JP2013166820A - Sealing material for solar cell - Google Patents
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- JP2013166820A JP2013166820A JP2012029702A JP2012029702A JP2013166820A JP 2013166820 A JP2013166820 A JP 2013166820A JP 2012029702 A JP2012029702 A JP 2012029702A JP 2012029702 A JP2012029702 A JP 2012029702A JP 2013166820 A JP2013166820 A JP 2013166820A
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- 239000003566 sealing material Substances 0.000 title claims abstract description 38
- 150000001451 organic peroxides Chemical class 0.000 claims abstract description 74
- 239000005038 ethylene vinyl acetate Substances 0.000 claims abstract description 63
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims abstract description 63
- 239000003085 diluting agent Substances 0.000 claims abstract description 59
- 239000000203 mixture Substances 0.000 claims abstract description 48
- 230000005484 gravity Effects 0.000 claims abstract description 31
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000008393 encapsulating agent Substances 0.000 claims description 10
- 229930195733 hydrocarbon Natural products 0.000 claims description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 4
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- 239000003208 petroleum Substances 0.000 claims description 3
- 238000004132 cross linking Methods 0.000 abstract description 30
- 238000005187 foaming Methods 0.000 abstract description 28
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 230000000052 comparative effect Effects 0.000 description 19
- 238000000034 method Methods 0.000 description 8
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- 238000000465 moulding Methods 0.000 description 7
- 150000001875 compounds Chemical class 0.000 description 6
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- 238000010248 power generation Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
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- 238000005259 measurement Methods 0.000 description 4
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- 238000007789 sealing Methods 0.000 description 4
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- DMWVYCCGCQPJEA-UHFFFAOYSA-N 2,5-bis(tert-butylperoxy)-2,5-dimethylhexane Chemical compound CC(C)(C)OOC(C)(C)CCC(C)(C)OOC(C)(C)C DMWVYCCGCQPJEA-UHFFFAOYSA-N 0.000 description 3
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- 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
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- XMNIXWIUMCBBBL-UHFFFAOYSA-N 2-(2-phenylpropan-2-ylperoxy)propan-2-ylbenzene Chemical compound C=1C=CC=CC=1C(C)(C)OOC(C)(C)C1=CC=CC=C1 XMNIXWIUMCBBBL-UHFFFAOYSA-N 0.000 description 1
- BRQMAAFGEXNUOL-UHFFFAOYSA-N 2-ethylhexyl (2-methylpropan-2-yl)oxy carbonate Chemical compound CCCCC(CC)COC(=O)OOC(C)(C)C BRQMAAFGEXNUOL-UHFFFAOYSA-N 0.000 description 1
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- POZWNWYYFQVPGC-UHFFFAOYSA-N 3-methoxysilylpropyl 2-methylprop-2-enoate Chemical compound CO[SiH2]CCCOC(=O)C(C)=C POZWNWYYFQVPGC-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
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- 239000004641 Diallyl-phthalate Substances 0.000 description 1
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- 239000005977 Ethylene Substances 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- QOYVOTWLPFJZOC-UHFFFAOYSA-N NAS-3 Natural products COc1cc2OC(=CC(=O)c2c(O)c1OC)c3c(O)cc(O)c(OC)c3OC QOYVOTWLPFJZOC-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- NOZAQBYNLKNDRT-UHFFFAOYSA-N [diacetyloxy(ethenyl)silyl] acetate Chemical compound CC(=O)O[Si](OC(C)=O)(OC(C)=O)C=C NOZAQBYNLKNDRT-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 125000003668 acetyloxy group Chemical group [H]C([H])([H])C(=O)O[*] 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- ZPOLOEWJWXZUSP-AATRIKPKSA-N bis(prop-2-enyl) (e)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C\C(=O)OCC=C ZPOLOEWJWXZUSP-AATRIKPKSA-N 0.000 description 1
- ZPOLOEWJWXZUSP-WAYWQWQTSA-N bis(prop-2-enyl) (z)-but-2-enedioate Chemical compound C=CCOC(=O)\C=C/C(=O)OCC=C ZPOLOEWJWXZUSP-WAYWQWQTSA-N 0.000 description 1
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 description 1
- 230000009172 bursting Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229940088336 primor Drugs 0.000 description 1
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- 229940070710 valerate Drugs 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- 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
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- Compositions Of Macromolecular Compounds (AREA)
- Photovoltaic Devices (AREA)
- Sealing Material Composition (AREA)
Abstract
Description
本発明は、太陽電池のセルを封止する太陽電池用封止材に関連し、特に、エチレン-酢酸ビニル共重合体（以下、ＥＶＡと称す場合がある）を架橋剤である有機過酸化物によって架橋する太陽電池用封止材に関するものである。 The present invention relates to a solar cell encapsulant that seals cells of a solar cell, and in particular, an organic peroxide that is an ethylene-vinyl acetate copolymer (hereinafter sometimes referred to as EVA) as a crosslinking agent. It is related with the sealing material for solar cells bridge | crosslinked by.
近年、水力・風力・原子力発電や太陽光・熱発電、バイオマス発電などの二次エネルギーが、化石燃料の代替エネルギー源として注目されており、中でも無尽蔵の太陽光のエネルギーを電気エネルギーに変換することのできる太陽電池による発電方式が注目され、開発が進められている。 In recent years, secondary energy such as hydropower, wind power, nuclear power generation, solar power generation, thermal power generation, and biomass power generation has been attracting attention as an alternative energy source for fossil fuels. A solar power generation system that can be used is attracting attention and is being developed.
一般的な太陽電池モジュールの基本的構成は、図１に示すように、複数の太陽電池用セル（太陽電池素子）１０１が、表面（光入射側）保護用のガラス板１０２と耐候性を有するバックカバー１０３とによって挟持され、ガラス板１０２とバックカバー１０３との間には、これらを接着し、太陽電池用セル１０１を封止するためのＥＶＡ（エチレン−酢酸ビニル共重合体）やポリビニルブチラールなどの熱可塑性透明樹脂から成る封止材１０４が介装されている。
As shown in FIG. 1, the basic configuration of a general solar battery module is that a plurality of solar battery cells (solar battery elements) 101 have weather resistance with a
太陽電池モジュールに用いられるＥＶＡ封止材は、ＥＶＡと有機過酸化物を含む組成物を押出成形、もしくはカレンダー成形によりシート状に成形したものである。ＥＶＡに加えられた有機過酸化物が熱により分解してＥＶＡを架橋させると、架橋度の指標となるゲル分率が向上される。ＥＶＡのゲル分率を向上することによりＥＶＡ封止材の耐熱性及び強度を向上することができ、屋外等の環境下で使用される太陽電池にはゲル分率が８０％以上であるＥＶＡが必要である。したがって、屋外等で使用される太陽電池を提供するためには、有機過酸化物をＥＶＡ中に含有させてＥＶＡを架橋することが不可欠となっている。そのため、有機過酸化物による架橋においては、加熱により有機過酸化物を分解させる工程が必要となる。 The EVA sealing material used for the solar cell module is obtained by molding a composition containing EVA and an organic peroxide into a sheet by extrusion molding or calendar molding. When the organic peroxide added to EVA is decomposed by heat to crosslink EVA, the gel fraction serving as an index of the degree of crosslinking is improved. By improving the gel fraction of EVA, the heat resistance and strength of the EVA sealing material can be improved. For solar cells used in environments such as outdoors, EVA having a gel fraction of 80% or more is used. is necessary. Therefore, in order to provide a solar cell used outdoors or the like, it is essential to include EVA in the EVA to crosslink the EVA. Therefore, in the crosslinking with the organic peroxide, a step for decomposing the organic peroxide by heating is required.
従来、ＥＶＡ中に含有させる有機過酸化物としては、下記式（II）に示す２，５−ジメチル−２，５−ジ（ｔ−ブチルパーオキシ）ヘキサン（II）のような1時間半減期温度（Ｔ１ｈ）が１３８℃であるジアルキルパーオキサイド型のものが用いられることがあった。その場合、分解および架橋反応をする時間が遅いために、封止工程における生産性が低いという問題点があった。なお、半減期温度とは有機過酸化物の半分が分解する温度のことである。 Conventionally, as an organic peroxide to be contained in EVA, a one-hour half-life such as 2,5-dimethyl-2,5-di (t-butylperoxy) hexane (II) represented by the following formula (II) A dialkyl peroxide type having a temperature (T 1h ) of 138 ° C. was sometimes used. In that case, there is a problem that the productivity in the sealing process is low because the time for the decomposition and crosslinking reaction is slow. The half-life temperature is a temperature at which half of the organic peroxide is decomposed.
しかしながら、Ｔ１ｈが１００〜１３０℃と低いパーオキシエステル型のような有機過酸化物を使用すると、短時間での架橋が可能になるものの、封止材に有機過酸化物の分解物に起因するものと思われる発泡（膨れ）現象が起こる問題が生じ易いことが知られている。発泡は、ＥＶＡ封止材の密着性を低下させる要因となり、封止性能が低下、太陽電池の寿命と発電効率が低下するという問題が生じる。 However, when an organic peroxide such as a peroxyester type having a low T 1h of 100 to 130 ° C. is used, crosslinking in a short time is possible, but the sealing material is caused by a decomposition product of the organic peroxide. It is known that the problem of foaming (swelling) phenomenon that seems to occur easily occurs. Foaming causes a decrease in the adhesion of the EVA sealing material, resulting in a problem that the sealing performance is lowered and the lifetime and power generation efficiency of the solar cell are lowered.
そこで特許文献１には、Ｔ１ｈが１３０〜１６０℃のジアルキルパーオキサイド型の有機過酸化物と、Ｔ１ｈが１００〜１３５℃のアルキルパーオキシエステル型、もしくは、パーオキシケタール型の有機過酸化物を特定の割合で配合することにより、架橋時間の短縮と発泡の問題を解決する方法が示されている。しかしながら、太陽電池市場の拡大に伴い、更なる架橋時間の短縮が望まれるようになり、Ｔ１ｈが高いジアルキルパーオキサイド型の有機過酸化物を含まずに、さらに短時間で架橋することが求められている。 Therefore, Patent Document 1, an organic peroxide dialkyl peroxide type T 1h is 130 to 160 ° C., alkyl peroxyester type T 1h is 100 to 135 ° C., or an organic peroxide of peroxyketal type A method for shortening the crosslinking time and solving the problem of foaming by blending the products in a specific ratio is shown. However, with the expansion of the solar cell market, further shortening of the cross-linking time is desired, and it is required to cross-link in a shorter time without including a dialkyl peroxide type organic peroxide having a high T 1h. It has been.
また、特許文献２には、下記式（III）に示されるＴ１ｈが１２６．５℃と低いパーオキシケタール型の有機過酸化物、ｎ−ブチル４，４−ジ（ｔ−ブチルパーオキシ）バレレート（III）のみを用いた場合、有機過酸化物の分解によって生じたガスによる太陽電池セルの移動が多く、製品の不具合が生じることが示されている。この問題に対して、Ｔ１ｈが９２.１℃と低いパーオキシエステル型の有機過酸化物であって、下記式（IV）に示されるｔ−ブチルパーオキシ２−エチルヘキサノエート（IV）を加えることにより、ガスによる不具合解決と速架橋が同時に達成されたことが示されている。しかしながら、Ｔ１ｈが著しく低い有機過酸化物（IV）を含んでおり、封止材を成形する段階で分解・架橋が進むため、早期架橋（スコーチ）の問題が生じた。 Patent Document 2 discloses a peroxyketal type organic peroxide having a low T 1h of 126.5 ° C. represented by the following formula (III), n-butyl 4,4-di (t-butylperoxy). It has been shown that when only valerate (III) is used, there are many movements of solar cells by the gas generated by the decomposition of the organic peroxide, resulting in product defects. To solve this problem, a peroxyester type organic peroxide having a T 1h as low as 92.1 ° C., which is t-butylperoxy 2-ethylhexanoate (IV) represented by the following formula (IV): It is shown that the problem solving by gas and rapid crosslinking were achieved at the same time. However, since the organic peroxide (IV) having a remarkably low T 1h is included and decomposition and crosslinking proceed at the stage of molding the encapsulant, there is a problem of early crosslinking (scorch).
これに対し、下記式（I）で表される有機過酸化物（I）（１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサン）については、Ｔ１ｈが１１１．１℃で速架橋可能であるとともに、その理論は必ずしも明らかではないが、それ自体の熱分解による発泡が起こりにくいことが知られている。なお、この有機過酸化物（I）については、特許文献３に速架橋可能な有機過酸化物として挙げられているとともに、特許文献４で、架橋工程で熱分解することによるガスの発生を高く抑制して発泡を抑えられる有機過酸化物の一つとして挙げられている。したがって、この有機過酸化物（I）を用いれば、発泡を抑制しながらの速架橋が期待される。 On the other hand, for the organic peroxide (I) (1,1-bis (t-butylperoxy) cyclohexane) represented by the following formula (I), T 1h can be rapidly crosslinked at 111.1 ° C. At the same time, the theory is not necessarily clear, but it is known that foaming by its own thermal decomposition hardly occurs. This organic peroxide (I) is listed as an organic peroxide capable of rapid crosslinking in Patent Document 3, and in Patent Document 4, generation of gas due to thermal decomposition in the crosslinking process is increased. It is listed as one of the organic peroxides that can suppress foaming. Therefore, when this organic peroxide (I) is used, rapid crosslinking while suppressing foaming is expected.
ところで、一般に、有機過酸化物は、自己反応性を有するために取り扱い時の危険性が非常に高い。そのため、安全性を確保するために、希釈剤無しでは消防法第５類第２種に該当する比較的安全性の高い有機過酸化物しか工業的には使用されないのが実情である。有機過酸化物（I）のような工業純品で消防法第５類第１種に該当する危険性の高い有機過酸化物を用いる場合には、当該有機過酸化物に希釈剤を加えることにより、第５類第２種に該当する混合物にして使用される。その場合、有機過酸化物の希釈剤としては、一般にトルエン、エチルベンゼン、炭化水素溶剤が用いられる。 In general, organic peroxides have a high risk of handling because of their self-reactivity. Therefore, in order to ensure safety, the fact is that only organic peroxides that are relatively safe and fall under the Fire Service Law Type 5 Type 2 are used industrially without a diluent. When using a high-risk organic peroxide that falls under Class 5 Class 1 of the Fire Service Act for industrial pure products such as organic peroxide (I), add a diluent to the organic peroxide. Therefore, it is used as a mixture corresponding to the second type of the fifth class. In that case, toluene, ethylbenzene, or a hydrocarbon solvent is generally used as a diluent for the organic peroxide.
ところが、太陽電池用封止材の製造においては、希釈剤を添加すると、安全性が高まる一方で希釈剤によって発泡が引き起こされる問題があった。したがって、これまでの工業的な太陽電池用封止材の製造においては、有機過酸化物（I）の使用は困難とされていた。 However, in the production of a solar cell encapsulant, when a diluent is added, there is a problem that foaming is caused by the diluent while safety is improved. Therefore, it has been difficult to use organic peroxides (I) in the production of industrial solar cell encapsulants.
しかしながら、特許文献３でも、特許文献４でも、希釈剤による発泡の問題は考慮されていない。なお、発泡の抑制を目的とした特許文献４では、工業純品で消防法第５類第２種に該当する比較的安全性の高い有機過酸化物である、１，１−ビス（ｔ−ヘキシルパーオキシ）−３,３,５−トリメチルシクロヘキサンやｔｅｒｔ−ブチルパーオキシ２−エチルヘキシルモノカーボネート、２,５−ジメチル−２,５ジ（ｔｅｒｔ−ブチルパーオキシ）ヘキサンが、特に好ましいとされている。これらは、希釈剤の添加が不要であり、希釈剤による発泡の問題は生じない。したがって、より速架橋可能な有機過酸化物（I）を工業的な太陽電池用封止材の製造に用いる場合に引き起こされる希釈剤による発泡の問題は未だ解決されていないと言える。 However, neither Patent Document 3 nor Patent Document 4 considers the problem of foaming due to a diluent. In Patent Document 4 for the purpose of suppressing foaming, 1,1-bis (t-), which is an industrially pure product and a relatively safe organic peroxide corresponding to the Class 5 Class 2 of the Fire Service Act. Hexylperoxy) -3,3,5-trimethylcyclohexane and tert-butylperoxy 2-ethylhexyl monocarbonate and 2,5-dimethyl-2,5 di (tert-butylperoxy) hexane are particularly preferred. Yes. These do not require the addition of a diluent and do not cause foaming problems due to the diluent. Therefore, it can be said that the foaming problem due to the diluent caused when the organic peroxide (I) capable of faster crosslinking is used in the production of an industrial solar cell encapsulant has not yet been solved.
そこで、本発明者は、有機過酸化物（I）を工業的に実用化すべく鋭意検討した。その結果、有機過酸化物（I）に対してある特定の比重の希釈剤を特定の割合で用いることによって安全性を高め、そのうえで、ＥＶＡに対して特定の割合で含有させることで、太陽電池用封止材の発泡が抑制されることを見出し、本発明を完成させるに至った。 Therefore, the present inventor has intensively studied to put the organic peroxide (I) into practical use. As a result, safety is improved by using a specific ratio of a diluent with a specific ratio with respect to the organic peroxide (I), and then the solar cell is contained at a specific ratio with respect to EVA. The present inventors have found that the foaming of the sealing material is suppressed and completed the present invention.
すなわち、本発明は、ＥＶＡに対して速架橋が可能な有機過酸化物（I）を含有させるあたり、有機過酸化物（I）を希釈剤で希釈して安全性を確保しつつも、希釈剤に起因する発泡を抑制することを目的とする。 That is, in the present invention, when the organic peroxide (I) capable of rapid crosslinking with EVA is contained, the organic peroxide (I) is diluted with a diluent to ensure safety. It aims at suppressing the foaming resulting from an agent.
そのための手段として、本発明の太陽電池用封止材は、酢酸ビニルより形成される構造単位を２５〜３５重量％有するエチレン-酢酸ビニル共重合体（Ａ）と、上記式（I）に示す有機過酸化物（I）及び希釈剤（Ｂ）を含む組成物（Ｃ）の含有量が、前記エチレン-酢酸ビニル共重合体（Ａ）１００重量部に対して、０．１〜４．０重量部であり、組成物（Ｃ）中の有機過酸化物（I）と希釈剤（Ｂ）との重量比（I：Ｂ）が、１００：２０〜５０であり、希釈剤（Ｂ）の比重が０．７５以上、０．８７以下であることを特徴とする。 As a means therefor, the encapsulant for solar cells of the present invention has an ethylene-vinyl acetate copolymer (A) having 25 to 35% by weight of structural units formed from vinyl acetate, and the above formula (I). The content of the composition (C) containing the organic peroxide (I) and the diluent (B) is 0.1 to 4.0 with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer (A). Parts by weight, and the weight ratio (I: B) of the organic peroxide (I) to the diluent (B) in the composition (C) is 100: 20 to 50, and the diluent (B) The specific gravity is 0.75 or more and 0.87 or less.
このとき、前記希釈剤（Ｂ）がイソパラフィン系炭化水素、及び石油系炭化水素から選ばれる少なくとも１種の飽和炭化水素からなることが好ましい。 At this time, it is preferable that the diluent (B) is composed of at least one kind of saturated hydrocarbon selected from isoparaffin hydrocarbons and petroleum hydrocarbons.
本発明の太陽電池用封止材によれば、ガスの生成が少ない有機過酸化物（I）と、所定比重の希釈剤（Ｂ）を所定の割合で混合させた組成物（Ｃ）を用いることにより、工業的にも安全性が保たれつつも、該組成物（Ｃ）をＥＶＡに対して所定の割合で混合することで発泡を防止しながら短時間で架橋させてＥＶＡのゲル分率を十分に向上することができる。 According to the sealing material for solar cells of the present invention, the composition (C) obtained by mixing the organic peroxide (I) with less gas generation and the diluent (B) having a specific gravity at a predetermined ratio is used. Thus, while maintaining safety industrially, the composition (C) is cross-linked in a short time while preventing foaming by mixing the composition (C) at a predetermined ratio with EVA, and the gel fraction of EVA Can be improved sufficiently.
本発明の太陽電池用封止材（以下、単に封止材又はＥＶＡ封止材と称する場合がある）は、エチレン−酢酸ビニル共重合体（ＥＶＡ）（Ａ）と、有機過酸化物（I）と希釈剤（Ｂ）とを含む組成物（Ｃ）と、を含んでおり、太陽電池モジュールにおいて太陽電池用セルを封止するために用いられる。以下において、その構成を説明する。 The solar cell encapsulant of the present invention (hereinafter sometimes simply referred to as encapsulant or EVA encapsulant) comprises an ethylene-vinyl acetate copolymer (EVA) (A) and an organic peroxide (I ) And a diluent (B) and a composition (C), and is used for sealing a solar cell in a solar cell module. The configuration will be described below.
＜エチレン−酢酸ビニル共重合体（ＥＶＡ）（Ａ）＞
エチレン−酢酸ビニル共重合体（ＥＶＡ）（Ａ）はエチレンと酢酸ビニルとの共重合体であり、本発明で用いられるＥＶＡ（Ａ）は、酢酸ビニルを構造単位で２５〜３５重量％含んでいる。この酢酸ビニル含有率が３５重量％を超えると、粘着性が増大して取り扱いが困難になる。一方、酢酸ビニル含有率が２５重量％未満になると、封止材が硬くなるため加工性が低下し、また、封止材は硬化に伴い緩衝材としての機能が低下するため、封止材で保護されている太陽電池用セルが衝撃により割れやすくなるので好ましくない。
<Ethylene-vinyl acetate copolymer (EVA) (A)>
The ethylene-vinyl acetate copolymer (EVA) (A) is a copolymer of ethylene and vinyl acetate, and EVA (A) used in the present invention contains 25 to 35% by weight of vinyl acetate as a structural unit. Yes. When the vinyl acetate content exceeds 35% by weight, the tackiness increases and handling becomes difficult. On the other hand, when the vinyl acetate content is less than 25% by weight, the sealing material becomes hard and the workability is lowered. Also, the sealing material has a function as a cushioning material as it is cured. Since the protected solar cell is easily broken by impact, it is not preferable.
＜組成物（Ｃ）＞
組成物（Ｃ）は、上記式（I）で表される有機過酸化物（I）、すなわち、１，１−ビス（ｔ−ブチルパーオキシ）シクロヘキサンと希釈剤（Ｂ）とを含む。有機過酸化物（I）は、熱分解時におけるガスの発生が少なく、Ｔ１ｈが１１１．１℃と低いためにゲル分率が８０％以上になるようＥＶＡを速架橋することができる。しかし、自己反応性が非常に高いために取り扱い時の危険性が高く、工業的に使用するためには、希釈剤を添加することにより安全性を高める必要がある。
<Composition (C)>
The composition (C) contains an organic peroxide (I) represented by the above formula (I), that is, 1,1-bis (t-butylperoxy) cyclohexane and a diluent (B). Organic peroxide (I) generates less gas during thermal decomposition, and T 1h is as low as 111.1 ° C., so that EVA can be rapidly crosslinked so that the gel fraction is 80% or more. However, since the self-reactivity is very high, the danger at the time of handling is high, and in order to use it industrially, it is necessary to increase safety by adding a diluent.
＜希釈剤（Ｂ）＞
希釈剤（Ｂ）は、有機過酸化物（I）の安全性を高め、かつそれ自体が発泡の要因とならないことが求められる。希釈剤（Ｂ）としては、比重が０．７５以上、０．８７以下の希釈剤を用いる。より好ましくは、比重を０．７８以上、０．８２以下、さらに好ましくは０．７８以上、０．８０以下とする。希釈剤（Ｂ）の比重が０．７５未満になると発泡を引き起こし、０．８７を超えると架橋阻害を引き起こし、ゲル分率が低下する。希釈剤（Ｂ）としては、液状の飽和炭化水素が好適である。より具体的には、イソパラフィン系炭化水素、石油系炭化水素が挙げられ、さらにはこれら２種以上を比重が上記範囲となるように混合した希釈剤などが挙げられる。
<Diluent (B)>
The diluent (B) is required to enhance the safety of the organic peroxide (I) and not itself cause foaming. As the diluent (B), a diluent having a specific gravity of 0.75 or more and 0.87 or less is used. More preferably, the specific gravity is 0.78 or more and 0.82 or less, more preferably 0.78 or more and 0.80 or less. When the specific gravity of the diluent (B) is less than 0.75, foaming is caused, and when it exceeds 0.87, crosslinking is inhibited and the gel fraction is lowered. As the diluent (B), liquid saturated hydrocarbon is suitable. More specifically, examples include isoparaffinic hydrocarbons and petroleum hydrocarbons, and further include a diluent in which two or more of these are mixed so that the specific gravity falls within the above range.
比重は、ＪＩＳ Ｚ ８８０４−１９９４に準じて１５℃で測定を行った。この規格で示される比重とは、１５℃で測定された液体の質量と、それと同体積の圧力１０１３２５Ｐａのもとにおける４℃の純粋な水の質量との比のことであり、無名数で表される。 The specific gravity was measured at 15 ° C. according to JIS Z 8804-1994. The specific gravity shown in this standard is the ratio of the mass of a liquid measured at 15 ° C. to the mass of pure water at 4 ° C. under the same volume of pressure 101325 Pa. Is done.
希釈剤（Ｂ）は有機過酸化物（I）の合成時に添加し、その際の添加量を変えることにより、有機過酸化物（I）と希釈剤（Ｂ）との重量比（I：Ｂ）が、１００：２０〜５０（すなわち、１００：２０〜１００：５０）の範囲で調節される組成物（Ｃ）が得られる。 Diluent (B) is added during the synthesis of organic peroxide (I), and the weight ratio (I: B) of organic peroxide (I) to diluent (B) is changed by changing the amount added. ) Is adjusted in the range of 100: 20 to 50 (that is, 100: 20 to 100: 50), the composition (C) is obtained.
有機過酸化物（I）と希釈剤（Ｂ）を混合し、組成物（Ｃ）を得ることも可能であるが、有機過酸化物（I）は工業純品で消防法第５類第１種に該当する自己反応性の高い化合物であるため、そのような方法は安全性に問題があるため避けることが望ましい。 It is possible to obtain a composition (C) by mixing the organic peroxide (I) and the diluent (B). Since it is a highly self-reactive compound corresponding to a species, it is desirable to avoid such a method because it has a safety problem.
このとき有機過酸化物（I）と希釈剤（Ｂ）との重量比（I：Ｂ）は、１００：２０〜５０（すなわち、１００：２０〜１００：５０）である。有機過酸化物（I）１００重量部に対して、希釈剤（Ｂ）が２０重量部より少ないと、組成物（Ｃ）の自己反応性が高く、消防法第５類第１種に該当するため、取り扱い時の危険性が高く、工業的な使用が困難となる。一方、有機過酸化物（I）１００重量部に対して、希釈剤（Ｂ）が５０重量部より多くなると、過剰な希釈剤（Ｂ）が発泡を引き起こす。 At this time, the weight ratio (I: B) of the organic peroxide (I) to the diluent (B) is 100: 20 to 50 (that is, 100: 20 to 100: 50). If the diluent (B) is less than 20 parts by weight with respect to 100 parts by weight of the organic peroxide (I), the composition (C) has high self-reactivity and falls under the Fire Service Law Class 5 Class 1 Therefore, the danger at the time of handling is high and industrial use becomes difficult. On the other hand, when the diluent (B) is more than 50 parts by weight with respect to 100 parts by weight of the organic peroxide (I), the excessive diluent (B) causes foaming.
また、組成物（Ｃ）の比重については、上記ＪＩＳ規格によって測定が可能であるが、有機過酸化物（I）と希釈剤（Ｂ）の重量比とそれぞれの比重から算出することも可能である。 The specific gravity of the composition (C) can be measured according to the above JIS standard, but can also be calculated from the weight ratio of the organic peroxide (I) and the diluent (B) and the specific gravity of each. is there.
ＥＶＡ封止材中における組成物（Ｃ）の含有量は、ＥＶＡ１００重量部に対して０．１〜４．０重量部とし、より好ましくは０．３〜３．０重量部とする。ＥＶＡ１００重量部に対して有機過酸化物（I）の含有量が０．１重量部未満では、架橋反応後のＥＶＡのゲル分率（架橋度）が低く、架橋時間が長くなるため、実用に適さない。一方、ＥＶＡ１００重量部に対して有機過酸化物（I）の含有量が４．０重量部を超えると、過剰な有機過酸化物（I）及び希釈剤（Ｂ）が発泡を引き起こす。さらにはＥＶＡの架橋が速くなり過ぎて、太陽電池モジュール製造時の取り扱いが困難となり好ましくない。 The content of the composition (C) in the EVA sealing material is 0.1 to 4.0 parts by weight, more preferably 0.3 to 3.0 parts by weight with respect to 100 parts by weight of EVA. When the content of the organic peroxide (I) is less than 0.1 parts by weight with respect to 100 parts by weight of EVA, the gel fraction (crosslinking degree) of EVA after the crosslinking reaction is low and the crosslinking time becomes long. Not suitable. On the other hand, when the content of the organic peroxide (I) exceeds 4.0 parts by weight with respect to 100 parts by weight of EVA, excess organic peroxide (I) and diluent (B) cause foaming. Furthermore, EVA cross-linking becomes too fast, and handling at the time of manufacturing a solar cell module becomes difficult.
このように有機過酸化物（I）と希釈剤（Ｂ）とを所定の割合で混合した組成物（Ｃ）は、工業的に安全に使用することができる。さらに、ＥＶＡ（Ａ）に対して適当な量で添加した場合、発泡に問題がないゲル分率８０％以上の架橋されたＥＶＡを得ることができる。 Thus, the composition (C) in which the organic peroxide (I) and the diluent (B) are mixed at a predetermined ratio can be used industrially safely. Furthermore, when added in an appropriate amount with respect to EVA (A), a crosslinked EVA having a gel fraction of 80% or more with no problem in foaming can be obtained.
（その他の添加剤）
本発明の封止材には、必要に応じてその他種々の添加剤を配合することができる。例えば、接着性を高めるためにカップリング剤を配合することができる。カップリング剤としては、例えば有機珪素化合物や有機チタン化合物を挙げることができる。有機珪素化合物としては、ビニル基、メタクリロキシアルキル基、アクリロキシアルキル基、エポキシ基のような反応性有機基と、ハロゲン、アルコキシ基、アセトキシ基のような加水分解性基とを有する化合物を例示できる。具体的には、ビニルトリエトキシシラン、ビニルトリス（β−メトキシエトキシ）シラン、γ−メタクリロキシプロピルメトキシシラン、ビニルトリアセトキシシランのような不飽和基を有する化合物の１種または２種以上を使用できる。カップリング剤は、ＥＶＡ１００重量部に対して、０．１〜１０重量部程度、好ましくは０．５〜５重量部程度配合すればよい。
(Other additives)
Various other additives can be blended in the sealing material of the present invention as necessary. For example, a coupling agent can be blended in order to improve adhesiveness. Examples of the coupling agent include organic silicon compounds and organic titanium compounds. Examples of organosilicon compounds include compounds having reactive organic groups such as vinyl groups, methacryloxyalkyl groups, acryloxyalkyl groups, and epoxy groups, and hydrolyzable groups such as halogens, alkoxy groups, and acetoxy groups. it can. Specifically, one or more of compounds having an unsaturated group such as vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloxypropylmethoxysilane, and vinyltriacetoxysilane can be used. . The coupling agent may be blended in an amount of about 0.1 to 10 parts by weight, preferably about 0.5 to 5 parts by weight with respect to 100 parts by weight of EVA.
また、架橋速度や架橋効率を高めるために、架橋助剤を配合することができる。架橋助剤としては、例えば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等を挙げることができる。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のようなポリ（メタ）アクリロキシ化合物の１種または２種以上を使用できる。 Moreover, in order to improve a crosslinking speed and crosslinking efficiency, a crosslinking adjuvant can be mix | blended. Examples of the crosslinking aid include polyunsaturated compounds such as polyallyl compounds and poly (meth) acryloxy compounds. Specifically, polyallyl compounds such as triallyl isocyanurate, triallyl cyanate, diallyl phthalate, diallyl fumarate, diallyl maleate, poly (meth) acryloxy compounds such as ethylene glycol diacrylate, ethylene glycol dimethacrylate 1 type (s) or 2 or more types can be used.
さらに、本発明の効果を阻害しない範囲で、酸化防止剤、光安定剤、紫外線吸収剤、着色剤などを配合することもできる。酸化防止剤としては、例えばフェノール系安定剤、硫黄系安定剤、燐酸系安定剤などが挙げられる。光安定剤としては、例えばヒンダードアミン系光安定剤等が挙げられる。紫外線吸収剤としては、例えばベンゾフェノン系、ベンゾトリアゾール系等が挙げられる。着色剤としては、例えば酸化チタン等が挙げられる。 Furthermore, antioxidants, light stabilizers, ultraviolet absorbers, colorants, and the like can be blended within a range that does not impair the effects of the present invention. Examples of the antioxidant include a phenol stabilizer, a sulfur stabilizer, and a phosphoric acid stabilizer. Examples of the light stabilizer include hindered amine light stabilizers. Examples of the ultraviolet absorber include benzophenone and benzotriazole. Examples of the colorant include titanium oxide.
（製造方法）
封止材は、ＥＶＡ（Ａ）、有機過酸化物（I）と希釈剤（Ｂ）とを含む組成物（Ｃ）、及び必要に応じて適宜配合されるその他の添加剤を含む組成物を、単軸押出機、２軸押出機、バンバリーミキサー、ニーダー、オープンロールなどの汎用の混練装置を使用して、実質的に有機過酸化物が分解しない温度、具体的には５０〜１１０℃程度で混練し、一般的には押出成形やカレンダー成形等によりシート状にされる。シート状とする場合は、その厚みは０．１〜１．０ｍｍ程度とすればよい。なお、封止材の形状は、太陽電池モジュールの形状などに合わせて適宜変更可能であり、シート状に限定されるものではない。
(Production method)
The sealing material is a composition containing EVA (A), a composition (C) containing an organic peroxide (I) and a diluent (B), and other additives appropriately blended as necessary. , A temperature at which the organic peroxide is not substantially decomposed using a general kneading apparatus such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or an open roll, specifically about 50 to 110 ° C. Are kneaded and generally formed into a sheet by extrusion molding, calendar molding, or the like. In the case of a sheet shape, the thickness may be about 0.1 to 1.0 mm. In addition, the shape of a sealing material can be suitably changed according to the shape of a solar cell module, etc., and is not limited to a sheet form.
その後は、従来から公知の方法にて太陽電池モジュールを製造すればよい。すなわち、太陽電池用セルを少なくとも２枚の封止材で挟み、その両外側にガラス板及びバックカバーを重ね合わせた状態で、有機過酸化物の分解温度以上、具体的には１１５℃以上、好ましくは１２０℃以上の温度で加熱・加圧することにより接着・封止することで、太陽電池モジュールを製造できる。なお、より接着性を高めるため、ガラス板やバックカバーは予めプライマー処理しておくと好ましい。また、封止材は太陽電池用セルにラミネートしておくこともできる。 Thereafter, the solar cell module may be manufactured by a conventionally known method. That is, sandwiching the solar cell between at least two sealing materials, in a state where the glass plate and the back cover are overlapped on both outer sides, the organic peroxide decomposition temperature or higher, specifically 115 ° C. or higher, Preferably, a solar cell module can be manufactured by bonding and sealing by heating and pressurizing at a temperature of 120 ° C. or higher. In addition, in order to improve adhesiveness, it is preferable that the glass plate and the back cover are previously primed. Moreover, the sealing material can also be laminated on the solar cell.
加熱は、有機過酸化物がほぼ完全に分解するまで行うことが好ましい。この加熱処理により、ＥＶＡが架橋され、封止材とその他の構成要素とが強固に接着される。加熱処理は、二段階で行うこともできる。例えば、真空条件下において１〜５分程度加熱して仮接着を行い、次いで常圧下にてさらに５〜３０分程度加熱して完全に接着することもできる。このようにして製造される太陽電池モジュールの封止材においては、ＥＶＡの架橋密度の指標となるゲル分率が８０％以上、好ましくは９０％以上となっていることが好ましい。 Heating is preferably performed until the organic peroxide is almost completely decomposed. By this heat treatment, EVA is crosslinked, and the sealing material and other components are firmly bonded. The heat treatment can also be performed in two stages. For example, it can be temporarily bonded by heating for about 1 to 5 minutes under vacuum conditions, and then further bonded for about 5 to 30 minutes under normal pressure for complete bonding. In the sealing material of the solar cell module manufactured as described above, it is preferable that the gel fraction serving as an index of the crosslinking density of EVA is 80% or more, preferably 90% or more.
以下、本発明を実施例により説明する。本発明は、以下の実施例により制限されるものではない。 Hereinafter, the present invention will be described with reference to examples. The present invention is not limited by the following examples.
＜組成物（Ｃ）の合成＞
まず、以下の（I）〜（V）の有機過酸化物（ＰＯ）と、飽和炭化水素溶剤からなる希釈剤（Ｂ）（希釈剤１〜７）を用い、実施例および比較例に使用する組成物（Ｃ）を合成した。各組成物（Ｃ）の組成を実施例については表１、２に、比較例については表３、４に示す。組成物（Ｃ）の合成に関しては、従来知られている有機過酸化物（ＰＯ）の合成反応時に希釈剤（Ｂ）を添加する手順で行った。得られた組成物（Ｃ）を用いて下記消防法判定による安全性の判定、および比重測定を行った。判定結果を、実施例については表１、２に、比較例については表３、４に示す。
［有機過酸化物（ＰＯ）］
（I） 1,1-ビス（t-ブチルパーオキシ）シクロヘキサン（日油株式会社製『パーヘキサC』）
（II） 2,5-ジメチル-2,5-ジ（t-ブチルパーオキシ）ヘキサン（日油株式会社製『パーヘキサ25B』）
（III） n-ブチル-4,4-ビス（t-ブチルパーオキシ）バレレート（日油株式会社製『パーヘキサV』）
（IV） t-ブチルパーオキシ-2-エチルヘキサノエート（日油株式会社製『パーブチルＯ』）
（V） ジクミルパーオキサイド（日油株式会社製『パークミルD』）
［希釈剤（Ｂ）］
（１）日油株式会社製『NAS-4』
（２）日油株式会社製『NAS-5H』
（３）日油株式会社製『NAS-3』
（４）日油株式会社製『ポリブテン0SH』
（５）エクソンモービル社製『プライモールN27』
（６）日油株式会社製『NAS-2』
（７）日油株式会社製『ポリブテン30SH』
<Synthesis of Composition (C)>
First, the following (I) to (V) organic peroxides (PO) and a diluent (B) (diluents 1 to 7) made of a saturated hydrocarbon solvent are used in Examples and Comparative Examples. Composition (C) was synthesized. The composition of each composition (C) is shown in Tables 1 and 2 for Examples, and Tables 3 and 4 for Comparative Examples. The composition (C) was synthesized by a procedure in which the diluent (B) was added during the synthesis reaction of a conventionally known organic peroxide (PO). Using the obtained composition (C), safety determination and specific gravity measurement were performed by the following Fire Service Law determination. The determination results are shown in Tables 1 and 2 for Examples, and Tables 3 and 4 for Comparative Examples.
[Organic peroxide (PO)]
(I) 1,1-bis (t-butylperoxy) cyclohexane (“Perhexa C” manufactured by NOF Corporation)
(II) 2,5-Dimethyl-2,5-di (t-butylperoxy) hexane (“Perhexa 25B” manufactured by NOF Corporation)
(III) n-Butyl-4,4-bis (t-butylperoxy) valerate (“Perhexa V” manufactured by NOF Corporation)
(IV) t-Butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by NOF Corporation)
(V) Dicumyl peroxide (“PARK Mill D” manufactured by NOF Corporation)
[Diluent (B)]
(1) "NAS-4" made by NOF Corporation
(2) NOF “NAS-5H”
(3) "NAS-3" manufactured by NOF Corporation
(4) NOF Corporation "Polybutene 0SH"
(5) “Primor N27” manufactured by ExxonMobil
(6) “NAS-2” manufactured by NOF Corporation
(7) NOF Corporation “Polybutene 30SH”
＜消防法判定＞
組成物（Ｃ）について、消防法で規定された圧力容器試験を行い、消防法判定を行った。細孔径９．０ｍｍ、および１．０ｍｍのオリフィス板での破裂回数を求めた。９．０ｍｍのオリフィス板で５回以上破裂した場合、危険性の高い消防法の第５類第１種に分類した。９．０ｍｍのオリフィス板で４回以下、かつ１．０ｍｍのオリフィス板で５回以上破裂した場合を、比較的安全性の高い消防法の第５類第２種に分類した。
<Fire Service Law Judgment>
About the composition (C), the pressure vessel test prescribed | regulated by the Fire Service Act was done, and the Fire Service Act judgment was performed. The number of bursts with an orifice plate having a pore diameter of 9.0 mm and 1.0 mm was determined. If it bursts 5 times or more with a 9.0 mm orifice plate, it was classified as Class 5 Class 1 of the Fire Service Act with high risk. Cases of bursting 4 times or less with a 9.0 mm orifice plate and 5 times or more with a 1.0 mm orifice plate were classified as Class 5 and Type 2 of the fire safety law with relatively high safety.
＜比重測定＞
組成物（Ｃ）について、ＪＩＳ Ｚ ８８０４：１９９４に準じて比重測定を行った。今回用いた有機過酸化物や希釈剤、それらからなる組成物の各比重は、上記ＪＩＳ規格による手法で測定が可能である。しかしこの組成物の比重は、構成される有機過酸化物と希釈剤の比重から算出することもまた可能であり、その計算式は以下に示される。表１等に示されるように各重量比と、得られる組成物（Ｃ）の比重には相関性がある。例として、比重０．９４３の有機過酸化物（I）と比重０．７９２の希釈剤（１）の重量比と、得られる組成物の比重の相関関係を表５、および図２に示した。
［式１］ ρ１２＝（Ｗ１＋Ｗ２）／（Ｗ１／ρ１＋Ｗ２／ρ２）
ρ１２：物質１と物質２の混合物の比重
Ｗ１、Ｗ２：物質１と物質２のそれぞれの重量
ρ１、ρ２：物質１と物質２のそれぞれの比重
<Specific gravity measurement>
The specific gravity of the composition (C) was measured according to JIS Z 8804: 1994. The specific gravity of the organic peroxide and diluent used this time and the composition comprising them can be measured by the method according to the JIS standard. However, the specific gravity of this composition can also be calculated from the specific gravity of the organic peroxide and diluent, and the calculation formula is shown below. As shown in Table 1 and the like, there is a correlation between the respective weight ratios and the specific gravity of the resulting composition (C). As an example, the correlation between the weight ratio of the organic peroxide (I) having a specific gravity of 0.943 and the diluent (1) having a specific gravity of 0.792 and the specific gravity of the resulting composition is shown in Table 5 and FIG. .
[Formula 1] ρ12 = (W1 + W2) / (W1 / ρ1 + W2 / ρ2)
ρ12: Specific gravity W1 of the mixture of substance 1 and substance 2, W2: Weight of substance 1 and substance 2 respectively ρ1, ρ2: Specific gravity of substance 1 and substance 2
＜封止材の成形＞
次に、得られた各組成物（Ｃ）を用い、酢酸ビニル含有量が２８重量％のＥＶＡ（Ａ）１００重量部に対して、表１〜４に示される重量比で組成物（Ｃ）を混合し、８０℃で押出成型により加熱圧延することにより０．５ｍｍ厚のＥＶＡ封止材を成形し、実施例及び比較例の各ＥＶＡ封止材を得た。
<Molding of sealing material>
Next, using each composition (C) obtained, the composition (C) at a weight ratio shown in Tables 1 to 4 with respect to 100 parts by weight of EVA (A) having a vinyl acetate content of 28% by weight. Were mixed and heated and rolled by extrusion at 80 ° C. to form an EVA sealing material having a thickness of 0.5 mm, thereby obtaining each EVA sealing material of Examples and Comparative Examples.
得られたそれぞれのＥＶＡ封止材を用い、発泡試験、スコーチ試験及びゲル分率の測定を行った。その結果を実施例については表１、２に、比較例については表３、４に示す。 Using each obtained EVA sealing material, the foaming test, the scorch test, and the measurement of the gel fraction were performed. The results are shown in Tables 1 and 2 for Examples and Tables 3 and 4 for Comparative Examples.
＜発泡試験＞
各実施例および比較例において作製されたＥＶＡ封止材を縦３ｃｍ、横６ｃｍに切り出し、ＭＳパウチフィルム（株式会社明光商会製）に挟み、加熱してラミネート加工したものを１３５℃で１０分間加熱し、その際に発生するガスによるフィルムの膨れを目視で観察し、評価した。比較例３−１と同等レベルの膨らみであった場合を◎、僅かにふくらみが大きい場合を○、膨らみが顕著に大きい場合を×として評価した。
<Foaming test>
The EVA sealing material produced in each example and comparative example was cut into a length of 3 cm and a width of 6 cm, sandwiched between MS pouch films (manufactured by Meiko Shokai Co., Ltd.), heated and laminated, and heated at 135 ° C. for 10 minutes. Then, the swelling of the film due to the gas generated at that time was visually observed and evaluated. A case where the bulge was the same level as in Comparative Example 3-1 was evaluated as ◎, a case where the bulge was slightly large was evaluated as ◯, and a case where the bulge was significantly large was evaluated as x.
＜スコーチ試験＞
ＪＩＳ Ｋ ６３００−２：２００１に準じて、各実施例および比較例の封止材を用いて、ＪＳＲトレーディング（株）製キュラストメーターＶ型により、上型及び下型の温度を１００℃に設定し、±１°の振幅角度でトルク測定を行った。１００℃で架橋した場合の最小トルク値から０．1Ｎ・ｍに達するまでの時間をスコーチ時間として求めた。スコーチ時間が１３分以上の場合を○、１３分未満の場合を×として評価した。
<Scorch test>
In accordance with JIS K 6300-2: 2001, the temperature of the upper mold and the lower mold is set to 100 ° C. using the Clastast V type manufactured by JSR Trading Co., Ltd., using the sealing materials of the examples and comparative examples. The torque was measured with an amplitude angle of ± 1 °. The time required to reach 0.1 N · m from the minimum torque value when crosslinked at 100 ° C. was determined as the scorch time. The case where the scorch time was 13 minutes or more was evaluated as ◯, and the case where it was less than 13 minutes was evaluated as ×.
＜ゲル分率の測定＞
各実施例および比較例において作製されたＥＶＡ封止材を用いて、ＪＳＲトレーディング（株）製キュラストメーターにより、１３５℃で１０分架橋を行った。架橋後のＥＶＡ封止材を秤量し（Ｘｇ）、これを１１０℃のキシレン中に１２時間浸漬して、１１０℃のキシレン中で洗浄・乾燥させた２００メッシュの金網で不溶解分をろ過し、金網上の残渣を真空乾燥して乾燥残渣の重量を測定し（Ｙｇ）、ゲル分率を算出した（ゲル分率（重量％）＝（Ｙ／Ｘ）×１００）。
<Measurement of gel fraction>
Using the EVA sealing material produced in each example and comparative example, crosslinking was performed at 135 ° C. for 10 minutes using a curast meter manufactured by JSR Trading Co., Ltd. The EVA sealing material after cross-linking is weighed (Xg), immersed in xylene at 110 ° C. for 12 hours, and the insoluble matter is filtered through a 200 mesh wire net washed and dried in xylene at 110 ° C. The residue on the wire net was vacuum dried, the weight of the dried residue was measured (Yg), and the gel fraction was calculated (gel fraction (% by weight) = (Y / X) × 100).
比較例３−１のＥＶＡ封止材は、Ｔ１ｈが高い有機過酸化物（II）を含んでいたため、発泡しにくい反面、ゲル分率が短時間で向上しなかった。比較例３−２のＥＶＡ封止材は、Ｔ１ｈが低い有機過酸化物（IV）を含んでいたため、ＥＶＡ封止材を成形する温度に近い１００℃におけるトルク値上昇が速かった。そのため、早期架橋（スコーチ）を起こし易く、成形時の取り扱いが困難であった。比較例３−３のＥＶＡ封止材は、芳香族の有機過酸化物（V）を含んでいたため、発泡が顕著であった。加えて、組成物（Ｃ）の比重が高く、取り扱いが困難であった。 Since the EVA sealing material of Comparative Example 3-1 contained an organic peroxide (II) having a high T 1h , it was difficult to foam, but the gel fraction did not improve in a short time. Since the EVA sealing material of Comparative Example 3-2 contained an organic peroxide (IV) having a low T 1h , the torque value increased at 100 ° C. close to the temperature for molding the EVA sealing material. Therefore, early crosslinking (scorch) is likely to occur, and handling during molding is difficult. Since the EVA sealing material of Comparative Example 3-3 contained an aromatic organic peroxide (V), foaming was significant. In addition, the specific gravity of the composition (C) was high and handling was difficult.
これに対し、実施例１−１〜３−４においては、Ｔ１ｈがより高く発泡しにくい有機過酸化物（II）を含む比較例３−１と遜色ない程度に発泡が少なく、且つ、短時間で速架橋が可能であり、ゲル分率が８０％以上のＥＶＡ封止材が得られた。実施例１−１〜３−４と比較例１−１〜２−２の結果について消防法判定に着目すると、組成物（Ｃ）は、有機過酸化物（Ｉ）１００重量部に対して希釈剤（Ｂ）を２０重量部以上含むことで、より安全性の高い消防法の第５類第２種に判定される。すなわち、有機過酸化物（Ｉ）の自己反応性を低く抑えることができ、より安全な使用が可能なことがわかる。一方、比較例１−１及び１−２のＥＶＡ封止材は、組成物（Ｃ）の自己反応性が高く、安全な使用が困難であった。また、実施例２−１，２と比較例１−４とを比較すると、組成物（Ｃ）の組成が、有機過酸化物（Ｉ）１００重量部に対して希釈剤（Ｂ）が５０重量部以下であると発泡しにくいことがわかる。これらのことから、組成物（Ｃ）は、有機過酸化物（Ｉ）１００重量部に対して希釈剤（Ｂ）を２０〜５０重量部とすることがわかる。 On the other hand, in Examples 1-1 to 3-4, T 1h is higher and foaming is less than that of Comparative Example 3-1 including organic peroxide (II) which is difficult to foam, and short. An EVA sealing material capable of rapid crosslinking in time and having a gel fraction of 80% or more was obtained. When focusing attention on the fire fighting method determination for the results of Examples 1-1 to 3-4 and Comparative Examples 1-1 to 2-2, the composition (C) was diluted with respect to 100 parts by weight of the organic peroxide (I). By containing 20 parts by weight or more of the agent (B), it is determined as a Class 5 type 2 of the Fire Service Act with higher safety. That is, it can be seen that the self-reactivity of the organic peroxide (I) can be kept low and safer use is possible. On the other hand, the EVA sealing materials of Comparative Examples 1-1 and 1-2 had high self-reactivity of the composition (C) and were difficult to use safely. Further, when Examples 2-1 and 2 and Comparative Example 1-4 were compared, the composition (C) had a diluent (B) of 50 weights per 100 parts by weight of the organic peroxide (I). It turns out that it is hard to foam that it is below a part. From these, it can be seen that the composition (C) contains 20 to 50 parts by weight of the diluent (B) with respect to 100 parts by weight of the organic peroxide (I).
実施例１−１〜１−４と比較例１−３との比較から、ＥＶＡ（Ａ）１００重量部に対する組成物（Ｃ）の重量比が０．１〜４重量部であると発泡しにくいことがわかる。一方、組成物（Ｃ）の重量比が５以上であると多くの発泡が見られた。 From comparison between Examples 1-1 to 1-4 and Comparative Example 1-3, foaming is difficult when the weight ratio of the composition (C) to 100 parts by weight of EVA (A) is 0.1 to 4 parts by weight. I understand that. On the other hand, many foaming was seen when the weight ratio of the composition (C) was 5 or more.
実施例１−１，３−１〜３−４と比較例２−１との比較から、希釈剤（Ｂ）の比重が０．７５より小さいと、発泡しやすくなることがわかる。また、実施例１−１，３−１〜３−４と比較例２−２とを比較すると、希釈剤（Ｂ）の比重が０．８７を超えると、架橋阻害を起こし、ゲル分率が短時間で向上しないことがわかる。これらのことから、希釈剤（Ｂ）の比重は０．７５以上、０．８７以下とすることがわかる。また、実施例１−１，３−１の結果から、希釈剤（Ｂ）の比重が０．７８以上、０．８２以下であると、より発泡しにくいことがわかり、希釈剤（Ｂ）の比重が０．７８以上、０．８０以下であると、短時間でのゲル分率がより高くなることがわかる。 From comparison between Examples 1-1, 3-1 to 3-4 and Comparative Example 2-1, it can be seen that when the specific gravity of the diluent (B) is smaller than 0.75, foaming is likely to occur. Moreover, when Examples 1-1 and 3-1 to 3-4 are compared with Comparative Example 2-2, when the specific gravity of the diluent (B) exceeds 0.87, crosslinking is inhibited, and the gel fraction is increased. It turns out that it does not improve in a short time. From these things, it turns out that the specific gravity of a diluent (B) shall be 0.75 or more and 0.87 or less. In addition, from the results of Examples 1-1 and 3-1, it can be seen that when the specific gravity of the diluent (B) is 0.78 or more and 0.82 or less, foaming is more difficult, and the diluent (B) It can be seen that when the specific gravity is 0.78 or more and 0.80 or less, the gel fraction in a short time becomes higher.
１０１ 太陽電池用セル
１０２ ガラス板
１０３ バックカバー
１０４ 封止材
101
Claims (2)
前記組成物（Ｃ）の含有量が、前記エチレン-酢酸ビニル共重合体（Ａ）１００重量部に対して、０．１〜４．０重量部であり、
前記組成物（Ｃ）中の有機過酸化物（I）と希釈剤（Ｂ）との重量比（I：Ｂ）が、１００：２０〜５０であり、
前記希釈剤（Ｂ）の比重が０．７５以上、０．８７以下であることを特徴とする太陽電池用封止材。
A composition comprising an ethylene-vinyl acetate copolymer (A) having a structural unit of 25 to 35% by weight formed from vinyl acetate, an organic peroxide (I) represented by the following formula (I), and a diluent (B) A solar cell encapsulant comprising an object (C),
The content of the composition (C) is 0.1 to 4.0 parts by weight with respect to 100 parts by weight of the ethylene-vinyl acetate copolymer (A),
The weight ratio (I: B) of the organic peroxide (I) and the diluent (B) in the composition (C) is 100: 20-50,
The solar cell sealing material, wherein the diluent (B) has a specific gravity of 0.75 or more and 0.87 or less.
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| JP2011140588A (en) * | 2010-01-08 | 2011-07-21 | Nof Corp | Ethylene-vinyl acetate copolymer composition and crosslinked product |
| JP2011151388A (en) * | 2009-12-24 | 2011-08-04 | Mitsubishi Plastics Inc | Solar cell sealing material and solar cell module produced using the same |
| JP2012099713A (en) * | 2010-11-04 | 2012-05-24 | Achilles Corp | Solar cell sealing material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2011151388A (en) * | 2009-12-24 | 2011-08-04 | Mitsubishi Plastics Inc | Solar cell sealing material and solar cell module produced using the same |
| JP2011140588A (en) * | 2010-01-08 | 2011-07-21 | Nof Corp | Ethylene-vinyl acetate copolymer composition and crosslinked product |
| JP2012099713A (en) * | 2010-11-04 | 2012-05-24 | Achilles Corp | Solar cell sealing material |
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