是,在现有的密封膜中,除EVA和有机过氧化物以外,通过还添加二苯甲酮系等紫外线吸收剂,苯酚系、硫系、磷系、胺系、受阻酚系、受阻胺系、肼系等光稳定剂,防变色剂等,以谋求抗紫外线性能的提高。
专利文献1:日本特开平06-177412号公报
发明内容
发明要解决的问题
然而,即使是使用了现有的密封膜的太阳能电池,在长期使用时仍会发生密封膜的劣化,存在引起发电性能、美观性降低等问题。为此,需要密封膜进一步提高抗紫外线性能。
因此,本发明的目的在于,提供具有优异的抗紫外线性能的太阳能电池用密封膜。
用于解决问题的方案
本发明人等鉴于上述课题进行各种研究的结果,发现在含有乙烯乙酸乙烯酯共聚物的密封膜中,通过并用苯并三唑系紫外线吸收剂和受阻胺系光稳定剂,利用双方的显著的协同效果,而使得提高抗紫外线性能成为可能。然而,当为确保充分的抗紫外线性能而大量添加苯并三唑系紫外线吸收剂和受阻胺系光稳定剂时,存在这些添加剂所导致的密封膜的透明性降低的情况。另一方面,当苯并三唑系紫外线吸收剂和受阻胺系光稳定剂的添加量过少时,存在无法充分地提高抗紫外线性能的情况。因此,苯并三唑系紫外线吸收剂和受阻胺系光稳定剂需要分别添加既不降低密封膜的透明性又能提高抗紫外线性能的量。
在此,为了解决上述问题,本发明使用一种太阳能电池用密封膜,其特征在于:
含有乙烯乙酸乙烯酯共聚物、有机过氧化物、苯并三唑系紫外线吸收剂和受阻胺系光稳定剂,
相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述苯并三唑系紫外线吸收剂的含量为0.01~0.3质量份,
相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述受阻胺系光稳定剂的含量为0.01~2质量份。
下面列出本发明的太阳能电池用密封膜的优选形态。
(1)相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述苯并三唑系紫外线吸收剂的含量为0.05~0.1质量份。
(2)相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述受阻胺系光稳定剂的含量为0.05~1.5质量份。
(3)前述苯并三唑系紫外线吸收剂与前述受阻胺系光稳定剂的质量比为1∶1~1∶5。
(4)前述苯并三唑系紫外线吸收剂为2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚、2-[5-氯(2H)-苯并三唑-2-基]-4-甲基-6-叔丁基苯酚和/或2,2′-亚甲基双-[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚。
(5)前述受阻胺系光稳定剂为双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯和/或聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}-1,6-己二基{(2,2,6,6-四甲基-4-哌啶基)亚氨}]。
(6)前述有机过氧化物为选自过氧化氢系化合物、过氧化二烷基系化合物和过氧化酮系化合物组成的组中的至少一种。
(7)相对于100质量份所述乙烯乙酸乙烯酯共聚物,前述有机过氧化物的含量为0.2~1.5质量份。
(8)相对于100质量份所述乙烯乙酸乙烯酯共聚物,前述乙烯乙酸乙烯酯共聚物的乙酸乙烯酯含量为20~35质量份。
发明的效果
本发明的太阳能电池用密封膜通过组合使用苯并三唑系紫外线吸收剂和受阻胺系光稳定剂,并使它们的含量最优化,从而实现即便在长期使用时仍能显著抑制黄变、粘合性的降低,具有优异的抗紫外线性能。进而,前述太阳能电池用密封膜不会由于添加苯并三唑系紫外线吸收剂和受阻胺系光稳定剂而导致透明性降低,而可长期维持高紫外线吸收性。因此,通过前述太阳能电池用密封膜,可提供抑制内部所含单元等的劣化、可自发电开始初期以来的长时间内发挥高发电性能的太阳能电池。
附图说明
图1为表示通常的太阳能电池的截面图。
符号说明
11 受光面侧透明保护部件
12 背面侧保护部件
13A 受光面侧密封膜
13B 背面侧密封膜
14 太阳能电池单元
具体实施方式
本发明的太阳能电池用密封膜,其特征在于,作为基本成分含有乙烯乙酸乙烯酯共聚物、有机过氧化物、苯并三唑系紫外线吸收剂和受阻胺系光稳定剂,实现了苯并三唑系紫外线吸收剂和受阻胺系光稳定剂的含量的最优化。
在前述太阳能电池用密封膜中,相对于100质量份前述乙烯乙酸乙烯酯共聚物,苯并三唑系紫外线吸收剂的含量为0.01~0.3质量份,优选为0.05~0.3质量份,特别优选为0.05~0.1质量份。进而,相对于100质量份前述乙烯乙酸乙烯酯共聚物,前述太阳能电池用密封膜中的受阻胺系光稳定剂的含量为0.01~2质量份,优选为0.05~0.2质量份,特别优选为0.05~1.5质量份。通过确定它们的含量,可防止添加剂所导致的透明性降低,同时赋予密封膜优异的抗紫外线性能。
前述苯并三唑系紫外线吸收剂(A)和前述受阻胺系光稳定剂(B)的质量比(A∶B)为1∶1~1∶5,特别优选为1∶1~1∶3。
在本发明的密封膜中使用的苯并三唑系紫外线吸收剂,优选为在330~360nm、特别是在340~350nm的范围内具有最大吸收波长的物质。只要为这样的紫外线吸收剂,则可高度吸收照射光所含的紫外线中特别可能引起乙烯乙酸乙烯酯共聚物的光劣化的紫外线。
作为前述紫外线吸收剂,具体来说可优选列举出2-[2′-羟基-5′-(羟甲基)苯基]-2H-苯并三唑、2-[2′-羟基-5′-(2-羟乙基)苯基]-2H-苯并三唑、2-[2′-羟基-5′-(3-羟丙基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-甲基-5′-(羟甲基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-甲基-5′-(2-羟乙基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-甲基-5′-(3-羟丙基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-叔丁基-5′-(羟甲基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-叔丁基-5′-(2-羟乙基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-叔丁基-5′-(2-羟乙基)苯基]-5-氯-2H-苯并三唑、2-[2′-羟基-3′-叔丁基-5′-(3-羟丙基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-叔辛基-5′-(羟甲基)苯基]-2H-苯并三唑、2-[2′-羟基-3′叔辛基-5′-(2-羟乙基)苯基]-2H-苯并三唑、2-[2′-羟基-3′-叔辛基-5′-(3-羟丙基)苯基]-2H-苯并三唑等,或2,2′-亚甲基双[6-(2H-苯并三唑-2-基)-4-(羟甲基)苯酚]、2,2′-亚甲基双[6-(2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]、2,2′-亚甲基双[6-(5-氯-2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]、2,2′-亚甲基双[6-(5-溴-2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]、2,2′-亚甲基双[6-(2H-苯并三唑-2-基)-4-(3-羟丙基)苯酚]、2,2′-亚甲基双[6-(5-氯-2H-苯并三唑-2-基)-4-(3-羟丙基)苯酚]、2,2′-亚甲基双[6-(5-溴-2H-苯并三唑-2-基)-4-(3-羟丙基)苯酚]、2,2′-亚甲基双[6-(2H-苯并三唑-2-基)-4-(4-羟丁基)苯酚]、2,2′-亚甲基双[6-(5-氯-2H-苯并三唑-2-基)-4-(4-羟丁基)苯酚]、2,2′-亚甲基双[6-(5-溴-2H-苯并三唑-2-基)-4-(4-羟丁基)苯酚]、3,3-{2,2′-双[6-(2H-苯并三唑-2-基)-1-羟基-4-(2-羟乙基)苯基]}丙烷、2,2-{2,2′-双[6-(2H-苯并三唑-2-基)-1-羟基-4-(2-羟乙基)苯基]}丁烷、2,2′-氧双[6-(2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]、2,2′-双[6-(2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]硫化物、2,2′-双[6-(2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]亚砜、2,2′-双[6-(2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]砜、2,2′-双[6-(2H-苯并三唑-2-基)-4-(2-羟乙基)苯酚]胺、2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚、2-[5-氯(2H)-苯并三唑-2-基]-4-甲基-6-叔丁基苯酚、和2,2′-亚甲基双-[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚等。这些可使用单独一种,也可混合使用两种以上。
作为前述苯并三唑系紫外线吸收剂,可特别优选列举出2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚、2-[5-氯(2H)-苯并三唑-2-基]-4-甲基-6-叔丁基苯酚和2,2′-亚甲基双-[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚等。这些紫外线吸收剂可吸收照射光所含的紫外线中特别可能引起乙烯乙酸乙烯酯共聚物的光劣化的、具有330nm波长的紫外线,可赋予密封膜以优异的抗紫外线性能。
本发明的密封膜所用的受阻胺系光稳定剂,只要为现有的公知的即可使用,并没有特别的限定。
作为低分子量的受阻胺系光稳定剂,可列举出由70重量%癸二酸双(2,2,6,6-四甲基-1(辛氧基)-4-哌啶基)酯、1,1-二甲基乙基过氧化氢与辛烷的反应产物(分子量737)和30重量%聚丙烯所组成的物质;(1,2,2,6,6-五甲基-4-哌啶基)[[3,5-双(1,1-二甲基乙基)-4-羟苯基]甲基]丁基丙二酸酯(分子量685);双(1,2,2,6,6-五甲基-4-哌啶基)癸二酸酯和甲基-1,2,2,6,6-五甲基-4-哌啶基癸二酸酯的混合物(分子量509);双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯(分子量481);四(2,2,6,6-四甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯(分子量791);四(1,2,2,6,6-五甲基-4-哌啶基)-1,2,3,4-丁烷四甲酸酯(分子量847);2,2,6,6-四甲基-4-哌啶基-1,2,3,4-丁烷四甲酸酯和十三烷基-1,2,3,4-丁烷四甲酸酯的混合物(分子量900);1,2,2,6,6-五甲基-4-哌啶基-1,2,3,4-丁烷四甲酸酯和十三烷基-1,2,3,4-丁烷四甲酸酯的混合物(分子量900)等。
作为高分子量的受阻胺系光稳定剂,可列举出聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}-1,6-己二基{(2,2,6,6-四甲基-4-哌啶基)亚氨}](分子量2000~3100);琥珀酸二甲酯与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物(分子量3100~4000);N,N’,N’,N”-四(4,6-双-(丁基-(N-甲基-2,2,6,6-四甲基哌啶基-4-基)氨基)-三嗪-2-基)-4,7-二氮杂癸烷-1,10-二胺(分子量2286)和、上述琥珀酸二甲酯与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物的混合物;以及二丁基胺·1,3,5-三嗪·N,N’-双(2,2,6,6-四甲基-4-哌啶基-1,6-己二胺与N-(2,2,6,6-四甲基-4-哌啶基)丁胺的缩聚物(分子量2600~3400)、和聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}-1,6-己二基{(2,2,6,6-四甲基-4-哌啶基)亚氨}](分子量2000~3100)等。上述受阻胺系光稳定剂可使用单独一种,也可混合使用两种以上。
作为前述受阻胺系光稳定剂,可特别优选列举出双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯和聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}-1,6-己二基{(2,2,6,6-四甲基-4-哌啶基)亚氨}](分子量2000~3100)。它们可与苯并三唑系紫外线吸收剂高度发挥协同效果,可赋予密封膜以优异的抗紫外线性能。
本发明的密封膜还含有有机过氧化物作为交联剂。由此,通过使EVA发生交联,从而可获得粘合性优异的密封膜。作为前述有机过氧化物,可使用任何在100℃以上的温度下分解、产生自由基的物质。有机过氧化物通常通过考虑成膜温度、组合物的制备条件、固化温度、被粘物的耐热性、贮藏稳定性而进行选择。特别优选10小时半衰期的分解温度在70℃以上的有机过氧化物。
前述有机过氧化物从可在长期使用中高度抑制黄变、得到具有优异的抗紫外线性能的密封膜的观点考虑,优选使用过氧化氢系化合物、过氧化二烷基系化合物和过氧化酮系化合物。这些可使用单独一种,也可混合使用两种以上。
作为前述过氧化氢系化合物,可列举出例如萜烷过氧化氢、1,1,3,3-四甲基丁基过氧化氢、枯烯过氧化氢、叔己基过氧化氢等。
作为前述过氧化二烷基系化合物,可列举出例如3-二叔丁基过氧化物、叔丁基-α-枯基过氧化物、二-α-枯基过氧化物、1,4-双((过氧化叔丁基)异丙基)苯、1,3-双((过氧化叔丁基)异丙基)苯、2,5-二甲基-2,5-双(过氧化叔丁基)苯、2,5-二甲基-2,5-双(过氧化叔丁基)己烷、2,5-二甲基-2,5-双(过氧化叔丁基)己炔、α,α′-双(叔丁基过氧化异丙基)苯、正丁基-4,4-双(过氧化叔丁基)丁烷、2,2-双(过氧化叔丁基)丁烷、1,1-双(过氧化叔丁基)-3,3,5-三甲基环己烷等。
作为前述过氧化酮系化合物,可列举出例如过氧化甲乙酮、过氧化甲基异丁基酮、过氧化环己酮、过氧化甲基环己酮等。
其中,从可得到具有优异的抗紫外线性能的太阳能电池用密封膜的观点考虑,特别优选使用过氧化二烷基系化合物、特别是2,5-二甲基-2,5-双(过氧化叔丁基)己烷。
相对于100质量份乙烯乙酸乙烯酯共聚物,前述密封膜中有机过氧化物的含量优选为0.2~1.5质量份,更优选为0.5~1.0质量份。前述有机过氧化物的含量过少时,得到的密封膜的透明性有可能降低,过多时有可能与其他成分的相容性变差、无法得到充分的抗紫外线性能。
本发明的太阳能电池用密封膜使用乙烯乙酸乙烯酯共聚物(EVA)作为有机树脂。还可附属使用聚乙烯醇缩醛系树脂(例如聚乙烯醇缩甲醛、聚乙烯醇缩丁醛(PVB树脂)、改性PVB)、氯乙烯树脂。在此情况下特别优选PVB。
相对于100质量份乙烯乙酸乙烯酯共聚物,上述乙烯乙酸乙烯酯共聚物中乙酸乙烯酯的含量优选为20~35质量份,更优选为20~30质量份,特别优选为24~28质量份。由此可形成具有优异的透明性、且由紫外线照射所引起的EVA劣化低的密封膜。
本发明的太阳能电池用密封膜以提高与发电元件的粘合力为目的,还可含有硅烷偶联剂。作为用于上述目的的硅烷偶联剂,可列举出公知的物质,例如γ-氯丙基三甲氧基硅烷;乙烯基三氯硅烷;乙烯基三乙氧基硅烷;乙烯基三(β-甲氧基乙氧基)硅烷;γ-甲基丙烯酰氧基丙基三甲氧基硅烷;β-(3,4-乙氧基环己基)乙基三甲氧基硅烷;γ-环氧丙氧基丙基三甲氧基硅烷;乙烯基三乙酰氧基硅烷;γ-巯基丙基三甲氧基硅烷;γ-氨基丙基三甲氧基硅烷;N-β-(氨基乙基)-γ-氨基丙基三甲氧基硅烷等。相对于100质量份乙烯乙酸乙烯酯共聚物,这些硅烷偶联剂优选使用5质量份以下,更优选使用0.1~2质量份。
进而,本发明的太阳能电池用密封膜为了提高乙烯乙酸乙烯酯共聚物的凝胶分数以提高耐久性而优选含有交联助剂(作为官能基具有自由基聚合性基的化合物)。作为用于该目的的交联助剂,可列举出公知的三烯丙基氰脲酸酯、三烯丙基异氰脲酸酯等3官能的交联助剂,此外还有(甲基)丙烯酸酯(如NK酯等)的单官能或2官能的交联助剂等。相对于100质量份EVA,这些交联助剂一般使用10质量份以下,优选0.1~5质量份,更优选0.5~3.5质量份。
另外,可以以提高乙烯乙酸乙烯酯共聚物的稳定性为目的,添加氢醌、氢醌单甲醚、对苯醌、甲基氢醌等,相对于100质量份乙烯乙酸乙烯酯共聚物,这些一般在5质量份以下使用。
本发明可根据需要进一步添加着色剂、抗老化剂、防变色剂等。作为着色剂的例子有金属氧化物、金属粉末等无机颜料、偶氮系、酞菁系、偶氮系、酸性或碱性染料系色淀等有机颜料。作为抗老化剂,可列举出胺系、苯酚系、联苯基系。
本发明的太阳能电池用密封膜的厚度通常为20μm~2mm即可。
本发明的太阳能电池用密封膜可通过将含有上述各种成分的组合物进行挤出成形、压延成形等加热压延而成膜等,按常规方法进行制造。另外,还可通过将前述组合物溶解于溶剂,将该溶液用适宜的涂布机(coater)在适宜的支承体上涂布、干燥形成涂膜而可得到片状物。此外,加热温度一般为50~90℃。
太阳能电池中的密封膜为了将单元密封而进行交联固化。本发明的太阳能电池用密封膜即使是为了密封太阳能电池而进行交联固化后,仍具有优异的抗紫外线性能、高度抑制由紫外线照射所导致的黄变、粘合性降低等劣化。进而,还可抑制由于通过添加苯并三唑系紫外线吸收剂和受阻胺系光稳定剂所导致的密封膜的透明性的降低,可长期维持高紫外线吸收性。
即,使本发明的太阳能电池用密封膜进行交联直至凝胶分数达到80~95%,用在295~400nm的紫外线强度为100mW/cm2的紫外线照射50小时后,与玻璃基板的粘合力为13N/cm以上,特别优选为15~25N/cm。
使前述太阳能电池用密封膜进行交联直至凝胶分数达到80~95%,用在295~400nm的紫外线强度为100mW/cm2的紫外线照射50小时后,紫外线照射前后的黄色指数的差(ΔYI)为2.5以下,特别优选为2.0以下,最优选为1.0以下。
进而,前述太阳能电池用密封膜进行交联直至凝胶分数为80~95%,用在295~400nm的紫外线强度为100mW/cm2的紫外线照射50小时后,波长330nm的透光率为5%以下,特别优选为3%以下。
其中,凝胶分数是表示太阳能电池用密封膜的交联的程度的指数。凝胶分数、与玻璃基板的粘合力、黄色指数的差(ΔYI)、和波长330nm的透光率的测定,可使用以下的实施例中所记载的方法来测定。
使用了本发明的太阳能电池用密封膜的太阳能电池的结构,并没有特别的限定,可举出通过在受光面侧透明保护性部件和背面侧保护性部件间隔着前述太阳能电池用密封膜交联一体化,从而密封太阳能电池用单元的结构等。
在前述太阳能电池中,为充分密封太阳能电池用单元,如图1所示,将受光面侧透明保护性部件11、受光面侧密封膜13A、太阳能电池用单元14、背面侧密封膜13B和背面侧保护性部件12层叠,按照加热加压等常规方法对密封膜进行交联固化即可。
为了进行前述加热加压,例如可将前述层叠体用真空层压机在温度135~180℃、进一步优选140~180℃、特别优选155~180℃、脱气时间0.1~5分钟、加压压力0.1~1.5kg/cm2、加压时间5~15分钟进行热压粘即可。该加热加压时,通过使受光面侧密封膜13A及背面侧密封膜13B中含有的乙烯乙酸乙烯酯共聚物交联,隔着受光面侧密封膜13A和背面侧密封膜13B使受光面侧透明保护性部件11、背面侧透明部材12和太阳能电池用单元14一体化,从而可密封太阳能电池用单元14。
在前述太阳能电池中,本发明的密封膜用于受光面侧密封膜或背面侧密封膜的至少一方即可,优选至少用于受光面侧密封膜,特别优选用于受光面侧密封膜和背面侧密封膜的两方。
此外,本发明将太阳能电池单元的受光照射的一侧称为“受光面侧”,将太阳能电池单元的受光面的相反一侧称为“背面侧”。
本发明的太阳能电池所使用的受光面侧透明保护性部件通常可为硅酸盐玻璃等玻璃基板。玻璃基板的厚度一般为0.1~10mm,优选为0.3~5mm。玻璃基板一般可为经过化学或热强化的物质。
本发明所使用的背面侧保护性部件为PET等塑料薄膜。
此外,本发明的太阳能电池如上所述特征在于用于受光面侧和背面侧的密封膜。因此,对于受光面侧透明保护性部件、背面侧保护性部件、和太阳能电池用单元等前述密封膜以外的部件而言,具有与现有公知的太阳能电池同样的结构即可,并没有特别的限定。
实施例
以下通过实施例说明本发明。但本发明不限定于以下实施例。
实施例1
根据表1所示的配方将各材料放入辊磨机、在70℃下混炼,将得到的组合物在70℃下延压成形,自然冷却后,得到太阳能电池用密封膜(厚度0.6mm)。
此外,在表1中若无特别记载,各材料的数值的单位为“质量份”。
实施例2~5和比较例1~6
除如表1所示的改变了紫外线吸收剂的种类和/或添加量以外,与实施例1同样地制作太阳能电池用密封膜。
抗紫外线性能的评价
1.粘合性
(1)紫外线照射
在玻璃基板(厚度3mm)上依次层叠太阳能电池用密封膜和脱模PET薄膜(厚度0.075mm)。将得到的层叠体用真空层压机在真空下、90℃下压粘2分钟后,在温度155℃的条件下加压加热45分钟。从而得到使密封膜交联固化直至凝胶分数达到80%以上的层叠体。
将交联固化后的层叠体,使用将金属卤化物灯作为光源的促进耐侯试验机(IWASAKI ELECTRIC CO.,LTD.制EYESUPER UV TESTER)在温度63℃的气氛下、用在295~400nm的紫外线强度为100mW/cm2的紫外线照射50小时后取出。
(2)粘合力的测定
在紫外线照射后的层叠体中,将太阳能电池用密封膜和玻璃基板之间的一部分剥离,并将剥离的部分折回180°。用拉伸试验机(岛津制作所社制Autograph AG-10KN)测定拉伸速度100mm/分钟的剥离力作为玻璃基板粘合力(N/cm)。结果示于表1。
2.黄色指数和透光率
(1)紫外线照射
用二张玻璃板(厚度3.0mm),按玻璃板/太阳能电池用密封膜/玻璃板的顺序层叠太阳能电池用密封膜。在与上述粘合性的评价相同的条件下,对所得层叠体加热加压,使密封膜交联固化直至凝胶分数达到80%以上。
(2)黄色指数的测定
使用色差计(Colour Computer SM-5-IS-2B Suga TestInstruments Co.,Ltd.制)根据JIS-K-7105-6(1981)标准测定紫外线照射前后的层叠体中密封膜的黄色指数的差(ΔYI)。结果总结示于表1。
(3)透光率的测定
使用分光光度计(岛津制作所社制MPC3100)测定紫外线照射后的层叠体中密封膜的波长330nm的透光率。结果总结并于表1。
3.凝胶分数
凝胶分数的测定,可通过秤量交联固化的太阳能电池用密封膜的重量(Ag),将其在120℃的二甲苯中浸渍24小时,用200目的金属丝网过滤不溶解组分,对金属丝网上的残渣进行真空干燥,测定干燥残渣的重量(Bg),根据下式计算而得到。
数1
凝胶分数[质量%]=(B/A)×100
表1
备注:
*1:相对于100质量份EVA,乙酸乙烯酯的含量为26质量份。
*2:2,5-二甲基-2,5-双(过氧化叔丁基)己烷
*3:2-羟基-4-正辛氧基二苯甲酮
*4:2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚
*5:双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯
通过上述实施例可知,本发明的密封膜即便是在经过长期的紫外线照射后,由于PET粘合力优异、黄色指数小、且可高度吸收具有330nm的波长的紫外线,因此高度抑制了由紫外线照射所导致的劣化。
产业上的适用性
通过本发明的密封膜,即便长期设置于易于受光的影响的室外的严酷环境下,仍可将入射光高效地聚集到太阳能电池用单元内,可实现发电性能优异的太阳能电池。
Claims (9)
1.一种太阳能电池用密封膜,其特征在于:
含有乙烯乙酸乙烯酯共聚物、有机过氧化物、苯并三唑系紫外线吸收剂和受阻胺系光稳定剂,
相对于100质量份所述乙烯乙酸乙烯酯共聚物,所述苯并三唑系紫外线吸收剂的含量为0.01~0.3质量份,
相对于100质量份所述乙烯乙酸乙烯酯共聚物,所述受阻胺系光稳定剂的含量为0.01~2质量份,
相对于100质量份所述乙烯乙酸乙烯酯共聚物,所述苯并三唑系紫外线吸收剂的含量为0.05~0.1质量份。
2.根据权利要求1所述的太阳能电池用密封膜,其特征在于,相对于100质量份所述乙烯乙酸乙烯酯共聚物,所述受阻胺系光稳定剂的含量为0.05~1.5质量份。
3.根据权利要求1所述的太阳能电池用密封膜,其特征在于,所述苯并三唑系紫外线吸收剂与所述受阻胺系光稳定剂的质量比为1∶1~1∶5。
4.根据权利要求1所述的太阳能电池用密封膜,其特征在于,所述苯并三唑系紫外线吸收剂为2-(2H-苯并三唑-2-基)-6-十二烷基-4-甲基苯酚、2-[5-氯(2H)-苯并三唑-2-基]-4-甲基-6-叔丁基苯酚和/或2,2′-亚甲基双-[6-(2H-苯并三唑-2-基)-4-(1,1,3,3-四甲基丁基)苯酚。
5.根据权利要求1所述的太阳能电池用密封膜,其特征在于,所述受阻胺系光稳定剂为双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯和/或聚[{6-(1,1,3,3-四甲基丁基)氨基-1,3,5-三嗪-2,4-二基}{(2,2,6,6-四甲基-4-哌啶基)亚氨基}-1,6-己二基{(2,2,6,6-四甲基-4-哌啶基)亚氨}]。
6.根据权利要求1所述的太阳能电池用密封膜,所述有机过氧化物为选自过氧化氢系化合物、过氧化二烷基系化合物和过氧化酮系化合物组成的组中的至少一种。
7.根据权利要求1所述的太阳能电池用密封膜,其特征在于,相对于100质量份所述乙烯乙酸乙烯酯共聚物,所述有机过氧化物的含量为0.2~1.5质量份。
8.根据权利要求1所述的太阳能电池用密封膜,其特征在于,相对于100质量份所述乙烯乙酸乙烯酯共聚物,所述乙烯乙酸乙烯酯共聚物的乙酸乙烯酯含量为20~35质量份。
9.一种太阳能电池,其特征在于,使用了权利要求1~8任一项所述的太阳能电池用密封膜。
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WO2009069543A1 (ja) | 2009-06-04 |
US8129451B2 (en) | 2012-03-06 |
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