JP5209540B2 - Solar cell sealing sheet and solar cell module - Google Patents
Solar cell sealing sheet and solar cell module Download PDFInfo
- Publication number
- JP5209540B2 JP5209540B2 JP2009044614A JP2009044614A JP5209540B2 JP 5209540 B2 JP5209540 B2 JP 5209540B2 JP 2009044614 A JP2009044614 A JP 2009044614A JP 2009044614 A JP2009044614 A JP 2009044614A JP 5209540 B2 JP5209540 B2 JP 5209540B2
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- Prior art keywords
- layer
- solar cell
- ethylene
- sheet
- copolymer
- Prior art date
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- 238000007789 sealing Methods 0.000 title claims description 50
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- 239000005977 Ethylene Substances 0.000 claims description 64
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- 239000004711 α-olefin Substances 0.000 claims description 55
- 229920000089 Cyclic olefin copolymer Polymers 0.000 claims description 37
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- 238000004132 cross linking Methods 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 15
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
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- 239000000155 melt Substances 0.000 claims description 6
- 239000010410 layer Substances 0.000 description 165
- 230000001681 protective effect Effects 0.000 description 39
- 239000000463 material Substances 0.000 description 38
- 239000011521 glass Substances 0.000 description 25
- 239000000853 adhesive Substances 0.000 description 17
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- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 description 2
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- FETUUKHOLDNMQO-UHFFFAOYSA-N 6-benzoyl-1-hydroxy-3-methoxycyclohexa-2,4-diene-1-carboxylic acid Chemical compound C1=CC(OC)=CC(O)(C(O)=O)C1C(=O)C1=CC=CC=C1 FETUUKHOLDNMQO-UHFFFAOYSA-N 0.000 description 1
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- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 description 1
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- 239000003063 flame retardant Substances 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
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- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
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- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
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- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
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- MQWFLKHKWJMCEN-UHFFFAOYSA-N n'-[3-[dimethoxy(methyl)silyl]propyl]ethane-1,2-diamine Chemical compound CO[Si](C)(OC)CCCNCCN MQWFLKHKWJMCEN-UHFFFAOYSA-N 0.000 description 1
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- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
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- 150000002978 peroxides Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960000969 phenyl salicylate Drugs 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- 239000002685 polymerization catalyst Substances 0.000 description 1
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- 230000002265 prevention Effects 0.000 description 1
- 150000003902 salicylic acid esters Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
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- 229910001220 stainless steel Inorganic materials 0.000 description 1
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- DLSMLZRPNPCXGY-UHFFFAOYSA-N tert-butylperoxy 2-ethylhexyl carbonate Chemical compound CCCCC(CC)COC(=O)OOOC(C)(C)C DLSMLZRPNPCXGY-UHFFFAOYSA-N 0.000 description 1
- CIHOLLKRGTVIJN-UHFFFAOYSA-N tert‐butyl hydroperoxide Chemical compound CC(C)(C)OO CIHOLLKRGTVIJN-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- NZNAAUDJKMURFU-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) butane-1,2,3,4-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 NZNAAUDJKMURFU-UHFFFAOYSA-N 0.000 description 1
- NAQGCFBMSYBDFZ-UHFFFAOYSA-N tetrakis(2,2,6,6-tetramethylpiperidin-4-yl) propane-1,1,2,3-tetracarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(C(=O)OC1CC(C)(C)NC(C)(C)C1)C(=O)OC1CC(C)(C)NC(C)(C)C1 NAQGCFBMSYBDFZ-UHFFFAOYSA-N 0.000 description 1
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- 229910052718 tin Inorganic materials 0.000 description 1
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- 229960001295 tocopherol Drugs 0.000 description 1
- 229930003799 tocopherol Natural products 0.000 description 1
- 235000010384 tocopherol Nutrition 0.000 description 1
- 239000011732 tocopherol Substances 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
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- OIRRCMCATRAYJG-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 1H-triazine-2,4,6-tricarboxylate Chemical compound CC1(NC(CC(C1)OC(=O)N1NC(=CC(=N1)C(=O)OC1CC(NC(C1)(C)C)(C)C)C(=O)OC1CC(NC(C1)(C)C)(C)C)(C)C)C OIRRCMCATRAYJG-UHFFFAOYSA-N 0.000 description 1
- DYSUTBVWFJRUKW-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 2-acetyloxypropane-1,2,3-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(C(=O)OC1CC(C)(C)NC(C)(C)C1)(OC(=O)C)CC(=O)OC1CC(C)(C)NC(C)(C)C1 DYSUTBVWFJRUKW-UHFFFAOYSA-N 0.000 description 1
- HBUNLJQRZABWAM-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) 2-hydroxypropane-1,2,3-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)CC(O)(C(=O)OC1CC(C)(C)NC(C)(C)C1)CC(=O)OC1CC(C)(C)NC(C)(C)C1 HBUNLJQRZABWAM-UHFFFAOYSA-N 0.000 description 1
- HAJIOQHUJLPSAL-UHFFFAOYSA-N tris(2,2,6,6-tetramethylpiperidin-4-yl) benzene-1,3,5-tricarboxylate Chemical compound C1C(C)(C)NC(C)(C)CC1OC(=O)C1=CC(C(=O)OC2CC(C)(C)NC(C)(C)C2)=CC(C(=O)OC2CC(C)(C)NC(C)(C)C2)=C1 HAJIOQHUJLPSAL-UHFFFAOYSA-N 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
- GVJHHUAWPYXKBD-IEOSBIPESA-N α-tocopherol Chemical compound OC1=C(C)C(C)=C2O[C@@](CCC[C@H](C)CCC[C@H](C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-IEOSBIPESA-N 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
- Photovoltaic Devices (AREA)
Description
本発明は、太陽電池モジュールにおける太陽電池素子を固定するための太陽電池封止用シート、及び該太陽電池封止用シートにより太陽電池素子が封止された太陽電池モジュールに関する。 The present invention relates to a solar cell sealing sheet for fixing a solar cell element in a solar cell module, and a solar cell module in which a solar cell element is sealed with the solar cell sealing sheet.
近年の環境問題の高まりを背景に、クリーンなエネルギーとして水力発電、風力発電、並びに太陽光発電が脚光を浴びている。このうち、太陽光発電は、太陽電池モジュールの発電効率等の性能向上が著しい一方、価格の低下が進んだこと、国や自治体が住宅用太陽光発電システム導入促進事業を進めてきたことから、ここ数年その普及が著しく進んでいる。 Against the background of increasing environmental problems in recent years, hydroelectric power generation, wind power generation, and solar power generation are attracting attention as clean energy. Of these, solar power generation has seen significant improvements in performance, such as power generation efficiency of solar cell modules, while price declines have progressed, and national and local governments have promoted the introduction of residential solar power generation systems. The spread has been remarkable in recent years.
太陽光発電は、シリコンセル等半導体（太陽電池素子）を用いて太陽光エネルギーを直接電気エネルギーに変換するが、ここで用いられている太陽電池素子は直接外気と接触するとその機能が低下するため、一般に太陽電池素子を封止材ないし保護膜で挟み、緩衝とともに、異物の混入や水分等の侵入を防いでいる。 Photovoltaic power generation directly converts solar energy into electrical energy using a semiconductor (solar cell element) such as a silicon cell, but the function of the solar cell element used here is reduced when it directly contacts the outside air. In general, a solar cell element is sandwiched between a sealing material or a protective film, and together with buffering, foreign matter and moisture are prevented from entering.
太陽電池素子を封止する封止用シートとしては、透明性、柔軟性、加工性、耐久性の面から酢酸ビニル含有量が２５〜３３質量％のエチレン・酢酸ビニル共重合体の架橋物の使用が一般的である（例えば、特許文献１参照）。
ところが、エチレン・酢酸ビニル共重合体は、酢酸ビニル含有量が高い場合、その透湿性が高くなり、それに伴い太陽光が入射する上部透明保護材やバックシート等の種類や接着条件等によっては上部透明保護材やバックシートに対する接着性が低下することがある。そのため、バリア性の高いバックシートを使用し、また、モジュール周囲の封止をバリア性の高いブチルゴムでシーリングをして防湿に努めているが、太陽電池の普及に伴い、年々高い耐久性（接着性等の性能維持）が求められるようになってきており、よりレベルの高い対策が求められている。 However, when the vinyl acetate content is high, the ethylene / vinyl acetate copolymer has a high moisture permeability, and the upper transparent protective material or backsheet to which sunlight is incident is accompanied by the upper part depending on the type and bonding conditions. Adhesiveness to the transparent protective material or the back sheet may be reduced. For this reason, a back sheet with a high barrier property is used, and sealing around the module is sealed with a butyl rubber with a high barrier property to prevent moisture. However, with the widespread use of solar cells, the durability (adhesion) has been increasing year by year. Maintenance of performance such as performance) has been required, and higher level countermeasures are required.
本発明は、上記の課題を解決するために成されたものである。即ち、
本発明の目的は、エチレン酢酸ビニル共重合体が持つ優れた柔軟性、加工性、耐久性、架橋性等を生かしつつ、しかも酢酸ビニルの比率の比較的高いエチレン・酢酸ビニル共重合体を用いた場合でも、従来の太陽電池封止用シートに比べ、保護材（太陽光入射側の上部保護材及び太陽電池素子を介して上部保護材の逆側に配された下部保護材の双方）に対する接着性及び接着安定性が大幅に向上した太陽電池封止用シート、及び耐久性に優れ、電池性能がより安定した太陽電池モジュールを提供することにある。
The present invention has been made to solve the above problems. That is,
An object of the present invention is to use an ethylene / vinyl acetate copolymer having a relatively high vinyl acetate ratio while taking advantage of the excellent flexibility, processability, durability, crosslinkability, etc. of the ethylene vinyl acetate copolymer. Even in the case of the conventional solar cell sealing sheet, the protective material (both the upper protective material on the sunlight incident side and the lower protective material arranged on the opposite side of the upper protective material via the solar cell element) An object of the present invention is to provide a solar cell sealing sheet with greatly improved adhesion and adhesion stability, and a solar cell module with excellent durability and more stable battery performance.
前記課題を達成するための具体的手段は以下の通りである。即ち、本発明は、
＜１＞ 酢酸ビニルに由来の構成単位の含有量が５〜４０質量％のエチレン・酢酸ビニル共重合体を主成分に含む（Ａ）層と、エチレン由来の構成単位と炭素数３〜２０のα−オレフィン由来の構成単位とを含み、エチレン由来の構成単位含量が５０〜９０モル％、かつ炭素数３〜２０のα−オレフィン由来の構成単位含量が５０〜１０モル％であり、Ｘ線による結晶化度が４０％以下である非晶性又は低結晶性のエチレン・α−オレフィン系共重合体を主成分に含む（Ｂ）層と、の少なくとも２層を含み、
前記エチレン・酢酸ビニル共重合体及び前記エチレン・α−オレフィン系共重合体のメルトフローレート（ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重）が、それぞれ０．１〜１５０ｇ／１０分の範囲にあり、
前記（Ａ）層の厚みと前記（Ｂ）層の厚みとの比率［（Ａ）／（Ｂ）］が９／１〜１／９である架橋性積層シートを有する太陽電池封止用シートである。
Specific means for achieving the above object are as follows. That is, the present invention
<1> (A) layer containing ethylene / vinyl acetate copolymer having 5 to 40% by mass of a constituent unit derived from vinyl acetate as a main component, a constituent unit derived from ethylene and 3 to 20 carbon atoms a structural unit content derived from ethylene, the structural unit content derived from ethylene is 50 to 90 mol%, and the structural unit content derived from an α-olefin having 3 to 20 carbon atoms is 50 to 10 mol%, and X-ray And (B) layer containing an amorphous or low crystalline ethylene / α-olefin copolymer as a main component having a crystallinity by 40% or less , and at least two layers,
The melt flow rate (JIS K7210-1999, 190 ° C., 2160 g load) of the ethylene / vinyl acetate copolymer and the ethylene / α-olefin copolymer is in the range of 0.1 to 150 g / 10 min. ,
The ratio of the thickness of the the thickness of the (A) layer (B) layer [(A) / (B)] sheet for sealing a solar cell having a 9 / 1-1 / 9 der Ru crosslinkable laminated sheet It is.
＜２＞ 前記＜１＞に記載の太陽電池封止用シートにおいては、エチレン・酢酸ビニル共重合体を主成分に含む（Ａ）層及び非晶性又は低結晶性のα−オレフィン系共重合体を主成分に含む（Ｂ）層はそれぞれ、架橋剤、架橋助剤、シランカップリング剤、紫外線吸収剤、光安定剤、及び酸化防止剤から選ばれる１種以上の添加剤が配合されてなることが好ましい。 < 2 > In the solar cell sealing sheet according to <1 >, the (A) layer containing an ethylene / vinyl acetate copolymer as a main component and an amorphous or low-crystalline α-olefin copolymer weight Each of the layers (B) containing the coalescence as a main component is blended with one or more additives selected from a crosslinking agent, a crosslinking aid, a silane coupling agent, an ultraviolet absorber, a light stabilizer, and an antioxidant. It is preferable to become.
＜３＞ 前記＜１＞又は前記＜２＞に記載の太陽電池封止用シートにおいては、エチレン・酢酸ビニル共重合体を主成分に含む層（Ａ）及び非晶性又は低結晶性のα−オレフィン系共重合体を主成分に含む（Ｂ）層の少なくとも一方のゲル分率（対象層（試料）１ｇをキシレン１００ｍｌに浸漬し、１１０℃で２４時間加熱後、２０メッシュ金網で濾過したときの未溶解分の質量分率［％］）が、それぞれ７０％以上であることが好ましい。 < 3 > In the solar cell sealing sheet according to <1> or <2>, the layer (A) containing an ethylene / vinyl acetate copolymer as a main component and an amorphous or low-crystalline α -Gel fraction of at least one of the layer (B) containing the olefin copolymer as a main component (1 g of the target layer (sample) was immersed in 100 ml of xylene, heated at 110 ° C for 24 hours, and then filtered through a 20 mesh wire mesh. The mass fraction [%] of the undissolved portion is preferably 70% or more.
＜４＞ 前記＜１＞〜前記＜３＞のいずれか１つに記載の太陽電池封止用シートを備えた太陽電池モジュールである。 < 4 > A solar cell module comprising the solar cell sealing sheet according to any one of <1> to < 3 >.
本発明によれば、従来から使用されているエチレン・酢酸ビニル共重合体からなる太陽電池封止用シートの特性である優れた柔軟性、加工性、耐候性、架橋特性などを維持したまま、保護材（太陽光入射側の上部保護材及び太陽電池素子を介して上部保護材の逆側に配された下部保護材の双方）との間の接着性及び接着安定性（例えば、ガラス、又はポリエステル、アクリル樹脂、ポリカーボネートなどの樹脂製のバックシートとの間の接着性及び接着安定性）が、従来の太陽電池封止用シートに比べて大幅に向上した封止材用シートを提供することができる。また、
本発明によれば、耐久性に優れ、電池性能がより安定した太陽電池モジュールを提供することができる。
According to the present invention, while maintaining excellent flexibility, workability, weather resistance, cross-linking characteristics, etc., which are characteristics of a sheet for sealing a solar cell made of an ethylene / vinyl acetate copolymer, which has been conventionally used, Adhesiveness and adhesion stability between the protective material (both the upper protective material on the sunlight incident side and the lower protective material arranged on the opposite side of the upper protective material via the solar cell element) (for example, glass, or To provide a sheet for encapsulating material in which adhesion and adhesion stability with a back sheet made of resin such as polyester, acrylic resin, polycarbonate, etc. are significantly improved as compared with conventional solar cell encapsulating sheets. Can do. Also,
According to the present invention, it is possible to provide a solar cell module having excellent durability and more stable battery performance.
本発明の太陽電池封止用シートは、酢酸ビニルに由来の構成単位の含有量（共重合比）が５〜４０質量％のエチレン・酢酸ビニル共重合体を主成分に含む（Ａ）層（以下、単に「（Ａ）層」という場合がある。）と、エチレン由来の構成単位と炭素数３〜２０のα−オレフィン由来の構成単位とを含み、エチレン由来の構成単位含量が５０〜９０モル％、かつ炭素数３〜２０のα−オレフィン由来の構成単位含量が５０〜１０モル％であり、Ｘ線による結晶化度が４０％以下である非晶性又は低結晶性のエチレン・α−オレフィン系共重合体を主成分に含む（Ｂ）層（以下、単に「（Ｂ）層」という場合がある。）と、の少なくとも２層を含み、
前記エチレン・酢酸ビニル共重合体及び前記エチレン・α−オレフィン系共重合体のメルトフローレート（ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重）を、それぞれ０．１〜１５０ｇ／１０分の範囲とし、（Ａ）層の厚みと（Ｂ）層の厚みとの比率［（Ａ）／（Ｂ）］を９／１〜１／９とする。また、（Ａ）層及び（Ｂ）層の全体の厚みは０．２〜２ｍｍの範囲にあることが好ましい。
The solar cell sealing sheet of the present invention includes an ethylene / vinyl acetate copolymer having a content (copolymerization ratio) of a structural unit derived from vinyl acetate of 5 to 40% by mass as a main component (A) layer ( Hereinafter, it may be simply referred to as “(A) layer”), a structural unit derived from ethylene and a structural unit derived from an α-olefin having 3 to 20 carbon atoms, and the content of the structural unit derived from ethylene is 50 to 90. Amorphous and low-crystalline ethylene / α having a constituent unit content derived from an α-olefin of 50 to 10 mol% and a crystallinity by X-ray of 40% or less. -(B) layer containing an olefin copolymer as a main component (hereinafter sometimes referred to simply as "(B) layer") , and at least two layers,
The melt flow rate (JIS K7210-1999, 190 ° C., 2160 g load) of the ethylene / vinyl acetate copolymer and the ethylene / α-olefin copolymer is in the range of 0.1 to 150 g / 10 min, the ratio between the thickness of the (a) and the thickness of the layer (B) layer [(a) / (B)] shall be the 9 / 1-1 / 9. Moreover, it is preferable that the whole thickness of (A) layer and (B) layer exists in the range of 0.2-2 mm.
太陽電池封止用シートとしては、（Ａ）層と（Ｂ）層とからなる２層構造の積層体〔（Ａ）層／（Ｂ）層〕、あるいは（Ａ）層を中間層とし、その両側にそれぞれ（Ａ）層に隣接して外層として（Ｂ）層を設けてなる（Ｂ）層／（Ａ）層／（Ｂ）層の３層構造の積層体から構成されることが好ましい。このうち、太陽光が入射する側の上部保護材及び太陽電池素子を介して上部保護材と逆側に配される下部保護材との接着性及びその安定性の面から、特に、エチレン・酢酸ビニル共重合体を主成分に含む（Ａ）層を中間層とし、その両面に外層として「非晶性又は低結晶性のα−オレフィン系共重合体を主成分に含む（Ｂ）層」を設けてなる３層から構成されることが好ましい。 As a solar cell sealing sheet, a laminate of (A) layer and (B) layer ([A) layer / (B) layer] or (A) layer is used as an intermediate layer. It is preferable to be composed of a laminate of a three-layer structure of (B) layer / (A) layer / (B) layer in which (B) layer is provided as an outer layer adjacent to (A) layer on both sides. Among these, in view of the adhesion and stability of the upper protective material on the side where sunlight enters and the lower protective material disposed on the opposite side to the upper protective material via the solar cell element, ethylene / acetic acid is particularly preferred. The (A) layer containing a vinyl copolymer as a main component is an intermediate layer, and “B (layer) containing an amorphous or low-crystalline α-olefin copolymer as a main component” is used as an outer layer on both sides. It is preferable to be composed of three layers.
本発明においては、（Ａ）層の両側に（Ａ）層に隣接して外層として（Ｂ）層が設けられた上記の３層構成のシートの場合、両外層の（Ｂ）層は、非晶性又は低結晶性のα−オレフィン系共重合体を主成分に含む（Ｂ）層であれば、その共重合体の種類、組成、配合組成、厚み等は同一であってもよく、また異なっていてもよい。
また、本発明においては（Ａ）層は、単一層であることが好ましいが、エチレン・酢酸ビニル共重合体の重合組成、物性あるいは配合組成などの異なる複数のエチレン・酢酸ビニル共重合体を主成分とした層からなる多層構成になっていてもよい。
例えば、前記（Ａ）層／（Ｂ）層の２層構造又は前記（Ｂ）層／（Ａ）層／（Ｂ）層の３層構造を含む４層構造以上であってもよく、例えば、（Ａ）層／（Ｂ）層／（Ａ）層／（Ｂ）層の４層構造や、（Ｂ）層／（Ａ）層／（Ｂ）層／（Ａ）層／（Ｂ）層の５層構造などに構成されてもよい。
In the present invention, in the case of the above-mentioned three-layered sheet in which the (B) layer is provided as an outer layer adjacent to the (A) layer on both sides of the (A) layer, the (B) layers of both outer layers are non- As long as it is a layer (B) containing a crystalline or low crystalline α-olefin copolymer as a main component, the type, composition, blending composition, thickness, etc. of the copolymer may be the same. May be different.
In the present invention, the layer (A) is preferably a single layer, but it is mainly composed of a plurality of ethylene / vinyl acetate copolymers having different polymerization compositions, physical properties or blending compositions of the ethylene / vinyl acetate copolymers. It may have a multilayer structure composed of layers as components.
For example, it may be a two-layer structure of (A) layer / (B) layer or a four-layer structure or more including a three-layer structure of (B) layer / (A) layer / (B) layer. (A) layer / (B) layer / (A) layer / (B) layer, or (B) layer / (A) layer / (B) layer / (A) layer / (B) layer A five-layer structure or the like may be used.
前記（Ａ）層及び前記（Ｂ）層において、「主成分」とは、各層の全質量に対して、６０質量％以上（６０〜１００質量％）であることをいう。 In the (A) layer and the (B) layer, the “main component” means 60 mass% or more (60 to 100 mass%) with respect to the total mass of each layer.
前記（Ａ）層には、少量（例えば、エチレン・酢酸ビニル共重合体に対して５０質量％以下）であれば、エチレン・（メタ）アクリル酸エステル共重合体が含まれてもよい。 The layer (A) may contain an ethylene / (meth) acrylate copolymer as long as it is a small amount (for example, 50% by mass or less based on the ethylene / vinyl acetate copolymer).
本発明において、（Ａ）層に主成分として用いるエチレン・酢酸ビニル共重合体を構成する酢酸ビニル由来の構成単位の含有量は、５〜４０質量％であり、好ましくは１５〜４０質量％、特に好ましくは１８〜３５質量％である。酢酸ビニル由来の構成単位の含有量が５質量％を下回るものを使用すると、太陽電池封止用シートの柔軟性が低下するので好ましくない。また、酢酸ビニル由来の構成単位の含有量が４０質量％を上回るものを使用すると、太陽電池封止用シートのベタツキが顕著となり、著しく加工性を損ない、また、保護材（特に上部保護材（中でもガラス）及び下部保護材）に対する接着性も低下するので好ましくない。また、本発明において、酢酸ビニル由来の構成単位の含有量が５質量％以上のエチレン・酢酸ビニル共重合体を用いると、太陽電池封止用シートの透明性が大幅に向上するので、透明性の観点からは酢酸ビニル由来の構成単位の含有量が１５質量％以上のものを使用するのが好ましい。 In this invention, content of the structural unit derived from the vinyl acetate which comprises the ethylene-vinyl acetate copolymer used as a main component for (A) layer is 5-40 mass%, Preferably it is 15-40 mass%, Most preferably, it is 18-35 mass%. If the content of the structural unit derived from vinyl acetate is less than 5% by mass, the flexibility of the solar cell sealing sheet is unfavorable. Moreover, when the content of the structural unit derived from vinyl acetate exceeds 40% by mass, the sticking of the solar cell sealing sheet becomes remarkable, the workability is remarkably impaired, and the protective material (particularly the upper protective material ( Among them, the adhesiveness to glass) and the lower protective material) is also lowered, which is not preferable. In the present invention, when an ethylene / vinyl acetate copolymer having a vinyl acetate-derived constituent unit content of 5% by mass or more is used, the transparency of the solar cell sealing sheet is greatly improved. From this viewpoint, it is preferable to use a vinyl acetate-derived structural unit having a content of 15% by mass or more.
また、エチレン・酢酸ビニル共重合体の１９０℃、２１６０ｇ荷重におけるメルトフローレート（ＪＩＳ Ｋ７２１０−１９９９に準拠）は、加工性及び機械強度の点から、０．１〜１５０ｇ／１０分の範囲にあることが好ましく、０．３〜１００ｇ／１０分の範囲がより好ましい。 In addition, the melt flow rate (based on JIS K7210-1999) of the ethylene / vinyl acetate copolymer at 190 ° C. and a load of 2160 g is in the range of 0.1 to 150 g / 10 minutes from the viewpoint of workability and mechanical strength. The range of 0.3 to 100 g / 10 min is more preferable.
次に、（Ｂ）層に主成分として使用される、非晶性又は低結晶性のエチレン・α−オレフィン系共重合体（以下、単に「α−オレフィン系共重合体」ともいう。）について説明する。
非結晶性又は低結晶性のα−オレフィン系共重合体としては、２種以上のα−オレフィンの共重合体、あるいはα−オレフィンと他のモノマーとの共重合体などが含まれる。
ここで、非晶性とは、結晶性を有しない、すなわち示差走査熱量測定により明確な融点ピークが認められないことをいい、また、低結晶性とは、結晶化度が４０％以下であることをいう。なお、結晶化度については後述する。
Next, an amorphous or low crystalline ethylene / α-olefin copolymer (hereinafter, also simply referred to as “α-olefin copolymer”) used as a main component in the layer (B). explain.
Examples of the amorphous or low crystalline α-olefin copolymer include copolymers of two or more α-olefins, copolymers of α-olefins and other monomers, and the like.
Here, the term “amorphous” means that there is no crystallinity, that is, a clear melting point peak is not recognized by differential scanning calorimetry, and low crystallinity means that the crystallinity is 40% or less. That means. The crystallinity will be described later.
本発明における非結晶性又は低結晶性のエチレン・α−オレフィン系共重合体は、下記要件（ａ）〜（ｂ）を満たす。
（ａ）炭素数３〜２０のα−オレフィンに由来する構成単位が１０モル％以上である。
（ｂ）Ｘ線解析による結晶化度が４０％以下である。
Amorphous or low-crystalline ethylene · alpha-olefin copolymer in the present invention, satisfying the following requirements (a) ~ (b).
(A) The structural unit derived from a C3-C20 alpha olefin is 10 mol% or more.
(B) Crystallinity by X-ray analysis is 40% or less.
非結晶性又は低結晶性のα−オレフィン系共重合体において、該共重合体を構成する全構成単位（単量体単位）の含有量を１００モル％としたとき、炭素原子数が３〜２０のα−オレフィンに由来する構成単位の含有量は、１０モル％以上であり、より好ましくは１５モル％以上の重合体である。α−オレフィン由来の構成単位の含有割合が前記範囲内であると、透明性、耐ブリード性が良好である。特に透明性を考慮すると、１５モル％以上の重合体を使用するのが好ましい。 In the non-crystalline or low-crystalline α-olefin copolymer, when the content of all the structural units (monomer units) constituting the copolymer is 100 mol%, the number of carbon atoms is 3 to 3. the content of the repeating unit derived from a 20 α- olefin is 10 mol% or more, more preferably 15 mol% or more of the polymers. When the content ratio of the constituent unit derived from α-olefin is within the above range, transparency and bleed resistance are good. Considering the transparency in particular, it is preferable to use a polymer of 15 mol% or more.
前記炭素数３〜２０のα−オレフィンの具体例としては、プロピレン、１−ブテン、１−ペンテン、１−ヘキセン、１−へプテン、１−オクテン、１−ノネン、１−デセン、１−ウンデセン、１−ドデセン、１−トリデセン、１−テトラデセン、１−ペンタデセン、１−ヘキサデセン、１−ヘプタデセン、１−オクタデセン、１−ナノデセン、１−エイコセン等の直鎖状のα−オレフィン；３−メチル−１−ブテン、３−メチル−１−ペンテン、４−メチル−１−ペンテン、２−エチル−１−ヘキセン、２，２，４−トリメチル−１−ペンテン等の分岐状のα−オレフィンなどが例示され、これらは２種類を組み合わせて使用することもできる。
中でも、α−オレフィンの炭素数は、汎用性（コストや量産性）の点で、３〜１０が好ましく、更には３〜８が好ましい。
Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. , 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nanodecene, 1-eicosene and the like linear α-olefins; 3-methyl- Examples include branched α-olefins such as 1-butene, 3-methyl-1-pentene, 4-methyl-1-pentene, 2-ethyl-1-hexene, and 2,2,4-trimethyl-1-pentene. These can also be used in combination of two types.
Among these, the number of carbon atoms of the α-olefin is preferably 3 to 10 and more preferably 3 to 8 in terms of versatility (cost and mass productivity).
非結晶性又は低結晶性のα−オレフィン系共重合体としては、好ましくは、エチレン・プロピレン共重合体（エチレン由来の構成単位含量が５０モル％以上のエチレン・プロピレン共重合体を意味する）、エチレン・１−ブテン共重合体（エチレン由来の構成単位含量が５０モル％以上のエチレン・１−ブテン共重合体を意味する）プロピレン・エチレン共重合体（プロピレン由来の構成単位含量が５０モル％以上のプロピレン・エチレン共重合体を意味する）、プロピレン・１−ブテン共重合体（プロピレン由来の構成単位含量が５０モル％以上のプロピレン・１−ブテン共重合体を意味する）、プロピレン・プロピレン以外のα−オレフィンとエチレンとの共重合体、エチレン及びプロピレン以外のα−オレフィンとプロピレンとエチレンとの共重合体、プロピレン・１−ヘキセン共重合体であり、より好ましくは、エチレン・プロピレン共重合体、エチレン・１−ブテン共重合体、プロピレン・１−ブテン共重合体、プロピレン・１−ヘキセン共重合体、プロピレン・エチレン・１−ブテン共重合体、プロピレン・エチレン・１−ヘキセン共重合体であり、さらに好ましくは、エチレン・プロピレン共重合体、エチレン・１−ブテン共重合体、プロピレン・１−ブテン共重合体 であり、特に好ましくは、エチレン・プロピレン共重合体、エチレン・１−ブテン共重合体であり、最も好ましくはエチレン・プロピレン共重合体である。 The non-crystalline or low crystalline α-olefin copolymer is preferably an ethylene / propylene copolymer (meaning an ethylene / propylene copolymer having an ethylene-derived constituent unit content of 50 mol% or more). , Ethylene / 1-butene copolymer (meaning an ethylene / 1-butene copolymer having an ethylene-derived constituent unit content of 50 mol% or more) propylene / ethylene copolymer (propylene-derived constituent unit content of 50 mol) % Propylene / ethylene copolymer), propylene / 1-butene copolymer (meaning propylene / 1-butene copolymer having a propylene-derived constituent unit content of 50 mol% or more), propylene / Copolymer of α-olefin other than propylene and ethylene, α-olefin other than ethylene and propylene, propylene and ethylene Copolymer, propylene / 1-hexene copolymer, more preferably ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 1-butene copolymer, propylene / 1-hexene. Copolymer, propylene / ethylene / 1-butene copolymer, propylene / ethylene / 1-hexene copolymer, more preferably ethylene / propylene copolymer, ethylene / 1-butene copolymer, propylene / 1-butene copolymer, particularly preferably ethylene / propylene copolymer and ethylene / 1-butene copolymer, and most preferably ethylene / propylene copolymer.
太陽電池封止用シートにおいて、前記α−オレフィン系共重合体は、１種単独で用いてもよく、２種以上組み合わせて用いてもよい。 In the solar cell sealing sheet, the α-olefin-based copolymer may be used alone or in combination of two or more.
非結晶性又は低結晶性のα−オレフィン系共重合体は、エチレンを主成分として共重合成分に含むエチレン系共重合体であり、エチレン由来の構成単位含量が５０〜９０モル％、特に好ましくは７０〜９０モル％であって、炭素原子数が３〜２０のα−オレフィン由来の構成単位含量が５０〜１０モル％、特に好ましくは３０〜１０モル％であるエチレン・α−オレフィン共重合体である。 The non-crystalline or low-crystalline α-olefin copolymer is an ethylene copolymer containing ethylene as a main component in the copolymer component , and the ethylene-derived constituent unit content is particularly preferably 50 to 90 mol%. Is an ethylene / α-olefin copolymer whose content of constituent units derived from α-olefin having 3 to 20 carbon atoms is 50 to 10 mol%, particularly preferably 30 to 10 mol%. It is a coalescence.
非結晶性又は低結晶性のα−オレフィン系共重合体は、Ｘ線による結晶化度が４０％以下（０〜４０％）である。結晶化度が４０％以下のものは、透明性に優れる。中でも、結晶化度は、２０％以下（０〜２０％）が好ましい。 The non-crystalline or low crystalline α-olefin copolymer has a crystallinity by X- ray of 40% or less (0 to 40%). Those having a crystallinity of 40% or less are excellent in transparency. Among them, the crystallinity is preferably 20% or less (0 to 20%).
Ｘ線解析による結晶化度は、Ｘ線回折を利用したＸ線回折装置（型式：ＸＲＤ−７０００、（株）島津製作所製）を用いて測定される値である。 The crystallinity by X-ray analysis is a value measured using an X-ray diffractometer (model: XRD-7000, manufactured by Shimadzu Corporation) using X-ray diffraction.
上記のうち、前記非結晶性又は低結晶性のα−オレフィン系共重合体は、透明性の点で、（ａ）炭素数３〜１０のα−オレフィンに由来する構成単位が２０モル％以上（２０〜１００％）であって、かつ（ｂ）Ｘ線解析による結晶化度が０〜２０％であるα−オレフィン系共重合体が好ましい。 Among the above, the non-crystalline or low-crystalline α-olefin copolymer is (a) 20 mol% or more of structural units derived from an α-olefin having 3 to 10 carbon atoms in terms of transparency. An α-olefin copolymer that is (20 to 100%) and (b) has a crystallinity of 0 to 20% by X-ray analysis is preferable.
上記のような性状の非結晶性又は低結晶性のα−オレフィン系共重合体は、メタロセン系触媒を用いた、スラリー重合法、溶液重合法、塊状重合法、気相重合法等で製造できる。該触媒としては、例えば、特開昭５８−１９３０９号公報、特開昭６０−３５００５号公報、特開昭６０−３５００６号公報、特開昭６０−３５００７号公報、特開昭６０−３５００８号公報、特開昭６１−１３０３１４号公報、特開平３−１６３０８８号公報、特開平４−２６８３０７号公報、特開平９−１２７９０号公報、特開平９−８７３１３号公報、特開平１０−５０８０５５号公報、特開平１１−８０２３３号公報、特表平１０−５０８０５５号公報などに記載のメタロセン系触媒を例示することができる。また、メタロセン触媒を用いた製造方法の特に好ましい例として、欧州特許出願公開第１２１１２８７号明細書の方法を例示することができる。 The non-crystalline or low-crystalline α-olefin copolymer having the above properties can be produced by a slurry polymerization method, a solution polymerization method, a bulk polymerization method, a gas phase polymerization method or the like using a metallocene catalyst. . Examples of the catalyst include JP-A-58-19309, JP-A-60-35005, JP-A-60-35006, JP-A-60-35007, and JP-A-60-35008. Japanese Patent Laid-Open Nos. 61-130314, 3-163088, 4-268307, 9-12790, 9-87313, 10-5008055 Examples thereof include metallocene catalysts described in JP-A-11-80233 and JP-T-10-508055. Further, as a particularly preferred example of the production method using a metallocene catalyst, the method of EP-A-1211287 can be exemplified.
非結晶性又は低結晶性のα−オレフィン系共重合体は、メタロセン系触媒だけでなく、エチレンを主成分とする共重合体の場合は、可溶性バナジウム化合物と有機アルミニウムハライドとからなるバナジウム系触媒、あるいはシクロペンタジエニル基等が配位したジルコニウム化合物等のメタロセン化合物と有機アルミニウムオキシ化合物とからなるメタロセン系触媒の存在下に、エチレン及びその他α−オレフィン類を共重合させることによって製造することもできる。また、プロピレンを主成分とする共重合体の場合は、高活性チタン触媒成分あるいはメタロセン系触媒成分などの遷移金属化合物成分、有機アルミニウム成分、必要に応じて電子供与体、担体等を含む立体規則性オレフィン重合触媒の存在下に、プロピレンと他のα−オレフィンを共重合させることによって製造することもできる。 The non-crystalline or low-crystalline α-olefin copolymer is not only a metallocene catalyst, but in the case of a copolymer mainly composed of ethylene, a vanadium catalyst comprising a soluble vanadium compound and an organoaluminum halide. Or by copolymerizing ethylene and other α-olefins in the presence of a metallocene catalyst comprising a metallocene compound such as a zirconium compound coordinated with a cyclopentadienyl group and the like and an organoaluminum oxy compound. You can also. In the case of a copolymer mainly composed of propylene, a steric rule containing a transition metal compound component such as a highly active titanium catalyst component or a metallocene catalyst component, an organoaluminum component, and an electron donor, a carrier, etc. as necessary It can also be produced by copolymerizing propylene and another α-olefin in the presence of a hydrophilic olefin polymerization catalyst.
非結晶性又は低結晶性のα−オレフィン系共重合体としては、成形性、機械的強度などを考慮すると、ＡＳＴＭ Ｄ−１２３８に準拠し、２３０℃、２１６０ｇ荷重下で測定したメルトフローレート（ＭＦＲ）が、０．１〜１５０ｇ／１０分、特に０．５〜２０ｇ／１０分のものを使用するのが好ましい。 As the non-crystalline or low-crystalline α-olefin copolymer, in consideration of moldability, mechanical strength, and the like, a melt flow rate (measured at 230 ° C. under a load of 2160 g according to ASTM D-1238) ( MFR) is preferably from 0.1 to 150 g / 10 min, in particular from 0.5 to 20 g / 10 min.
本発明においては、エチレン・酢酸ビニル共重合体を主成分に含む（Ａ）層と、非晶性又は低結晶性のα−オレフィン系共重合体を主成分に含む（Ｂ）層とを設けて形成される太陽電池封止用シートの総厚を、実用性の観点から、０．１〜２ｍｍの範囲とすることが好ましい。 In the present invention, the (A) layer containing an ethylene / vinyl acetate copolymer as a main component and the (B) layer containing an amorphous or low-crystalline α-olefin copolymer as a main component are provided. From the viewpoint of practicality, it is preferable that the total thickness of the solar cell sealing sheet formed in a range of 0.1 to 2 mm.
本発明の太陽電池封止用シートにおいては、（Ａ）層の合計厚みと（Ｂ）層の合計厚みとの比率［（Ａ）層合計厚み／（Ｂ）層合計厚み］が、９／１〜１／９であり、より好ましくは８／２〜２／８の範囲である。こうした特定の積層比率とすることにより、接着性及びその安定性に優れ、しかも透明性、柔軟性、架橋性等に優れた太陽電池封止用シートを容易に得ることができる。
具体的には上記のように、（Ａ）層／（Ｂ）層からなる２層構造の積層体である場合、（Ａ）層の厚みと（Ｂ）層の厚みとの比率［(A)／(B)］を上記範囲とする。
In the solar cell sealing sheet of the present invention, the ratio of the total thickness of the (A) layer and the total thickness of the (B) layer [(A) total layer thickness / (B) total layer thickness] is 9/1. ~ 1/9 der is, more preferably in the range of 8/2 to 2/8. By setting it as such a specific lamination | stacking ratio, the sheet | seat for solar cell sealing excellent in adhesiveness and its stability, and excellent in transparency, a softness | flexibility, crosslinkability, etc. can be obtained easily.
Specifically, as described above, in the case of a laminate having a two-layer structure composed of (A) layer / (B) layer, the ratio between the thickness of (A) layer and the thickness of (B) layer [(A) / a (B)] shall be the above-mentioned range.
本発明の太陽電池封止用シートにおいては、非晶性又は低結晶性のα−オレフィン系共重合体を含む（Ｂ）層が太陽電池素子と当接するようにして太陽電池モジュールに組み込まれるのが好ましい。太陽電池モジュールに組み込む場合、例えば、上部透明保護基材／［(A)層/(B)層］積層シート／太陽電池素子／［(B)層/(A)層］積層シート／バックシート、又は、上部透明保護基材／［(B)層/(A)層/(B)層］積層シート／太陽電池素子／［(B)層/(A)層/(B)層］積層シート／バックシート、等の構造に構成することができる。
また、太陽電池封用シートが（Ｂ）層／（Ａ）層／（Ｂ）層の３層構造の場合、両外層をなす２つの（Ｂ）層の材料、厚み等は同じであっても、異なっていてもよい。
In the solar cell sealing sheet of the present invention, the (B) layer containing the amorphous or low crystalline α-olefin copolymer is incorporated into the solar cell module so as to be in contact with the solar cell element. Is preferred. When incorporated into a solar cell module, for example, upper transparent protective substrate / [(A) layer / (B) layer] laminated sheet / solar cell element / [(B) layer / (A) layer] laminated sheet / back sheet, Or upper transparent protective substrate / [(B) layer / (A) layer / (B) layer] laminated sheet / solar cell element / [(B) layer / (A) layer / (B) layer] laminated sheet / A back sheet or the like can be configured.
Moreover, when the solar cell sealing sheet has a three-layer structure of (B) layer / (A) layer / (B) layer, even if the materials, thicknesses, etc. of the two (B) layers constituting both outer layers are the same. , May be different.
本発明の太陽電池封止用シートは、太陽電池モジュールに組み込まれた状態においては、エチレン・酢酸ビニル共重合体含有層である（Ａ）層及びα−オレフィン系共重合体含有層である（Ｂ）層のいずれか１層、好ましくは（Ａ）層及び（Ｂ）層の両層がともに架橋可能な架橋性積層シートに構成されていることが好ましい。これにより、太陽電池モジュールとした場合に、透明性を維持しつつ、高温での使用時における溶融流れ防止等の耐熱性を付与することができる。そのためには、太陽電池封止用シートとして、（Ａ）層及び（Ｂ）層のいずれか１層、好ましくは両層に架橋剤あるいは架橋剤と架橋助剤が配合されていることが好ましい。 The solar cell sealing sheet of the present invention is an (A) layer that is an ethylene / vinyl acetate copolymer-containing layer and an α-olefin copolymer-containing layer in a state of being incorporated in a solar cell module ( It is preferable that any one of the B) layers, preferably both the (A) layer and the (B) layer, be formed into a crosslinkable laminate sheet. Thereby, when it is set as a solar cell module, heat resistance, such as melt flow prevention at the time of use at high temperature, can be provided, maintaining transparency. For that purpose, as a solar cell sealing sheet, it is preferable that a crosslinking agent or a crosslinking agent and a crosslinking assistant are blended in any one of (A) layer and (B) layer, preferably both layers.
前記架橋剤としては、分解温度（半減期が１時間である温度）が９０〜１８０℃、特に１００〜１５０℃の有機過酸化物を用いることが好ましい。このような有機過酸化物としては、例えば、ｔ−ブチルパーオキシイソプロピルカーボネート、ｔ−ブチルパーオキシ−２−エチルヘキシルカーボネート、ｔ−ブチルパーオキシアセテート、ｔ−ブチルパーオキシベンゾエート、ジクミルパーオキサイド、２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキサン、ジｔ−ブチルパーオキサイド、２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキシン−３、１，１−ビス（ｔ−ブチルパーオキシ）−３，３，５−トリメチルシクロヘキサン、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン、メチルエチルケトンパーオキサイド、２，５−ジメチルヘキシル−２，５−ビスパーオキシベンゾエート、ｔ−ブチルハイドロパーオキサイド、ｐ−メンタンハイドロパーオキサイド、ベンゾイルパーオキサイド、ｐ−クロルベンゾイルパーオキサイド、ｔ−ブチルパーオキシイソブチレート、ヒドロキシヘプチルパーオキサイド、ジクロヘキサノンパーオキサイドなどが挙げられる。 As the crosslinking agent, it is preferable to use an organic peroxide having a decomposition temperature (temperature at which the half-life is 1 hour) of 90 to 180 ° C., particularly 100 to 150 ° C. Examples of such organic peroxides include t-butyl peroxyisopropyl carbonate, t-butyl peroxy-2-ethylhexyl carbonate, t-butyl peroxyacetate, t-butyl peroxybenzoate, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, 1 , 1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, methyl ethyl ketone peroxide, 2,5-dimethylhexyl-2,5- Bisperoxybenzoate, t-butyl hydroperoxide, p-menthane hydride Peroxide, benzoyl peroxide, p- chlorobenzoyl peroxide, t- butyl peroxy isobutyrate, hydroxyheptyl peroxide, and di cyclohexanone peroxide.
架橋剤は、エチレン・酢酸ビニル共重合体１００質量部あるいは非晶性又は低結晶性のα−オレフィン系共重合体１００質量部に対し、０．１〜５質量部が効果的であり、特に０．３〜３質量部の割合で配合するのが効果的である。 The crosslinking agent is effective in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer or 100 parts by mass of an amorphous or low-crystalline α-olefin copolymer. It is effective to mix at a ratio of 0.3 to 3 parts by mass.
また、前記架橋助剤の具体例としては、ポリアリル化合物やポリ（メタ）アクリロキシ化合物のような多不飽和化合物を例示することができる。より具体的には、トリアリルイソシアヌレート、トリアリルシアヌレート、ジアリルフタレート、ジアリルフマレート、ジアリルマレエートのようなポリアリル化合物、エチレングリコールジアクリレート、エチレングリコールジメタクリレート、トリメチロールプロパントリメタクリレートのようなポリ（メタ）アクリロキシ化合物、ジビニルベンゼンなどを挙げることができる。
架橋助剤は、エチレン・酢酸ビニル共重合体１００質量部あるいは非晶性又は低結晶性のα−オレフィン系共重合体１００質量部に対し、５質量部以下が効果的であり、特に０．１〜３質量部の割合で配合するのが効果的である。
In addition, specific examples of the crosslinking aid include polyunsaturated compounds such as polyallyl compounds and poly (meth) acryloxy compounds. More specifically, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, etc. Examples include poly (meth) acryloxy compounds and divinylbenzene.
The crosslinking aid is effective in an amount of not more than 5 parts by mass with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer or 100 parts by mass of the amorphous or low crystalline α-olefin copolymer. It is effective to mix at a ratio of 1 to 3 parts by mass.
太陽電池封止材用シートの（Ａ）層及び（Ｂ）層の各層には、必要に応じ、その他種々の添加剤を配合することができる。このような添加剤として具体的には、シランカップリング剤、チタンカップリング剤のような接着付与剤、酸化防止剤、光安定剤、紫外線吸収剤、着色剤、光拡散剤、難燃剤、変色防止剤などを例示することができる。 Various other additives can be blended in each of the layers (A) and (B) of the solar cell encapsulant sheet, if necessary. Specific examples of such additives include adhesion imparting agents such as silane coupling agents and titanium coupling agents, antioxidants, light stabilizers, ultraviolet absorbers, colorants, light diffusing agents, flame retardants, and discoloration. An inhibitor etc. can be illustrated.
前記着色剤としては、顔料、無機化合物や染料等が挙げられる。特に白色の着色剤としては、酸化チタンや酸化亜鉛が挙げられる。 Examples of the colorant include pigments, inorganic compounds and dyes. In particular, examples of white colorants include titanium oxide and zinc oxide.
これら添加剤を太陽電池素子の受光側に配される太陽電池封止材用シートに配合する場合は、その透明性を損なうものは好ましくないが、太陽電池素子の受光側と反対面に配される太陽電池封止材用シートに配合する場合にはそのような制約を受けない。 When these additives are added to the solar cell encapsulant sheet disposed on the light receiving side of the solar cell element, it is not preferable to impair the transparency, but the additive is disposed on the surface opposite to the light receiving side of the solar cell element. There is no such restriction when blended into a solar cell encapsulant sheet.
前記接着付与剤は、保護材や太陽電池素子等に対する接着性を向上させるのに有用である。その例としては、アミノ基又はエポキシ基とともに、アルコキシ基のような加水分解可能な官能基を有するシランカップリング剤やチタンカップリング剤などを挙げることができる。シランカップリング剤として具体的には、γ−メタクリロキシプロピルトリメトキシシラン、γ−メタクリロキシプロピルメチルジメトキシシラン、γ−アクリロキシプロピルトリメトキシシラン、γ−アクリロキシプロピルメチルジメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルトリメトキシシラン、Ｎ−（β−アミノエチル）−γ−アミノプロピルメチルジメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−グリシドキシプロピルトリメトキシシランなどを例示することができる。 The adhesion-imparting agent is useful for improving adhesion to a protective material, a solar cell element, and the like. Examples thereof include a silane coupling agent and a titanium coupling agent having a hydrolyzable functional group such as an alkoxy group together with an amino group or an epoxy group. Specific examples of the silane coupling agent include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, N- (β -Aminoethyl) -γ-aminopropyltrimethoxysilane, N- (β-aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, etc. can do.
接着付与剤は、エチレン・酢酸ビニル共重合体１００質量部あるいは非晶性または低結晶性のα−オレフィン系共重合体層１００質量部に対し、５質量部以下が効果的であり、特に０．０２〜３質量部の割合で配合するのが効果的である。
本発明では、これらシランカップリング剤などの接着付与剤は、（Ｂ）層のみに配合してもよく、また（Ａ）層及び（Ｂ）層の両層に配合してもよい。
5 parts by mass or less is effective with respect to 100 parts by mass of the ethylene / vinyl acetate copolymer or 100 parts by mass of the amorphous or low crystalline α-olefin copolymer layer, and particularly 0 It is effective to blend at a ratio of 0.02 to 3 parts by mass.
In the present invention, these adhesion imparting agents such as a silane coupling agent may be blended only in the (B) layer, or in both the (A) layer and the (B) layer.
また、太陽光線中の紫外線に基づく封止材用シートの劣化を防ぐために、（Ａ）層及び（Ｂ）層のそれぞれに酸化防止剤、光安定剤、及び紫外線吸収剤の少なくとも１種を配合することが効果的である。 In addition, in order to prevent deterioration of the sheet for sealing material based on ultraviolet rays in sunlight, at least one of an antioxidant, a light stabilizer, and an ultraviolet absorber is blended in each of the layers (A) and (B). It is effective to do.
前記酸化防止剤としては、例えば、各種ヒンダードフェノール系やホスファイト系のものを使用することができる。ヒンダードフェノール系酸化防止剤の具体例としては、２，６−ジ−ｔ−ブチル−ｐ−クレゾール、２−ｔ−ブチル−４−メトキシフェノール、３−ｔ−ブチル−４−メトキシフェノール、２，６−ジ−ｔ−ブチル−４−エチルフェノール、２，２’−メチレンビス（４−メチル−６−ｔ−ブチルフェノール）、２，２’−メチレンビス（４−エチル−６−ｔ−ブチルフェノール）、４，４’−メチレンビス（２，６−ジ−ｔ−ブチルフェノール）、２，２’−メチレンビス［６−（１−メチルシクロヘキシル）−ｐ−クレゾール］、ビス［３,３−ビス（４−ヒドロキシ−３−ｔ−ブチルフェニル）ブチリックアシッド］グリコールエステル、４，４’−ブチリデンビス（６−ｔ−ブチル−ｍ−クレゾール）、２，２’−エチリデンビス（４−ｓｅｃ−ブチル−６−ｔ−ブチルフェノール）、２，２’−エチリデンビス（４，６−ジ−ｔ−ブチルフェノール）、１，１，３−トリス（２−メチル−４−ヒドロキシ−５−ｔ−ブチルフェニル）ブタン、１，３，５−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジル）−２，４，６−トリメチルベンゼン、２，６−ジフェニル−４−オクタデシロキシフェノール、テトラキス［メチレン−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］メタン、ｎ−オクタデシル−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、４，４’−チオビス（６−ｔ−ブチル−ｍ−クレゾール）、トコフェロール、３，９−ビス［１，１−ジメチル−２−［β−（３−ｔ−ブチル−４−ヒドロキシ−５−メチルフェニル）プロピオニルオキシ］エチル］２，４，８，１０−テトラオキサスピロ［５，５］ウンデカン、２，４，６−トリス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルチオ）−１，３，５−トリアジンなどを挙げることができる。
また、ホスファイト系酸化防止剤の具体例としては、３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルフォスファネートジメチルエステル、ビス（３，５−ジ−ｔ−ブチル−４−ヒドロキシベンジルホスホン酸エチル、トリス（２，４−ジ−ｔ−ブチルフェニル）ホスファネートなどを挙げることができる。
As the antioxidant, for example, various hindered phenols and phosphites can be used. Specific examples of the hindered phenol antioxidant include 2,6-di-t-butyl-p-cresol, 2-t-butyl-4-methoxyphenol, 3-t-butyl-4-methoxyphenol, 2 , 6-di-t-butyl-4-ethylphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4′-methylenebis (2,6-di-t-butylphenol), 2,2′-methylenebis [6- (1-methylcyclohexyl) -p-cresol], bis [3,3-bis (4-hydroxy) -3-t-butylphenyl) butyric acid] glycol ester, 4,4′-butylidenebis (6-t-butyl-m-cresol), 2,2′-ethylidenebis (4-sec) -Butyl-6-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butyl) Phenyl) butane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene, 2,6-diphenyl-4-octadecyloxyphenol, Tetrakis [methylene-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] methane, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,4′-thiobis (6-tert-butyl-m-cresol), tocopherol, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5) -Methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, 2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzylthio ) -1,3,5-triazine and the like.
Specific examples of phosphite antioxidants include 3,5-di-tert-butyl-4-hydroxybenzyl phosphinate dimethyl ester, bis (3,5-di-tert-butyl-4-hydroxybenzyl). Examples thereof include ethyl phosphonate and tris (2,4-di-t-butylphenyl) phosphinate.
前記光安定剤としては、例えば、ヒンダードアミン系のものを好適に使用することができる。ヒンダードアミン系の光安定剤として、例えば、４−アセトキシ−２，２，６，６−テトラメチルピペリジン、４−ステアロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−アクリロイルオキシ−２，２，６，６−テトラメチルピペリジン、４−ベンゾイルオキシ−２，２，６，６−テトラメチルピペリジン、４−シクロヘキサノイルオキシ−２，２，６，６−テトラメチルピペリジン、４−（ｏ−クロロベンゾイルオキシ）−２，２，６，６−テトラメチルピペリジン、４−（フェノキシアセトキシ）−２，２，６，６−テトラメチルピペリジン、１，３，８−トリアザ−７，７，９，９−テトラメチル−２，４−ジオキソ−３−ｎオクチル−スピロ［４，５］デカン、ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート、ビス（２，２，６，６−テトラメチル−４−ピペリジル）テレフタレート、ビス（１，２，２，６，６−ペンタメチル−４−ピペリジル）セバケート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）ベンゼン−１，３，５−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）−２−アセトキシプロパン−１，２，３−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）−２−ヒドロキシプロパン−１，２，３−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジル）トリアジン−２，４，６−トリカルボキシレート、トリス（２，２，６，６−テトラメチル−４−ピペリジン）ホスファイト、トリス（２，２，６，６−テトラメチル−４−ピペリジル）ブタン−１，２，３−トリカルボキシレート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）プロパン−１，１，２，３−テトラカルボキシレート、テトラキス（２，２，６，６−テトラメチル−４−ピペリジル）ブタン−１，２，３，４−テトラカルボキシレートなどを挙げることができる。 As said light stabilizer, a hindered amine type thing can be used conveniently, for example. Examples of hindered amine light stabilizers include 4-acetoxy-2,2,6,6-tetramethylpiperidine, 4-stearoyloxy-2,2,6,6-tetramethylpiperidine, 4-acryloyloxy-2, 2,6,6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 4-cyclohexanoyloxy-2,2,6,6-tetramethylpiperidine, 4- (o -Chlorobenzoyloxy) -2,2,6,6-tetramethylpiperidine, 4- (phenoxyacetoxy) -2,2,6,6-tetramethylpiperidine, 1,3,8-triaza-7,7,9 , 9-Tetramethyl-2,4-dioxo-3-noctyl-spiro [4,5] decane, bis (2,2,6,6-tetramethyl-4-piperidyl Sebacate, bis (2,2,6,6-tetramethyl-4-piperidyl) terephthalate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, Tris (2,2,6,6 -Tetramethyl-4-piperidyl) benzene-1,3,5-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-acetoxypropane-1,2,3-tri Carboxylate, tris (2,2,6,6-tetramethyl-4-piperidyl) -2-hydroxypropane-1,2,3-tricarboxylate, tris (2,2,6,6-tetramethyl-4 -Piperidyl) triazine-2,4,6-tricarboxylate, tris (2,2,6,6-tetramethyl-4-piperidine) phosphite, tris (2,2,6,6) Tetramethyl-4-piperidyl) butane-1,2,3-tricarboxylate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) propane-1,1,2,3-tetracarboxylate, Examples thereof include tetrakis (2,2,6,6-tetramethyl-4-piperidyl) butane-1,2,3,4-tetracarboxylate.
前記紫外線吸収剤としては、例えば、２−ヒドロキシ−４−メトキシベンゾフェノン、２，２′−ジヒドロキシ−４−メトキシベンゾフェノン、２−ヒドロキシ−４−メトキシ−２−カルボキシベンゾフェノン、２−ヒドロキシ−４−ｎ−オクトキシベンゾフェノンなどのベンゾフェノン系、２−（２′−ヒドロキシ−３′，５′−ジｔ−ブチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−５−メチルフェニル）ベンゾトリアゾール、２−（２′−ヒドロキシ−５−ｔ−オクチルフェニル）ベンゾトリアゾールなどのベンゾトリアゾール系、フェニルサリチレート、ｐ−オクチルフェニルサリチレートなどのサリチル酸エステル系のものが使用できる。 Examples of the ultraviolet absorber include 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2-carboxybenzophenone, 2-hydroxy-4-n. -Benzophenone series such as octoxybenzophenone, 2- (2'-hydroxy-3 ', 5'-di-t-butylphenyl) benzotriazole, 2- (2'-hydroxy-5-methylphenyl) benzotriazole, 2- A benzotriazole type such as (2'-hydroxy-5-t-octylphenyl) benzotriazole, or a salicylic acid ester type such as phenyl salicylate or p-octylphenyl salicylate can be used.
上記の酸化防止剤、光安定剤、及び紫外線吸収剤は、エチレン・酢酸ビニル共重合体あるいは非晶性又低結晶性のα−オレフィン系共重合体１００重量部に対し、それぞれ５質量部以下が効果的であり、特に０．１〜３質量部の割合で配合するのが効果的である。 The above antioxidant, light stabilizer, and ultraviolet absorber are each 5 parts by mass or less with respect to 100 parts by weight of ethylene / vinyl acetate copolymer or amorphous or low crystalline α-olefin copolymer. It is effective, and it is effective to mix | blend in the ratio of 0.1-3 mass parts especially.
本発明の太陽電池封止用シートにおいて、（Ａ）層中のエチレン・酢酸ビニル共重合体の含有量は、（Ａ）層の全質量に対して６０質量％以上が好ましく、より好ましくは８０質量％以上であり、また、（Ｂ）層中の非晶性又低結晶性のα−オレフィン系共重合体は、（Ｂ）層の全質量に対して６０質量％以上が好ましく、より好ましくは８０質量％以上である。 In the solar cell sealing sheet of the present invention, the content of the ethylene / vinyl acetate copolymer in the layer (A) is preferably 60% by mass or more, more preferably 80%, based on the total mass of the layer (A). The non-crystalline or low-crystalline α-olefin copolymer in the layer (B) is preferably 60% by weight or more, more preferably based on the total weight of the layer (B). Is 80% by mass or more.
本発明の太陽電池封止用シートの成形は、単層あるいは多層Ｔ−ダイ押出機、カレンダー成形機、単層あるいは多層インフレーション成形機などを使用する公知の方法によって行なうことができる。例えば、エチレン・酢酸ビニル共重合体と非晶性又は低結晶性のα−オレフィン系共重合体とのそれぞれに、有機過酸化物並びに必要に応じて添加される架橋助剤、接着付与剤、酸化防止剤、光安定剤、及び紫外線吸収剤等から選ばれる添加剤を予めドライブレンドして多層Ｔ−ダイ押出機の主押出機及び従押出機それぞれのホッパーから供給し、有機過酸化物が実質的に分解しない成形温度でシート状に多層押出成形することによって得ることができる。また、このような積層シートを予め作製せずに、例えば、エチレン・酢酸ビニル共重合体に有機過酸化物並びに必要に応じて添加される前記添加剤を予めドライブレンドして上記同様にシート状に押出成形したシート［（Ａ）層用シート］と、非晶性又は低結晶性のα−オレフィン系共重合体層に有機過酸化物並びに必要に応じて添加される前記添加剤を予めドライブレンドして上記同様にシート状に押出成形したシート［（Ｂ）層用シート］とを作製しておき、太陽電池モジュールの作製時に、保護材と太陽電池素子との間にエチレン・酢酸ビニル共重合体を主成分とする（Ａ）層用シートと非晶性又は低結晶性のα−オレフィン系共重合体を主成分とする（Ｂ）層用シートとを重ね合わせて、（Ａ）層用シート／（Ｂ）層用シート／太陽電池素子からなる封止構造を形成することもできる。 The solar cell sealing sheet of the present invention can be formed by a known method using a single-layer or multilayer T-die extruder, a calendar molding machine, a single-layer or multilayer inflation molding machine, or the like. For example, each of an ethylene / vinyl acetate copolymer and an amorphous or low-crystalline α-olefin copolymer, an organic peroxide, a crosslinking aid added as necessary, an adhesion-imparting agent, Additives selected from antioxidants, light stabilizers, UV absorbers, etc. are dry-blended in advance and supplied from the respective hoppers of the multi-layer T-die extruder and the organic peroxide It can be obtained by multilayer extrusion molding into a sheet at a molding temperature that does not substantially decompose. Further, without preparing such a laminated sheet in advance, for example, an organic peroxide and an additive added as necessary to an ethylene / vinyl acetate copolymer are dry-blended in advance to form a sheet in the same manner as above. The sheet [(A) layer sheet] extruded and the amorphous peroxide or low crystalline α-olefin copolymer layer and the above-mentioned additive added as needed are dried beforehand. A sheet [(B) layer sheet] which was blended and extruded into a sheet shape in the same manner as described above was prepared, and during the production of the solar cell module, ethylene / vinyl acetate was used between the protective material and the solar cell element. The (A) layer sheet is formed by superimposing the (A) layer sheet mainly composed of a polymer and the (B) layer sheet mainly composed of an amorphous or low crystalline α-olefin copolymer. Sheet / (B) layer sheet / solar power A sealing structure made of a pond element can also be formed.
本発明の太陽電池封止用シートを用い、太陽電池素子を上下２枚の保護材で挟んで固定することにより、太陽電池モジュールを作製することができる。このような太陽電池モジュールとしては、種々のタイプのものを例示することができる。例えば、太陽光が入射する側の上部透明保護材／封止用シート／太陽電池素子／封止用シート／下部保護材のように、太陽電池素子の両側から封止用シートで挟んだ構成のもの、ガラスなどの基板の表面上に形成された太陽電池素子を、上部透明保護材／封止用シート／太陽電池素子が形成された基板／封止用シート／下部保護材のように、基板上に形成された太陽電池素子の 両側から封止材で挟む構成のもの、上部透明保護材の内周面上に形成された太陽電池素子、例えばフッ素樹脂系シート上にアモルファス太陽電池素子をスパッタリング等で作成したものの上に封止用シートと下部保護材を形成させるような構成のものなどを挙げることができる。このような構成の太陽電池モジュールにおいて、本発明の太陽電池封止用シートが（Ｂ）層／（Ａ）層／（Ｂ）層の３層構造の場合は、一方の外層［（Ｂ）層］が太陽電池素子と当接し、他方の外層［（Ｂ）層］が上部透明保護材又は下部保護材と当接するように積層される。また、（Ａ）層／（Ｂ）層の２層構造の場合は、（Ｂ）層面が太陽電池素子と接するように、（Ａ）層面が上部保護材および下部保護材（バックシート）と接するように、あるいは（Ａ）層面が上部保護材及び下部保護材（バックシート）と接するように、（Ｂ）層面が太陽電池素子又はそれが形成された基板と接するように積層される。 A solar cell module can be produced by using the solar cell sealing sheet of the present invention and sandwiching and fixing the solar cell element between two upper and lower protective materials. Examples of such solar cell modules include various types. For example, the structure is sandwiched between the solar cell elements from both sides of the solar cell element, such as upper transparent protective material / sealing sheet / solar cell element / sealing sheet / lower protective material on the side where sunlight enters. A solar cell element formed on the surface of a substrate such as a glass or glass substrate, like an upper transparent protective material / a sheet for sealing / a substrate on which a solar cell element is formed / a sheet for sealing / a lower protective material Sputtered amorphous solar cell element on solar cell element formed on the inner peripheral surface of upper transparent protective material, for example, a structure sandwiched by sealing material from both sides of solar cell element formed above The thing of the structure etc. which form the sheet | seat for sealing and a lower protective material on what was produced by etc. can be mentioned. In the solar cell module having such a configuration, when the solar cell sealing sheet of the present invention has a three-layer structure of (B) layer / (A) layer / (B) layer, one outer layer [(B) layer ] Is in contact with the solar cell element, and the other outer layer [(B) layer] is laminated in contact with the upper transparent protective material or the lower protective material. In the case of the two-layer structure of (A) layer / (B) layer, the (A) layer surface is in contact with the upper protective material and the lower protective material (back sheet) so that the (B) layer surface is in contact with the solar cell element. Alternatively, the (B) layer surface is laminated so as to be in contact with the solar cell element or the substrate on which it is formed, so that the (A) layer surface is in contact with the upper protective material and the lower protective material (back sheet).
太陽電池素子としては、単結晶シリコン、多結晶シリコン、アモルファスシリコンなどのシリコン系、ガリウム−砒素、銅−インジウム−セレン、銅−インジウム−ガリウム−セレン、カドミウム−テルルなどのＩＩＩ−Ｖ族やＩＩ−ＶＩ族化合物半導体系等の各種太陽電池素子を用いることができる。本発明の太陽電池封止用シートは、封止材との耐久接着性の点で、特にアモルファスシリコン太陽電池素子の封止に有用である。 Examples of solar cell elements include silicon-based materials such as single crystal silicon, polycrystalline silicon, and amorphous silicon, III-V groups such as gallium-arsenic, copper-indium-selenium, copper-indium-gallium-selenium, cadmium-tellurium, and II. Various solar cell elements such as a group VI compound semiconductor can be used. The solar cell sealing sheet of the present invention is particularly useful for sealing an amorphous silicon solar cell element in terms of durable adhesiveness with a sealing material.
太陽電池モジュールを構成する上部保護材としては、太陽光が入射する入射面である観点から、ガラス、アクリル樹脂、ポリカーボネート、ポリエステル、フッ素含有樹脂などを例示することができる。また、下部保護材としては、金属や各種熱可塑性樹脂フィルムなどの単体もしくは多層のシートが挙げられ、例えば、錫、アルミ、ステンレススチールなどの金属、ガラス等の無機材料、ポリエステル、無機物蒸着ポリエステル、フッ素含有樹脂、ポリオレフィンなどの１層もしくは多層のシートを例示することができる。
本発明の太陽電池封止用シートは、これらの上部保護材及び／又は下部保護材に対して良好な接着性を示す。
Examples of the upper protective material constituting the solar cell module include glass, acrylic resin, polycarbonate, polyester, fluorine-containing resin, and the like from the viewpoint of an incident surface on which sunlight is incident. In addition, examples of the lower protective material include single or multilayer sheets such as metals and various thermoplastic resin films, for example, metals such as tin, aluminum, and stainless steel, inorganic materials such as glass, polyester, inorganic vapor-deposited polyester, A single layer or multilayer sheet of fluorine-containing resin or polyolefin can be exemplified.
The solar cell sealing sheet of the present invention exhibits good adhesion to these upper protective material and / or lower protective material.
太陽電池モジュールの製造は、太陽電池封止用シートが溶融する（かつ、架橋剤を含むときには架橋剤が実質的に分解しない）温度で、太陽電池素子や保護材に本発明の太陽電池封止用シートを仮接着し、次いで昇温して充分な接着と必要に応じ架橋を行なえばよい。接着、架橋は、例えば１００〜１８０℃程度の温度で、１０〜１２０分程度行なえばよい。最終的には、耐熱性の良好な太陽電池モジュールを得るために、太陽電池封止用シートにおけるエチレン・酢酸ビニル共重合体を主成分に含む（Ａ）層及び非晶性又は低結晶性のα−オレフィン系共重合体層を主成分に含み（Ｂ）層の両層のゲル分率（試料１ｇをキシレン１００ｍｌに浸漬し、１１０℃で２４時間加熱した後、２０メッシュ金網で濾過したときの未溶解分の質量分率）が７０％以上であることが好ましく、より好ましくは７０〜９８％であり、さらに好ましくは８０〜９５％程度になるように架橋するのがよい。したがって、これら諸条件を満足できるように両層の添加剤処方を選べばよく、例えば架橋剤等の種類及び配合量を適宜選択すればよい。 The solar cell module is produced by sealing the solar cell of the present invention to a solar cell element or a protective material at a temperature at which the solar cell sealing sheet melts (and the crosslinking agent does not substantially decompose when it contains a crosslinking agent). The adhesive sheet may be temporarily bonded and then heated to achieve sufficient bonding and crosslinking as necessary. Adhesion and crosslinking may be performed at a temperature of about 100 to 180 ° C. for about 10 to 120 minutes, for example. Finally, in order to obtain a solar cell module with good heat resistance, the (A) layer containing an ethylene / vinyl acetate copolymer as a main component in the solar cell sealing sheet and an amorphous or low crystalline property Gel fraction of both layers of the (B) layer containing an α-olefin copolymer layer as a main component (When 1 g of a sample is immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, and then filtered through a 20 mesh wire mesh. Is preferably 70% or more, more preferably 70 to 98%, and even more preferably about 80 to 95%. Therefore, the additive formulation of both layers may be selected so that these various conditions can be satisfied. For example, the type and blending amount of the crosslinking agent and the like may be appropriately selected.
以下、本発明を実施例により更に具体的に説明するが、本発明はその主旨を越えない限り、以下の実施例に限定されるものではない。なお、特に断りのない限り、「部」は質量基準である。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” is based on mass.
［実施例１］
下記に示すＥＶＡ−１（エチレン・酢酸ビニル共重合体）１００部に、下記架橋剤Ａ０．９６部、下記架橋剤Ｂ０．２４部、下記シランカップリング剤０．５部、下記酸化防止剤０．０３部、下記紫外線吸収剤０．３部、及び下記耐光安定剤０．１部を配合し、ＥＶＡ配合物を得た。次いで、下記ＶＬ１００部に、架橋剤Ａ０．９６部、架橋剤Ｂ０．２４部を添加し、下記シランカップリング剤０．３部、下記酸化防止剤０．０３部、下記紫外線吸収剤０．３部および下記耐光安定剤０．１部を配合して、ＶＬ配合物を得た。次に、０．２ｍｍ厚みのＥＶＡ配合物からなる（Ａ１）層シートと、０．２ｍｍ厚みのＶＬ配合物からなる（Ｂ１）層シートと、をそれぞれＴ−ダイ成形機を用いて、樹脂温度１００℃にて加工し作製した。
[Example 1]
To 100 parts of EVA-1 (ethylene / vinyl acetate copolymer) shown below, 0.96 part of the following crosslinking agent A, 0.24 part of the following crosslinking agent B, 0.5 part of the following silane coupling agent, and the following antioxidant 0 0.03 part, 0.3 part of the following ultraviolet absorber and 0.1 part of the following light stabilizer were blended to obtain an EVA blend. Next, 0.96 part of a crosslinking agent A and 0.24 part of a crosslinking agent B are added to 100 parts of the following VL, 0.3 part of the following silane coupling agent, 0.03 part of the following antioxidant, 0.3 part of the following ultraviolet absorber. Part and 0.1 part of the following light-resistant stabilizer were blended to obtain a VL blend. Next, the (A1) layer sheet composed of the 0.2 mm-thick EVA composition and the (B1) layer sheet composed of the 0.2-mm-thick VL composition were respectively used for the resin temperature using a T-die molding machine. Fabricated by processing at 100 ° C.
得られた（Ａ１）層シート及び（Ｂ１）層シートを用いて、下記表１に記載の構成の架橋性多層シート（太陽電池封止用シート）を予め作製し、この多層シートを青板ガラス基板（3.2mm厚、旭硝子社製）及びバックシート（トーヤルソーラー：東洋アルミニウム社製）と貼り合わせを行なった。このとき、（Ｂ１）層シートがガラス及びバックシートとそれぞれ接するようにガラス基板及びバックシートと貼り合わせ、１５０℃で３０分間加熱し架橋した後、ゲル分率、ガラス接着強度、バックシート接着強度の評価を下記に示す方法にて行なった。評価結果は下記表１に示す。 Using the obtained (A1) layer sheet and (B1) layer sheet, a crosslinkable multilayer sheet (solar cell sealing sheet) having the constitution described in Table 1 below was prepared in advance, and this multilayer sheet was produced as a blue plate glass substrate. (3.2 mm thickness, manufactured by Asahi Glass Co., Ltd.) and a back sheet (Toyal Solar: manufactured by Toyo Aluminum Co., Ltd.) were bonded together. At this time, the (B1) layer sheet was bonded to the glass substrate and the back sheet so as to be in contact with the glass and the back sheet, respectively, and heated and crosslinked at 150 ° C. for 30 minutes, and then the gel fraction, the glass adhesive strength, and the back sheet adhesive strength. Was evaluated by the method shown below. The evaluation results are shown in Table 1 below.
−材料−
・ＥＶＡ−１：エチレン・酢酸ビニル共重合体（エチレン／酢酸ビニル[質量比]＝７２／２８、ＭＦＲ（JIS K7210-1999、190℃、荷重2160g）＝１５ｇ／１０ｍｉｎ）
・ＶＬ：非晶性又は低結晶性のα−オレフィン共重合体（三井化学（株）製のタフマーＰ０２７５、密度８７０ｋｇ／ｍ３、ＭＦＲ（ASTM D-1238、230℃、荷重2160g）＝２．９ｇ／１０ｍｉｎ、結晶化度：２％）
・架橋剤Ａ：２，５−ジメチル−２，５−ビス（ｔ−ブチルパーオキシ）ヘキサン
・架橋剤Ｂ：ｔ−ブチルパーオキシ−２−エチルヘキシルカーボネート
・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：Ｉｒｇａｎｏｘ１０１０（チバ・スペシャリティーケミカルズ製）
・紫外線吸収剤：２‐ヒドロキシ−４−ｎ−オクトキシベンゾフェノン
・耐光安定剤：ビス（２，２，６，６−テトラメチル−４−ピペリジル）セバケート
-Material-
EVA-1: ethylene-vinyl acetate copolymer (ethylene / vinyl acetate [mass ratio] = 72/28, MFR (JIS K7210-1999, 190 ° C., load 2160 g) = 15 g / 10 min)
VL: amorphous or low crystalline α-olefin copolymer (Tafmer P0275 manufactured by Mitsui Chemicals, density 870 kg / m 3 , MFR (ASTM D-1238, 230 ° C., load 2160 g) = 2. 9g / 10min, crystallinity: 2%)
Crosslinking agent A: 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane Crosslinking agent B: t-butylperoxy-2-ethylhexyl carbonate Silane coupling agent: γ-methacryloxypropyl Trimethoxysilane and antioxidant: Irganox 1010 (Ciba Specialty Chemicals)
UV absorber: 2-hydroxy-4-n-octoxybenzophenoneLight stabilizer: bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate
−評価−
（１）架橋特性（ゲル分率）
前記同様にＴ−ダイ成形機を用いて作製した（Ａ１）層シート及び（Ｂ１）層シートを表１に記載の構成で積層後、１５０℃のオーブン中で３０分間加熱することにより架橋シートを作製した。この架橋シート１ｇを１００ｍｌのキシレンに浸漬し、１１０℃、２４時間加熱した後、金網で濾過して不溶解分を捕集し、乾燥後秤量することによってゲル分率［％］を求め、架橋特性を評価する指標とした。その結果を表１に示す。ゲル分率の値が大きいほど、良好に架橋が行なわれたことを示す。
-Evaluation-
(1) Cross-linking properties (gel fraction)
After laminating the (A1) layer sheet and the (B1) layer sheet prepared in the same manner as described above using the T-die molding machine in the same manner as described above, the crosslinked sheet was heated in an oven at 150 ° C. for 30 minutes. Produced. 1 g of this cross-linked sheet is immersed in 100 ml of xylene, heated at 110 ° C. for 24 hours, filtered through a wire mesh to collect the insoluble matter, and dried and weighed to obtain the gel fraction [%]. It was used as an index for evaluating characteristics. The results are shown in Table 1. The larger the gel fraction value, the better the crosslinking.
（２）ガラス接着強度
前記同様にＴ−ダイ成形機を用いて作製した（Ａ１）層シート及び（Ｂ１）層シートを表１に記載の構成で積層後、３ｍｍ厚みのガラス上に載せて、真空貼り合わせ機で１２５℃にて５分間貼り合わせた後、１４５℃で３０分かけてオーブン中で架橋および接着を行なった。冷却後、引張試験機で貼合部を剥離し、ガラスに対する接着力［Ｎ］を測定し、接着強度を評価した。なお、測定は、１０ｍｍ幅短冊、引張速度５０ｍｍ／分の条件で行なった。その結果を表１に示す。
(2) Glass adhesive strength (A1) layer sheet and (B1) layer sheet prepared using a T-die molding machine in the same manner as described above were stacked in the configuration described in Table 1 and placed on 3 mm thick glass. After bonding at 125 ° C. for 5 minutes with a vacuum bonding machine, crosslinking and adhesion were performed in an oven at 145 ° C. for 30 minutes. After cooling, the bonded part was peeled off with a tensile tester, the adhesive strength [N] to glass was measured, and the adhesive strength was evaluated. The measurement was performed under the conditions of a 10 mm width strip and a tensile speed of 50 mm / min. The results are shown in Table 1.
（３）バックシート接着強度
前記同様にＴ−ダイ成形機を用いて作製した（Ａ１）層シート及び（Ｂ１）層シートを表１に記載の構成で積層後、真空貼り合わせ機で１２５℃にて５分間ＰＥＴ系バックシート（トーヤルソーラー（プライマーなし）、東洋アルミニウム（株）製）と貼り合わを行なった。次いで、１４５℃で３０分かけてオーブン中で架橋および接着を行い、引張試験機で貼合部を剥離し、バックシートに対する接着力［Ｎ］を測定し、接着強度を評価した。なお、測定は、１０ｍｍ幅短冊、引張速度５０ｍｍ／分の条件で行なった。その結果を表１に示す。
(3) Back sheet adhesive strength After the (A1) layer sheet and the (B1) layer sheet prepared using a T-die molding machine in the same manner as described above were laminated in the configuration shown in Table 1, the pressure was increased to 125 ° C. with a vacuum laminating machine. 5 minutes and then bonded to a PET back sheet (Toyal Solar (no primer), manufactured by Toyo Aluminum Co., Ltd.). Next, crosslinking and adhesion were performed in an oven at 145 ° C. for 30 minutes, the bonded portion was peeled off with a tensile tester, the adhesive strength [N] to the back sheet was measured, and the adhesive strength was evaluated. The measurement was performed under the conditions of a 10 mm width strip and a tensile speed of 50 mm / min. The results are shown in Table 1.
（４）透明性
前記同様にＴ−ダイ成形機を用いて作製した（Ａ１）層シート及び（Ｂ１）層シートを表１に記載の構成で、青板ガラス２枚の間に挟むように積層後、ヘイズメーター（スガ試験機製）にてＪＩＳ−Ｋ７１０６に準じて全光線透過率を測定した。
(4) Transparency After laminating the (A1) layer sheet and (B1) layer sheet prepared using a T-die molding machine in the same manner as described above and sandwiched between two sheets of blue sheet glass in the configuration shown in Table 1. The total light transmittance was measured according to JIS-K7106 using a haze meter (manufactured by Suga Test Instruments).
［実施例２］
実施例１において、０．３ｍｍ厚みのＥＶＡ配合物からなる（Ａ２）層シートと、０．３ｍｍ厚みのＶＬ配合物からなる（Ｂ２）層シートと、をそれぞれＴ−ダイ成形機を用いて、樹脂温度１００℃にて作製した。これらのシートを用いて、下記表１に記載の構成の架橋性多層シート（太陽電池封止用シート）を予め作製し、この多層シートを、（Ａ２）層シートがガラス面に接し、（Ｂ２）層シートがバックシートに接するように、ガラス基板及びバックシート（トーヤルソーラー：東洋アルミニウム社製）と貼り合わせを行ない、１４５℃で３０分間加熱して架橋後、実施例１と同様にして、ゲル分率、ガラス接着強度、及びバックシート接着強度の評価を行なった。評価結果は下記表１に示す。
[Example 2]
In Example 1, a (A2) layer sheet composed of a 0.3 mm thick EVA composition and a (B2) layer sheet composed of a 0.3 mm thick VL composition were each used with a T-die molding machine. It was produced at a resin temperature of 100 ° C. Using these sheets, a crosslinkable multilayer sheet (solar cell sealing sheet) having the structure described in Table 1 below was prepared in advance, and the multilayer sheet (A2) was in contact with the glass surface, and (B2 ) Laminate the glass sheet and back sheet (Toyal Solar: manufactured by Toyo Aluminum Co., Ltd.) so that the layer sheet is in contact with the back sheet, and after heating and crosslinking at 145 ° C. for 30 minutes, in the same manner as in Example 1. The gel fraction, the glass adhesive strength, and the backsheet adhesive strength were evaluated. The evaluation results are shown in Table 1 below.
［実施例３］
実施例１において、０．２ｍｍ厚みのＥＶＡ配合物からなる（Ａ３）層シートと、０．４ｍｍ厚みのＶＬ配合物からなる（Ｂ３）層シートと、をそれぞれＴ−ダイ成形機を用いて、樹脂温度１００℃にて作製した。これらのシートを用いて、下記表１に記載の構成の架橋性多層シート（太陽電池封止用シート）を予め作製し、この多層シートを、（Ａ３）層シートがガラス面に接し、（Ｂ３）層シートがバックシートに接するように、ガラス基板及びバックシート（トーヤルソーラー：東洋アルミニウム社製）と貼り合わせを行ない、１４５℃で３０分間加熱して架橋後、ゲル分率、ガラス接着強度、及びバックシート接着強度の評価を行なった。評価結果は下記表１に示す。
[Example 3]
In Example 1, a (A3) layer sheet composed of an EVA composition having a thickness of 0.2 mm and a (B3) layer sheet composed of a VL composition having a thickness of 0.4 mm were each used with a T-die molding machine. It was produced at a resin temperature of 100 ° C. Using these sheets, a crosslinkable multilayer sheet (solar cell sealing sheet) having the structure described in Table 1 below was prepared in advance, and the multilayer sheet (A3) was in contact with the glass surface, and (B3 ) The glass sheet and the back sheet (Toyal Solar: manufactured by Toyo Aluminum Co., Ltd.) are bonded so that the layer sheet is in contact with the back sheet, heated at 145 ° C. for 30 minutes, crosslinked, gel fraction, and glass adhesive strength. , And evaluation of backsheet adhesive strength. The evaluation results are shown in Table 1 below.
［実施例４］
実施例２において、ＥＶＡ配合物に用いたＥＶＡ−１（酢酸ビニル：２８質量％）を、ＥＶＡ−２（エチレン／酢酸ビニル[質量比]＝９０／１０、ＭＦＲ＝１５ｇ／１０ｍｉｎ）に代えて、加工温度を１１０℃に変更したこと以外は、実施例２と同様にして、貼り合わせ、加熱架橋を行なうと共に、ゲル分率、ガラス接着強度、及びバックシート接着強度の評価を行なった。評価結果は下記表１に示す。
[Example 4]
In Example 2, EVA-1 (vinyl acetate: 28% by mass) used in the EVA formulation was replaced with EVA-2 (ethylene / vinyl acetate [mass ratio] = 90/10, MFR = 15 g / 10 min). Except that the processing temperature was changed to 110 ° C., lamination and heat crosslinking were performed in the same manner as in Example 2, and the gel fraction, glass adhesive strength, and backsheet adhesive strength were evaluated. The evaluation results are shown in Table 1 below.
［比較例１］
実施例１において、０．６ｍｍ厚みのＥＶＡ配合物からなる架橋性の（Ａ４）層シートをＴ−ダイ成形機を用いて樹脂温度１００℃にて加工し作製した。このシートを用いて、下記表１に記載の構成でガラス基板及びバックシート（トーヤルソーラー：東洋アルミニウム社製）と貼り合わせを行ない、ゲル分率、ガラス接着強度、及びバックシート接着強度の評価を行なった。評価結果は下記表１に示す。
[Comparative Example 1]
In Example 1, a crosslinkable (A4) layer sheet made of an EVA composition having a thickness of 0.6 mm was processed and produced at a resin temperature of 100 ° C. using a T-die molding machine. Using this sheet, the glass substrate and the back sheet (Toyal Solar: manufactured by Toyo Aluminum Co., Ltd.) were bonded together in the configuration shown in Table 1 below, and the gel fraction, glass bond strength, and back sheet bond strength were evaluated. Was done. The evaluation results are shown in Table 1 below.
［比較例２］
実施例２において、ＥＶＡ配合物に用いたＥＶＡ−１（酢酸ビニル：２８質量％）を、ＥＶＡ−３（エチレン／酢酸ビニル[質量比]＝５４／４６、ＭＦＲ＝２．５ｇ／１０ｍｉｎ）に代えたこと以外は、実施例２と同様にして、貼り合わせ、加熱架橋を行なうと共に、ゲル分率、ガラス接着強度、及びバックシート接着強度の評価を行なった。評価結果は下記表１に示す。
[Comparative Example 2]
In Example 2, EVA-1 (vinyl acetate: 28% by mass) used in the EVA formulation was changed to EVA-3 (ethylene / vinyl acetate [mass ratio] = 54/46, MFR = 2.5 g / 10 min). Except for having been replaced, in the same manner as in Example 2, bonding and heat crosslinking were performed, and the gel fraction, glass adhesive strength, and backsheet adhesive strength were evaluated. The evaluation results are shown in Table 1 below.
前記表１に示すように、実施例では、透明性を保持しつつ、ガラス及びバックシートの双方に対して優れた接着性を示した。これに対し、比較例１では、ガラスに対する接着性は良好であるが、バックシートに対する接着性が劣り、また比較例２では、バックシートとの接着性は良好であるが、ガラスとの間の接着性が顕著に劣っていた。 As shown in Table 1, in Examples, excellent adhesiveness to both glass and a back sheet was exhibited while maintaining transparency. On the other hand, in Comparative Example 1, the adhesion to the glass is good, but the adhesion to the back sheet is inferior, and in Comparative Example 2, the adhesion to the back sheet is good, but between the glass and The adhesiveness was remarkably inferior.
Claims (4)
エチレン由来の構成単位と炭素数３〜２０のα−オレフィン由来の構成単位とを含み、エチレン由来の構成単位含量が５０〜９０モル％、かつ炭素数３〜２０のα−オレフィン由来の構成単位含量が５０〜１０モル％であり、Ｘ線による結晶化度が４０％以下である非晶性又は低結晶性のエチレン・α−オレフィン系共重合体を主成分に含む（Ｂ）層と、の少なくとも２層を含み、
前記エチレン・酢酸ビニル共重合体及び前記エチレン・α−オレフィン系共重合体のメルトフローレート（ＪＩＳ Ｋ７２１０−１９９９、１９０℃、２１６０ｇ荷重）が、それぞれ０．１〜１５０ｇ／１０分の範囲にあり、
前記（Ａ）層の厚みと前記（Ｂ）層の厚みとの比率［（Ａ）／（Ｂ）］が９／１〜１／９である太陽電池封止用シート。 (A) layer containing, as a main component, an ethylene / vinyl acetate copolymer having a content of structural units derived from vinyl acetate of 5 to 40% by mass;
A structural unit derived from an ethylene-derived structural unit and a structural unit derived from an α-olefin having 3 to 20 carbon atoms, having an ethylene-derived structural unit content of 50 to 90 mol% and having 3 to 20 carbon atoms A layer (B) containing a non-crystalline or low-crystalline ethylene / α-olefin copolymer having a content of 50 to 10 mol% and a crystallinity by X-ray of 40% or less as a main component ; Including at least two layers,
The melt flow rate (JIS K7210-1999, 190 ° C., 2160 g load) of the ethylene / vinyl acetate copolymer and the ethylene / α-olefin copolymer is in the range of 0.1 to 150 g / 10 min. ,
The ratio of the thickness of the the thickness of the (A) layer (B) layer [(A) / (B)] is 4.5 / 1 to 1/9 der Ru sheet for sealing a solar cell.
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