JP2005306946A - Sealant for solar battery etc - Google Patents
Sealant for solar battery etc Download PDFInfo
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- JP2005306946A JP2005306946A JP2004123624A JP2004123624A JP2005306946A JP 2005306946 A JP2005306946 A JP 2005306946A JP 2004123624 A JP2004123624 A JP 2004123624A JP 2004123624 A JP2004123624 A JP 2004123624A JP 2005306946 A JP2005306946 A JP 2005306946A
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- thermoplastic elastomer
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- 239000000565 sealant Substances 0.000 title abstract description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920001577 copolymer Polymers 0.000 claims abstract description 29
- 229920002725 thermoplastic elastomer Polymers 0.000 claims abstract description 28
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 27
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000003860 storage Methods 0.000 claims abstract description 17
- 239000003566 sealing material Substances 0.000 claims description 54
- -1 diene hydrocarbon Chemical class 0.000 claims description 29
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000003792 electrolyte Substances 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 14
- 238000007789 sealing Methods 0.000 claims description 12
- 150000001451 organic peroxides Chemical class 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000000377 silicon dioxide Substances 0.000 claims description 7
- 239000007784 solid electrolyte Substances 0.000 abstract description 13
- 239000011244 liquid electrolyte Substances 0.000 abstract description 9
- 150000002430 hydrocarbons Chemical class 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 150000001993 dienes Chemical class 0.000 abstract 1
- 238000000576 coating method Methods 0.000 description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 10
- 239000011248 coating agent Substances 0.000 description 8
- 229910002012 Aerosil® Inorganic materials 0.000 description 7
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000853 adhesive Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000001070 adhesive effect Effects 0.000 description 5
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000010248 power generation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 4
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 230000001771 impaired effect Effects 0.000 description 4
- 229920000554 ionomer Polymers 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229920002633 Kraton (polymer) Polymers 0.000 description 3
- 239000005062 Polybutadiene Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000007765 extrusion coating Methods 0.000 description 3
- 239000003925 fat Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002857 polybutadiene Polymers 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002313 adhesive film Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- LYRFLYHAGKPMFH-UHFFFAOYSA-N octadecanamide Chemical compound CCCCCCCCCCCCCCCCCC(N)=O LYRFLYHAGKPMFH-UHFFFAOYSA-N 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 2
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- NOBYOEQUFMGXBP-UHFFFAOYSA-N (4-tert-butylcyclohexyl) (4-tert-butylcyclohexyl)oxycarbonyloxy carbonate Chemical compound C1CC(C(C)(C)C)CCC1OC(=O)OOC(=O)OC1CCC(C(C)(C)C)CC1 NOBYOEQUFMGXBP-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- AGXUVMPSUKZYDT-UHFFFAOYSA-L barium(2+);octadecanoate Chemical compound [Ba+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O AGXUVMPSUKZYDT-UHFFFAOYSA-L 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 1
- 150000001565 benzotriazoles Chemical class 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 229920006332 epoxy adhesive Polymers 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 230000009975 flexible effect Effects 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001195 polyisoprene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229940037312 stearamide Drugs 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003505 terpenes Chemical class 0.000 description 1
- 235000007586 terpenes Nutrition 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 229940035289 tobi Drugs 0.000 description 1
- NLVFBUXFDBBNBW-PBSUHMDJSA-N tobramycin Chemical compound N[C@@H]1C[C@H](O)[C@@H](CN)O[C@@H]1O[C@H]1[C@H](O)[C@@H](O[C@@H]2[C@@H]([C@@H](N)[C@H](O)[C@@H](CO)O2)O)[C@H](N)C[C@@H]1N NLVFBUXFDBBNBW-PBSUHMDJSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 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
- Y02E10/542—Dye sensitized solar cells
Landscapes
- Sealing Material Composition (AREA)
- Photovoltaic Devices (AREA)
- Sealing Battery Cases Or Jackets (AREA)
- Hybrid Cells (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
Description
本発明は、太陽電池、有機ＥＬ素子等の電極間を接合し、液体電解質、擬固体電解質、固体電解質、有機発光層等を封止し、かつフィルムタイプの太陽電池、有機ＥＬ素子等にも対応可能なフレキシブル性を有するシール材に関するものである。 This invention joins electrodes, such as a solar cell and an organic EL element, seals a liquid electrolyte, a quasi-solid electrolyte, a solid electrolyte, an organic light emitting layer, etc., and also applies to a film type solar cell, an organic EL element, etc. The present invention relates to a sealing material having flexibility.
近年、地球温暖化問題の解決に向け、二酸化炭素発生を伴わない太陽電池や風力発電のような再生可能エネルギーの研究開発が盛んに行われている。特に、無尽蔵に存在する太陽エネルギーを直接電気に変換でき、クリーンなエネルギーを入手できる太陽電池は、二酸化炭素削減のキーテクノロジーとして非常に期待されている。 In recent years, research and development of renewable energy such as solar cells and wind power generation without generating carbon dioxide has been actively conducted to solve the global warming problem. In particular, solar cells that can convert inexhaustible solar energy directly into electricity and obtain clean energy are highly expected as key technologies for carbon dioxide reduction.
太陽電池に関しては、まず最初にシリコン系Ｐｎ接合太陽電池が開発され、それ以降種々の太陽電池が開発されてきた。用いられた半導体は、主としてシリコンやＧaＡｓ、ＣｕｌｎＳｅ２等の化合物半導体に代表される無機系材料である。現在、無機系半導体を用いた太陽電池の中で最も安価なものがアモルファスシリコン太陽電池であるが、それにおいても、一般の火力発電に対抗できる低コスト化は将来にわたって困難であると予想されている。太陽電池が他の発電技術に対抗でき、今後さらに普及するためには、低コスト化が最大の課題となっている。 Regarding solar cells, first, silicon-based Pn junction solar cells have been developed, and since then various solar cells have been developed. The used semiconductor is mainly an inorganic material typified by a compound semiconductor such as silicon, GaAs, or CulSe 2 . At present, amorphous silicon solar cells are the cheapest solar cells using inorganic semiconductors, but even in that case, it is expected that cost reduction that can counter general thermal power generation will be difficult in the future. Yes. In order for solar cells to compete with other power generation technologies and become more widespread in the future, cost reduction is the biggest issue.
このような状況下、新しい発電原理に基づく色素増感太陽電池は、安価な酸化チタンを用いるものであり、またプラスチック化が可能であり、Ｒｏｌｌ ｔｏ Ｒｏｌｌの生産方式を用いることができ、大幅に低コスト化が可能な次世代太陽電池として注目を集めるようになった。この太陽電池において、変換効率が最も高いのは、液体電解質を用いた場合である。しかし、液体電解質を用いた場合には、液漏れ等の問題が起こり得ること、また液体電解質を用いた場合より変換効率は劣るが液漏れ等の問題が起こらない固体電解質を用いた場合にはガスバリア性が求められること、また基材がフレキシブルなプラスチックのためシール材にもフレキシブル性が求められること等から、シール材が太陽光発電システムの性能向上の重要なポイントとなる。 Under such circumstances, the dye-sensitized solar cell based on the new power generation principle uses inexpensive titanium oxide, can be made into a plastic, can use the production method of Roll to Roll, It has attracted attention as a next-generation solar cell capable of reducing costs. In this solar cell, the conversion efficiency is highest when a liquid electrolyte is used. However, when a liquid electrolyte is used, problems such as liquid leakage may occur, and when a solid electrolyte is used that does not cause problems such as liquid leakage, although the conversion efficiency is lower than when a liquid electrolyte is used. The sealing material is an important point for improving the performance of the photovoltaic power generation system because the gas barrier property is required and the base material is flexible plastic and the sealing material is also required to have flexibility.
さらに、次世代ディスプレイとして期待されている有機ＥＬは、従来の液晶ディスプレイと異なり、バックライトが不要、低消費電力、視野角が広い、動画表示に優れている、小型薄膜化が可能等、多くの特徴を備えている。しかし、有機発光層等が酸素や水分にふれると発光特性が急激に劣化するという弱点があり、有機ＥＬにおいてもシール材がディスプレイ寿命の延長の重要なポイントになっている。 Furthermore, unlike conventional liquid crystal displays, organic EL, which is expected as a next-generation display, does not require a backlight, has low power consumption, has a wide viewing angle, is excellent in video display, and can be made thin and thin. It has the characteristics of However, there is a weak point that when the organic light-emitting layer or the like is exposed to oxygen or moisture, the light emission characteristics are rapidly deteriorated, and the sealing material is an important point for extending the display life even in the organic EL.
従来、シール材としては、エポキシ系接着剤（特許文献１、２）、アイオノマー樹脂系接着フィルム等が用いられている。しかし、エポキシ系接着剤においては、加熱接着後、硬化してしまう為にフレキシブル性に乏しい。そして、特許文献１、２でのエポキシ系接着剤の使用は、ガラス基板においてである。また、アイオノマー樹脂系接着フィルムにおいては、電解質や有機発光層等の封止性が不十分で、短期間で電解質成分が抜けてしまうという問題を抱えている。
本発明の目的は、太陽電池、有機ＥＬ素子等の電極間を接合し、液体電解質、擬固体電解質、固体電解質、有機発光層等を封止し、かつフィルムタイプの太陽電池、有機ＥＬ素子等にも対応可能なフレキシブル性を有するシール材を提供するものである。 The object of the present invention is to join electrodes of solar cells, organic EL elements, etc., seal liquid electrolytes, quasi-solid electrolytes, solid electrolytes, organic light emitting layers, etc., and film type solar cells, organic EL elements, etc. The sealing material which has the flexibility which can respond also to this is provided.
（１）本発明は、スチレンとジエン系炭化水素の共重合体を主体とする熱可塑性エラストマーを含み、加熱処理前及び１２０℃、１分間の加熱処理後の２０〜８０℃での貯蔵弾性畢Ｇ′が３×１０５〜１×１０８Ｐａであることを特徴とするシール材に関する。 (1) The present invention includes a thermoplastic elastomer mainly composed of a copolymer of styrene and a diene hydrocarbon, and has a storage elastic modulus at 20 to 80 ° C. before the heat treatment and after the heat treatment at 120 ° C. for 1 minute. The sealing material is characterized in that G ′ is 3 × 10 5 to 1 × 10 8 Pa.
（２）本発明は、熱可塑性エラストマー１００重量部に対し、有機過酸化物を１０重量部以下の範囲で含むことを特徴とする、（１）に記載のシール材に関する。 (2) The present invention relates to the sealing material according to (1), wherein the organic peroxide is contained in an amount of 10 parts by weight or less with respect to 100 parts by weight of the thermoplastic elastomer.
（３）本発明は、熱可塑性エラストマー１００重量部に対し、充填剤を３０重量部以下の範囲で含むことを特徴とする、（１）または（２）に記載のシール材に関する。 (3) The present invention relates to the sealing material according to (1) or (2), wherein the filler is contained in an amount of 30 parts by weight or less with respect to 100 parts by weight of the thermoplastic elastomer.
（４）本発明は、充填剤が疎水化シリカ、又はチタニアであることを特徴とする、（３）に記載のシール材に関する。 (4) The present invention relates to the sealing material according to (3), wherein the filler is hydrophobized silica or titania.
（５）本発明は、熱可塑性エラストマー１００重量部に対し、アクリル系オリゴマーを８０重量部以下の範囲で含むことを特徴とする、（１）〜（４）のいずれか１つに記載のシール材に関する。 (5) The seal according to any one of (1) to (4), wherein the present invention contains acrylic oligomer in an amount of 80 parts by weight or less based on 100 parts by weight of the thermoplastic elastomer. Regarding materials.
（６）本発明は、熱可塑性エラストマー１００重量部に対し、シランカップリング剤を１０重量部以下の範囲で含むことを特徴とする、（１）〜（５）のいずれか１つに記載のシール材に関する。 (6) The present invention includes the silane coupling agent in a range of 10 parts by weight or less with respect to 100 parts by weight of the thermoplastic elastomer, as described in any one of (1) to (5) It relates to a sealing material.
（７）本発明は、太陽電池及び有機ＥＬ素子の電極間の接合又は電池の電解質及び有機発光層の封止に使用するための（１）〜（６）のいずれか１項に記載のシール材に関する。 (7) The seal according to any one of (1) to (6), wherein the present invention is used for bonding between a solar cell and an electrode of an organic EL element or sealing an electrolyte and an organic light emitting layer of the battery. Regarding materials.
本発明により、太陽電池、有機ＥＬ素子等の電極間を接合し、液体電解質、擬固体電解質、固体電解質、有機発光層等を封止し、かつフィルムタイプの太陽電池、有機ＥＬ素子等にも対応可能なフレキシブル性を有するシール材を得ることができる。 According to the present invention, the electrodes of solar cells, organic EL elements, etc. are joined together, the liquid electrolyte, pseudo solid electrolyte, solid electrolyte, organic light emitting layer, etc. are sealed, and the film type solar cells, organic EL elements, etc. It is possible to obtain a sealing material having a flexible property.
本発明において貯蔵弾性率Ｇ′は、応力と歪の比である複素弾性率Ｇ*の実数部と定義され、Ｇ′＝（σ０／γ０ｃ０ｓδ（σ０：時刻ｔ＝０における一定の応力、γ０：振幅、δ：位相差）により測定される。本発明のシール材の貯蔵弾性率Ｇ′は、加熱処理前及び１２０℃、１分間の加熱処理後の２０〜８０℃での貯蔵弾性率Ｇ′が３×１０５〜１×１０８Ｐａ、好ましくは３×１０５〜８×１０７Ｐａであり、特に好ましくは５×１０５〜５×１０７Ｐａである。シール材の貯蔵弾性率Ｇ′が３×１０５Ｐａを下回る場合には、シール材の形状維持が困難であり、液状の製品形態にする、或いはテープ、またはシート状の製品形態にする場合には、低温保存が必要となり、シール材製品としての保管方法が煩わしくなる。また、耐熱安定性が悪くなり、例えば、夏場の閉め切った車内、室内等の高温下で使用した場合に不具合が生じ易くなる。シール材の貯蔵弾性率Ｇ′が１×１０８Ｐａを超える場合には、シール材の粘着性が不足し、仮接着し難くなる。また、シール材のフレキシブル性が損なわれ、太陽電池、有機ＥＬ素子等の電極フィルムを折り曲げた際に追従することが難しく、シール材が剥れたり、割れたりする場合がある。 In the present invention, the storage elastic modulus G ′ is defined as the real part of the complex elastic modulus G * , which is the ratio of stress and strain, and G ′ = (σ 0 / γ 0 c0sδ (σ 0 : constant at time t = 0) (Stress, γ 0 : amplitude, δ: phase difference) The storage elastic modulus G ′ of the sealing material of the present invention is 20 ° C. to 20 ° C. before heat treatment and 120 ° C. and 1 minute after heat treatment. The storage elastic modulus G ′ is 3 × 10 5 to 1 × 10 8 Pa, preferably 3 × 10 5 to 8 × 10 7 Pa, and particularly preferably 5 × 10 5 to 5 × 10 7 Pa. When the storage elastic modulus G ′ is less than 3 × 10 5 Pa, it is difficult to maintain the shape of the sealing material, and in the case of a liquid product form, or a tape or sheet product form, Low temperature storage is required, and the storage method as a sealing material product becomes troublesome. Thermal stability is deteriorated, for example, when a vehicle in which Shimeki' the summer, tends to occur failure when used at high temperatures such as indoors. The storage modulus of the sealing member G 'exceeds 1 × 10 8 Pa is In addition, the adhesive of the sealing material is insufficient, and it becomes difficult to temporarily bond the sealing material, and the flexibility of the sealing material is impaired, and it is difficult to follow the electrode film of a solar cell, an organic EL element, etc. May peel off or crack.
本発明において使用される熱可塑性エラストマーとは、常温ではゴム弾性を示すが、高温では可塑化され、成形できる高分子材料を意味する。 The thermoplastic elastomer used in the present invention means a polymer material that exhibits rubber elasticity at room temperature but is plasticized and moldable at high temperature.
本発明において使用されるスチレンとジエン系炭化水素の共重合体を「主体」とするとは、熱可塑性エラストマー中にスチレンとジエン系炭化水素の共重合体が５０Ｗｔ％以上含有されていることを意味する。 The phrase “mainly” refers to the copolymer of styrene and diene hydrocarbon used in the present invention means that the thermoplastic elastomer contains a copolymer of styrene and diene hydrocarbon of 50 Wt% or more. To do.
本発明において使用されるジエン系炭化水素とは、ブタジエン、イソプレンなどの分子内に２重結合を２つ有する炭化水素を意味する。 The diene hydrocarbon used in the present invention means a hydrocarbon having two double bonds in the molecule, such as butadiene and isoprene.
本発明において使用されるスチレンとジエン系炭化水素の共重合体には、スチレンとジエン系炭化水素の共重合体、或いはスチレンとジエン系炭化水素の共重合体の部分水素添加変性物、或いはスチレンとジエン系炭化水素の共重合体の完全水素添加変性物等の種々のものが含まれることができ、例えば、スチレン−イソプレン共重合体、スチレン−ブタジエン共重合体、（α−メチル−スチレン）−イソプレン共重合体、（α−メチル−スチレン）−ブタジエン共重合体、スチレン−エチレン−１ブテン共重合体、スチレン−エチレン−プロピレン共重合体、（α−メチル−スチレン）−エチレン−１ブテン共重合体、（α−メチル−スチレン）−エチレン−プロピレン共重合体等を挙げることができるが、シール材の形状安走性と粘着性のバランスの点からは、スチレンとジエン系炭化水素の重量比が１０：９０〜５０：５０、特に１５：８５〜４５：５５のものを含むことがより好ましい。そして、スチレンとジエン系炭化水素の共重合体のメルトフローレート（ＭＦＲ：１９０℃、２１．２Ｎ）が、２０ｇ／１０min以下、特に１８ｇ／１０min以下のものを用いるのがより好ましい。そして、熱可塑性エラストマーは、上記のスチレンとジエン系炭化水素の共重合体を主体とするものであれば、種々のものを使用でき、例えば、クレイトンポリマージャパン製Ｄ１１１６、Ｄ４００Ｐ、日本ゼオン製クインタック３４６０、３４５０等が挙げられる。熱可塑性エラストマーには、スチレンとジエン系炭化水素の共重合体の他に５０Ｗｔ％未満のその他のエラストマー、例えばオレフィン系、塩化ビニル系、ブタンジエン系、ウレタン系熱可塑性エラストマー等を含めることができる。 The copolymer of styrene and diene hydrocarbon used in the present invention includes a copolymer of styrene and diene hydrocarbon, a partially hydrogenated modified product of styrene and diene hydrocarbon copolymer, or styrene. And various modifications such as a completely hydrogenated modified product of a copolymer of a diene hydrocarbon and a diene hydrocarbon, such as a styrene-isoprene copolymer, a styrene-butadiene copolymer, (α-methyl-styrene) -Isoprene copolymer, (α-methyl-styrene) -butadiene copolymer, styrene-ethylene-1 butene copolymer, styrene-ethylene-propylene copolymer, (α-methyl-styrene) -ethylene-1 butene Copolymer, (α-methyl-styrene) -ethylene-propylene copolymer, and the like. From the lance point, the weight ratio of styrene and diene hydrocarbon 10:90 50, in particular 15: 85 to 45: and more preferably contains 55 ones. It is more preferable to use a copolymer of styrene and diene hydrocarbon having a melt flow rate (MFR: 190 ° C., 21.2 N) of 20 g / 10 min or less, particularly 18 g / 10 min or less. Various thermoplastic elastomers can be used as long as they are mainly composed of the above-mentioned copolymer of styrene and diene hydrocarbons. 3460, 3450 and the like. In addition to the copolymer of styrene and diene hydrocarbon, the thermoplastic elastomer may include other elastomers of less than 50 Wt%, for example, olefin, vinyl chloride, butanediene, urethane thermoplastic elastomer and the like.
本発明で使用される充填剤は、シール材の形状安定性のために用いられ、添加することにより、形状安定性をよりよくするもので、シリカ、アルミナ、炭酸カルシウム、タルク、酸化チタン等の種々のものを１種以上使用することができるが、シリカ、又はチタニアを用いることが好ましい。シール材の表面平滑性の点からは、一次粒子の平均径が１００nm以下の充填剤を用いるのが好ましく、４０nm以下の充填剤を用いるのがより好ましい。また、防湿性の点からは、表面を疎水化処理したものを用いるのがより好ましい。充填剤の添加量としては、熱可塑性エラストマー１００重量部に対し３０重量部以下であることが好ましく、２０重量部以下であることが特に好ましい。３０重量部を超える場合には、シール材の粘着性が不足し、仮接着し難くなる場合がある。 The filler used in the present invention is used for the shape stability of the sealing material, and is added to improve the shape stability, such as silica, alumina, calcium carbonate, talc, titanium oxide, etc. One or more of various materials can be used, but it is preferable to use silica or titania. From the viewpoint of the surface smoothness of the sealing material, it is preferable to use a filler having an average primary particle diameter of 100 nm or less, and more preferably a filler having a diameter of 40 nm or less. Moreover, it is more preferable to use what hydrophobized the surface from a moisture-proof point. The addition amount of the filler is preferably 30 parts by weight or less, particularly preferably 20 parts by weight or less, relative to 100 parts by weight of the thermoplastic elastomer. When it exceeds 30 weight part, the adhesiveness of a sealing material may be insufficient and it may become difficult to temporarily bond.
本発明で使用されるアクリル系オリゴマーとは、熱や光で反応出来るアクリル基を少なくとも１つ以上有するオリゴマーを意味し、電解質封止性向上のために用いられ、添加することにより、電解質封止性がよりよくなる。使用されるアクリル系オリゴマーとしては、種々のものを使用でき、例えば、ウレタンアクリレート、エポキシアクリレート、ポリエステルアクリレート、ポリエーテルアクリレート、シリコンアクリレート、ポリブタジエンアクリレート等を挙げることができる。ウレタンアクリレートとしては、例えば、サートマー製ＣＮ９６４、ＣＮ３１０５等を挙げることができる。エポキシアクリレートとしては、例えば、昭和高分子製ＶＲ−９０、ＶＲ−７７等を挙げることができる。ポリエステルアクリレートとしては、例えば、東亞合成製アロニックスＭ−７１００、Ｍ−８０３０等を挙げることができる。ポリエーテルアクリレートとしては、例えば、サートマー製ＣＮ５０１等を挙げることができる。シリコンアクリレートとしては、例えば、特公昭５１−４２９６１号公報、特公昭５４−６５１２号公報等に開示されているもの等を挙げることができる。ポリブタジエンアクリレートとしては、例えば、新日本石油化学製ＭＭ−１０００−８０等を挙げることができる。アクリル系オリゴマーの添加量としては、熱可塑性エラストマー１００重量部に対し０以上８０重量部以下であることが好ましく、７０重量部以下であることが特に好ましい。８０重量部を超える場合には、形状安定性、及び／或いは、加熱接着後シール材のフレキシブル性が損なわれる場合がある。 The acrylic oligomer used in the present invention means an oligomer having at least one acrylic group capable of reacting with heat or light, and is used for improving the electrolyte sealing property. Sex is better. Various acrylic oligomers can be used, and examples thereof include urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, silicon acrylate, and polybutadiene acrylate. Examples of urethane acrylates include Sartomer CN964, CN3105, and the like. Examples of the epoxy acrylate include VR-90 and VR-77 manufactured by Showa Polymer Co., Ltd. Examples of the polyester acrylate include Aronix M-7100 and M-8030 manufactured by Toagosei Co., Ltd. Examples of the polyether acrylate include CN501 manufactured by Sartomer. Examples of the silicon acrylate include those disclosed in Japanese Patent Publication No. 51-42961 and Japanese Patent Publication No. 54-6512. Examples of the polybutadiene acrylate include MM-1000-80 manufactured by Shin Nippon Petrochemical Co., Ltd. The amount of the acrylic oligomer added is preferably from 0 to 80 parts by weight, particularly preferably 70 parts by weight or less, based on 100 parts by weight of the thermoplastic elastomer. If it exceeds 80 parts by weight, shape stability and / or flexibility of the sealing material after heat bonding may be impaired.
本発明のシール材で用いる有機過酸化物は、スチレンとジエン系炭化水素の共重合体を架橋させる目的で添加され、添加することにより電解質封止性がよりよくなる。幅広い材質の電極フィルムの選択を可能とする為に加熱接着時の温度を低くできる点から、１３０℃以下、好ましくは１２０℃以下で反応開始するものが好ましく、使用される有機過酸化物としては、ジ（４−ｔ−ブチルシクロヘキシル）パーオキシジカルボネート、ジラウロイルパーオキサイド等が挙げられる。そして、例えば日本油脂製のパーブチルＢ、パークミルＤ等が挙げられる。添加量としては、スチレンとジエン系炭化水素の共重合体を主体とする熱可塑性エラストマー１００重量部に対し１０重量部以下であり、８重量部以下であることが特に好ましい。１０重量部を超える場合には、加熱接着後シール材のフレキシブル性が損なわれる場合がある。 The organic peroxide used in the sealing material of the present invention is added for the purpose of crosslinking the copolymer of styrene and diene hydrocarbon, and the electrolyte sealing property is improved by the addition. From the point that the temperature at the time of heat bonding can be lowered in order to enable selection of an electrode film of a wide range of materials, those that start the reaction at 130 ° C. or lower, preferably 120 ° C. or lower are preferable. , Di (4-t-butylcyclohexyl) peroxydicarbonate, dilauroyl peroxide, and the like. Examples thereof include perbutyl B, park mill D, and the like made from Japanese fats and oils. The addition amount is 10 parts by weight or less, particularly preferably 8 parts by weight or less, based on 100 parts by weight of the thermoplastic elastomer mainly composed of a copolymer of styrene and a diene hydrocarbon. If it exceeds 10 parts by weight, the flexibility of the sealing material after heat bonding may be impaired.
本発明のシール材で用いるシランカップリング剤は、接着力向上の目的で添加され、添加することにより接着力がよりよくなる。使用されるシランカップリング剤としては、種々のものを使用でき、例えば、官能基にアミノ基、アクリロキシ基、メタクリロキシ基、エポキシ基、メルカプト基、クロロプロピル基、ビニル基等をもつシランカップリング剤を挙げることができる。添加量としては、熱可塑性エラストマー１００重量部に対し１０重量部以下であることが好ましく、８重量部以下であることが特に好ましい。１０重量部を超える場合には、加熱接着後シール材の接着力が損なわれる場合がある。 The silane coupling agent used in the sealing material of the present invention is added for the purpose of improving the adhesive strength, and the adhesive strength is improved by the addition. Various silane coupling agents can be used. For example, a silane coupling agent having an amino group, acryloxy group, methacryloxy group, epoxy group, mercapto group, chloropropyl group, vinyl group or the like as a functional group. Can be mentioned. The addition amount is preferably 10 parts by weight or less, particularly preferably 8 parts by weight or less, with respect to 100 parts by weight of the thermoplastic elastomer. When it exceeds 10 weight part, the adhesive force of the sealing material after heat bonding may be impaired.
本発明のシール材には、本発明の目的を損なわない範囲で必要に応じて、各種添加剤を配合することができる。すなわち、ステアリン酸、ステアリン酸アミド、ステアリン酸カルシウム、ステアリン酸バリウム、ステアリン酸亜鉛等の滑剤、フェノール系、フォスファイト系、チオエーテル系等の酸化防止剤、ベンゾトリアゾール系、ヒンダードアミン系、ベンゾエート系等の紫外線吸収剤、または安定剤、ガラスバルーン、シリカバルーン等の無機系中空粒子、アクリル系、高分子量ポリオレフィン系パウダー等の高分子微小球、カルボキシル系、アミノ系等のチタネート系カップリング剤、リン系、フッ素系、有機フッ素系等の界面活性剤、ロジン系、テルペン系、石油系、スチレン系、フェノール系等の水添樹脂等の粘着付与樹脂、スチレン−ブタジエン共重合体のエポキシ化物、ポリブタジエン、ポリイソプレン、ウレタンアクリレート、ポリ酢酸ビニル、ポリエチレンエチルアクリレート、ポリビニルアルコール、ポリアミド等のポリマーやオリゴマーを適宜添加することができる。 In the sealing material of the present invention, various additives can be blended as necessary within a range not impairing the object of the present invention. That is, lubricants such as stearic acid, stearamide, calcium stearate, barium stearate, zinc stearate, antioxidants such as phenols, phosphites, thioethers, benzotriazoles, hindered amines, benzoates, etc. Absorbents or stabilizers, inorganic hollow particles such as glass balloons and silica balloons, polymer microspheres such as acrylic and high molecular weight polyolefin powders, carboxylate and amino titanate coupling agents, phosphorous, Fluorine-based, organic fluorine-based surfactants, rosin-based, terpene-based, petroleum-based, styrene-based, phenol-based hydrogenated resins and other tackifying resins, styrene-butadiene copolymer epoxides, polybutadiene, poly Isoprene, urethane acrylate, poly Vinyl acid, polyethylene ethyl acrylate, polyvinyl alcohol, may be added as appropriate polymers and oligomers such as polyamide.
本発明のシール材は、公知の各種方法によって製造することができるが、例えば押出し塗工法、溶展塗工法が好ましい。押出し塗工法としては、スチレンとジエン系炭化水素の共重合体を主体とする熱可塑性エラストマーと有機過酸化物と必要に応じて充填剤、アクリル系オリゴマー、並びにシランカップリング剤を加熱混練し、押出すことによって製造することができる。溶展塗工法としては、スチレンとジエン系炭化水素の共重合体を主体とする熱可塑性エラストマーと有機過酸化物と必要に応じて充填剤、アクリル系オリゴマー、並びにシランカップリング剤を溶剤に分散させ、塗布、乾燥させることによって製造することができる。 The sealing material of the present invention can be produced by various known methods. For example, an extrusion coating method and a spread coating method are preferable. As an extrusion coating method, a thermoplastic elastomer mainly composed of a copolymer of styrene and a diene hydrocarbon, an organic peroxide, and if necessary, a filler, an acrylic oligomer, and a silane coupling agent are heated and kneaded, It can be manufactured by extrusion. As the spread coating method, a thermoplastic elastomer mainly composed of a copolymer of styrene and a diene hydrocarbon, an organic peroxide, and a filler, an acrylic oligomer, and a silane coupling agent as needed are dispersed in a solvent. And can be produced by coating and drying.
本発明のシール材は電極に仮接着後、加熱接着することにより液体電解質、凝固体電解質、固体電解質、有機発光層等を封止することができる。ここで「仮接着」とは電極にシール材を加熱ローラーを使用して仮固定することを意味し、加熱条件としては、１５〜８０℃が好ましく、２０〜７０℃であることが特に好ましい。「加熱接着」とは仮固定されたシール材と電極を９０〜１３０℃、０.５〜５分問、好ましくは１００〜１２５℃、１〜３分間加熱により接着することを意味する。 The sealing material of the present invention can seal a liquid electrolyte, a solid electrolyte, a solid electrolyte, an organic light-emitting layer, and the like by heat-bonding after temporary bonding to an electrode. Here, “temporary bonding” means that the sealing material is temporarily fixed to the electrode using a heating roller, and the heating condition is preferably 15 to 80 ° C., and particularly preferably 20 to 70 ° C. “Heat bonding” means that the temporarily fixed sealing material and electrode are bonded by heating at 90 to 130 ° C. for 0.5 to 5 minutes, preferably 100 to 125 ° C. for 1 to 3 minutes.
本発明のシール材の提供形態としては、押出し塗工法、溶展塗工法等により製造したテープ、或いはシート状のような塗布、乾燥後の状態でもかまわないし、溶媒等に分散させた液状で提供することもできる。
以下、本発明の実施例を挙げて具体的に説明するが、本発明はこれらの実施例に限定されるものではない。
As a form of providing the sealing material of the present invention, a tape manufactured by an extrusion coating method, a spread coating method or the like, or a sheet-like coating or drying state may be used, or a liquid dispersed in a solvent or the like is provided. You can also
EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.
［実施１］
スチレンとジエン系炭化水素の共重合体からなる熱可塑性エラストマー（日本ゼオン製クインタック３４６０；ＳＩＳ共重合体、スチレンとイソプレンの重量比２５：７５）／有機過酸化物（日本油脂製パーロイルＬ；ジラウロイルパーオキサイド）＝１００重量部／５重量部の組成物を混練、乾燥後の塗布厚が３０μｍになるよう溶展塗工してシール材を作成した。
[Implementation 1]
Thermoplastic elastomer made of a copolymer of styrene and diene hydrocarbon (Quintac 3460 manufactured by Nippon Zeon; SIS copolymer, weight ratio of styrene and isoprene 25:75) / organic peroxide (Parroyl L manufactured by Nippon Oil &Fats; Dilauroyl peroxide) = 100 parts by weight / 5 parts by weight of the composition was kneaded and melt-coated to a coating thickness of 30 μm after drying to prepare a sealing material.
［実施２］
スチレンとジエン系炭化水素の共重合体からなる熱可塑性エラストマー（クレイトンポリマージャパン製Ｄ１１１６；ＳＢＳ共重合体、スチレンとブタジエンの重量比２３：７７）／有機過酸化物（日本油脂製パーロイルＬ）／充填剤（日本アエロジル型アエロジルＲ９７６ｓ；疎水化シリカ）＝１００重量部／３重量部／１０重量部の組成物を混練、乾燥後の塗布厚が３０μｍになるよう溶展塗工してシール材を作成した。
[Implementation 2]
Thermoplastic elastomer composed of a copolymer of styrene and diene hydrocarbon (D1116 made by Kraton Polymer Japan; SBS copolymer, weight ratio of styrene and butadiene 23:77) / Organic peroxide (Parroyl L made by NOF Corporation) / Filler (Nippon Aerosil-type Aerosil R976s; Hydrophobized silica) = 100 parts by weight / 3 parts by weight / 10 parts by weight of the composition, and melt-coated so that the coating thickness after drying is 30 μm. Created.
［実施３］
スチレンとジエン系炭化水素の共重合体からなる熱可塑性エラストマー（日本ゼオン製クインタック３４６０）／有機過酸化物（日本油脂製パーロイルＬ）／充填剤（日本アエロジル製アエロジルＲ９７２；疎水化シリカ）／アクリレート系オリゴマー（サートマー製ＣＮ３１０５；ウレタンアクリレート）＝１００重量部／４重量部／１５重量部／３０重量部の組成物を混練、乾燥後の塗布厚が３０μｍになるよう溶展塗工してシール材を作成した。
[Implementation 3]
Thermoplastic elastomer composed of a copolymer of styrene and diene hydrocarbon (Quintac 3460 manufactured by Nippon Zeon) / Organic peroxide (Perroyl L manufactured by Nippon Oil & Fats) / Filler (Aerosil R972 manufactured by Nippon Aerosil); Hydrophobized silica / Acrylate oligomer (CN3105 manufactured by Sartomer; urethane acrylate) = 100 parts by weight / 4 parts by weight / 15 parts by weight / 30 parts by weight of the composition kneaded and spread coated to a coating thickness of 30 μm after drying and sealed Made the material.
［比較１］
スチレンとジエン系炭化水素の共重合体からなる熱可塑性エラストマー（クレイトンポリマージャパン製Ｄ４００Ｐ；ＳＢＳ共重合体、スチレンとブタジエンの重量比２４：７６）／有機過酸化物（日本油脂製パーロイルＬ）／アクリレート系オリゴマー（サートマー製ＣＮ９６４；ウレタンアクリレート）／充填剤（日本アエロジル製アエロジルＲ９７６ｓ）＝１００重量部／６重量部／１００重量部／２０重量部の組成物を混練、乾燥後の塗布厚が３０μｍになるよう溶展塗工してシール材を作成した。
[Comparison 1]
Thermoplastic elastomer made of a copolymer of styrene and diene hydrocarbon (D400P made by Kraton Polymer Japan; SBS copolymer, styrene and butadiene weight ratio 24:76) / organic peroxide (Nippon Yushi Fatty Parroyl L) / Acrylate oligomer (Sartomer CN964; urethane acrylate) / filler (Aerosil R976s, Nippon Aerosil) = 100 parts by weight / 6 parts by weight / 100 parts by weight / 20 parts by weight A composition having a coating thickness after drying of 30 μm A sealant was prepared by melt coating.
［比較２］
スチレンとジエン系炭化水素の共重合体からなる熱可塑性エラストマー（クレイトンポリマージャパャパン製Ｄ１１１６）／有機過酸化物（日本油脂製パーロイルＬ）／アクリレート系オリゴマー（昭和高分子製ＶＲ−９０；エポキシアクリレート）／充填剤（日本アエロジル製アエロジルＲ９７２）＝１００重量部／１０重量部／１００重量部／２０重量部の組成物を混練、乾燥後の塗布厚が３０μｍになるよう溶展塗工してシール材を作成した。
[Comparison 2]
Thermoplastic elastomer composed of a copolymer of styrene and diene hydrocarbon (D1116 manufactured by Kraton Polymer Japan) / Organic peroxide (Parroyl L manufactured by NOF Corporation) / Acrylate oligomer (VR-90 manufactured by Showa High Polymer; Epoxy) Acrylate) / Filler (Aerosil R972 manufactured by Nippon Aerosil Co., Ltd.) = 100 parts by weight / 10 parts by weight / 100 parts by weight / 20 parts by weight of the composition, and melt-coated to a coating thickness of 30 μm after drying. A sealing material was created.
［比較３］
アイオノマー樹脂（三井・デュポンポリケミカル（株）製ハイミラン１６５２）を厚さが３０μｍになるように加熱押出し成形してシール材を作成した。
[Comparison 3]
An ionomer resin (High Milan 1652 manufactured by Mitsui DuPont Polychemical Co., Ltd.) was heated and extruded to a thickness of 30 μm to prepare a seal material.
＜貯蔵弾性率Ｇ′の測定＞
実施１〜３、比較１〜３のシール材について、直径８mm×高さ５mmの円柱形状に成形したサンプル、及びそれを１２０℃で１分間加熱処理したサンプルについて、粘弾性測定装置（レオメトリックス製レオバイブロンＲＤＡ−II）を用い、振動数６．２８ｒaｄ／ｓの条件で、２０℃及び８０℃の貯蔵弾性率Ｇ′を測定した。
<Measurement of storage elastic modulus G '>
About the sealing materials of Examples 1 to 3 and Comparative Examples 1 to 3, a viscoelasticity measuring device (manufactured by Rheometrics) for a sample formed into a cylindrical shape having a diameter of 8 mm and a height of 5 mm and a sample heat-treated at 120 ° C. for 1 minute Storage modulus G ′ at 20 ° C. and 80 ° C. was measured using Leovibron RDA-II) at a frequency of 6.28 rad / s.
＜形状安定性の確認＞
実施１〜３、比較１〜３のシール材について、４０℃雰囲気下に３０日保存し、変形の有無について目視確認した（変形なし○、変形あり×）。
<Confirmation of shape stability>
About the sealing material of Examples 1-3 and Comparative 1-3, it preserve | saved for 30 days in a 40 degreeC atmosphere, and visually confirmed about the presence or absence of a deformation | transformation (no deformation | transformation (circle), deformation | transformation x).
［製法］
実施１〜３、比較１〜３のシール材について、外寸５０mm×５０mm、内寸４３mm×４３mmの□状に成形し、６０mm×５０mmのＩＴ０膜蒸着フィルム（株式会社トービ製ＯＴＥＣ−１１０）に３辺の端に合わせて貼付し、７０℃に保たれた金属板上に１分間置くことにより仮接着し、次に電解質０．０５ｍＬ（プロピレンカーボネート／Ｉ２＝１００／２）を中に入れた後にＩＴ０膜蒸着フィルムを貼付していない側のシール材面に別の６０mm×５０mmのＩＴ０膜蒸着フィルムを３辺の端に合わせて貼付し、７０℃に保たれた金属板上に１分間置くことにより仮接着し、さらに１２０℃に保たれた金属板上に１分間置くことにより接着させ、評価用サンプルを作成した。
[Production method]
The sealing materials of Examples 1 to 3 and Comparative Examples 1 to 3 were formed into a □ shape having an outer size of 50 mm × 50 mm and an inner size of 43 mm × 43 mm, and were formed into a 60 mm × 50 mm IT0 film deposition film (OTEC-110 manufactured by Tobi Corporation). Affixed to the edges of the three sides, temporarily bonded by placing on a metal plate maintained at 70 ° C. for 1 minute, and then put 0.05 mL of electrolyte (propylene carbonate / I 2 = 100/2) inside After that, another 60mm x 50mm IT0 film deposition film is attached to the side of the sealing material on the side where the IT0 film deposition film is not affixed so as to fit the edges of the three sides, and is placed on a metal plate kept at 70 ° C for 1 minute. The sample was temporarily bonded, and further adhered by placing it on a metal plate kept at 120 ° C. for 1 minute to prepare a sample for evaluation.
＜シール性能、及び外観評価＞
実施１〜３及び比較１〜３のシール材を用い、上記製法に基づき作成した評価用サンプルについて、「接着性」、「電解質封止性」、「フレキシブル性」の評価を行った。
<Seal performance and appearance evaluation>
About the sample for evaluation created based on the said manufacturing method using the sealing material of Examples 1-3 and Comparative 1-3, "adhesiveness", "electrolyte sealing property", and "flexibility" were evaluated.
「接着性」：インストロン型引張試験機（オリエンテック製ＲＴＭ−１００）を用い、両側のＩＴ０膜蒸着フィルムのシール材が接着していない部分各５mmをチャックで挟み（チャック間隔７mm）、３００mm／minの速度でＴ型剥離して、剥離挙動を目視確認した（凝集破壊○、界面剥離×）。 "Adhesiveness": Using an Instron type tensile tester (Orientec RTM-100), sandwich each 5mm part of the IT0 film deposition film where the sealing material is not adhered with a chuck (chuck interval 7mm), 300mm T-type peeling was performed at a speed of / min, and the peeling behavior was visually confirmed (cohesive failure ○, interface peeling ×).
「電解質封止性」：８０℃、８０％ＲＨ下に１週間保存し、電解質が抜けていないか目視確認した（電解質が液漏れしていない○、電解質が液漏れしている×）。 “Electrolyte sealing property”: stored for 1 week at 80 ° C. and 80% RH, and visually confirmed whether or not the electrolyte was removed (the electrolyte did not leak, ○, the electrolyte leaked).
「フレキシブル性」：インストロン型引張試験機（オリエンテック製ＲＴＭ−１００）を用い、サンプルの６０mmの方向の上下各５mmをチャックで挟み（チャック間隔：５０mm）、１０００mm／minの速度でチャック間隔３０mmにし、直ぐに５０mmにする操作を１０回繰り返した後の不具合の有無を目視確認した（不具合なし○、不具合あり×）。 “Flexibility”: Using an Instron type tensile tester (Orientec RTM-100), the sample is clamped at 5 mm above and below in the direction of 60 mm with a chuck (chuck interval: 50 mm), and the chuck interval is 1000 mm / min. It was visually confirmed whether there was a defect after repeating the operation of making it 30 mm and immediately making it 50 mm 10 times (no defect ○, defect ×).
表１の結果から明らかなように、本発明の実施１〜３のシール材は、良好な形状安定性、及び接着性、電解質封止性、フレキシブル性を示した。他方、比較１は良好な接着性、電解質封止性、フレキシブル性を示したが、形状安定性が悪い。このように加熱処理前及び１２０℃、１分間の加熱処理後の２０〜８０℃での貯蔵弾性率Ｇ′が３×１０５Ｐａを下回っている場合には、シール材の形状維持が困難であり、液状の製品形態にする、或いはテープ、またはシート状の製品形態にするならば、低温保存が必要となり、シール材製品としての保管方法が煩わしくなる。また、比較２は「接着性」の試験では界面剥離し、また、「フレキシブル性」の試験においてシール材と電極が剥れ、電解質の漏れが生じた。このように加熱処理前及び１２０℃、１分間の加熱処理後の２０〜８０℃での貯蔵弾性率Ｇ′が１×１０８Ｐａを超えた場合には、シール材が硬くなり、接着性やフレキシブル性が悪くなる。また、比較３は「接着性」の試験では界面剥離し、また、「電解質封止性」の試験では電解質成分が抜けてしまい、Ｉ２由来の褐色の電解質が脱色してしまった。このようにスチレンとジエン系炭化水素の共重合体を主体とする熱可塑性エラストマーではなく、アイオノマー樹脂を用いた場合には、接着性や電解質封止性が悪くなる。 As is apparent from the results in Table 1, the sealing materials of Examples 1 to 3 of the present invention exhibited good shape stability, adhesiveness, electrolyte sealing properties, and flexibility. On the other hand, Comparative Example 1 showed good adhesion, electrolyte sealing properties, and flexibility, but poor shape stability. As described above, when the storage elastic modulus G ′ at 20 to 80 ° C. before the heat treatment and after the heat treatment at 120 ° C. for 1 minute is lower than 3 × 10 5 Pa, it is difficult to maintain the shape of the sealing material. If it is in the form of a liquid product, or in the form of a tape or sheet, low temperature storage is required, and the storage method as a sealing material product becomes troublesome. In Comparative 2, the interface peeled in the “adhesiveness” test, and the sealing material and the electrode peeled off in the “flexibility” test, resulting in electrolyte leakage. As described above, when the storage elastic modulus G ′ at 20 to 80 ° C. before the heat treatment and after the heat treatment at 120 ° C. for 1 minute exceeds 1 × 10 8 Pa, the sealing material becomes hard, Flexibility is poor. In comparison 3, in the “adhesiveness” test, the interface peeled off, and in the “electrolyte sealing property” test, the electrolyte component was lost, and the brown electrolyte derived from I 2 was decolorized. As described above, when an ionomer resin is used instead of a thermoplastic elastomer mainly composed of a copolymer of styrene and a diene hydrocarbon, adhesion and electrolyte sealing properties are deteriorated.
本発明のシール材は、スチレンとジエン系炭化水素の共重合体を主体とする、熱可塑性エラストマーを含み、加熱処理前及び１２０℃、１分間の加熱処理後の２０〜８０℃での貯蔵弾性率Ｇ′が３×１０５〜１×１０８Ｐａとすることにより、太陽電池、有機ＥＬ素子等の電極間を接合することが可能であり、さらに、液体電解質、擬固体電解質、固体電解質、有機発光層等を封止し、かつ基材フィルムのフレキシブル性に追従することが可能なシール材を得ることができる。
The sealing material of the present invention contains a thermoplastic elastomer mainly composed of a copolymer of styrene and a diene hydrocarbon, and has a storage elasticity at 20 to 80 ° C. before heat treatment and after heat treatment at 120 ° C. for 1 minute. By setting the rate G ′ to 3 × 10 5 to 1 × 10 8 Pa, it is possible to join electrodes such as solar cells and organic EL elements, and further, liquid electrolytes, quasi-solid electrolytes, solid electrolytes, A sealing material capable of sealing the organic light emitting layer and the like and following the flexibility of the base film can be obtained.
Claims (7)
The sealing material of any one of Claims 1-6 for using for the joining between the electrode of a solar cell and an organic EL element, or sealing of the electrolyte of a battery, and an organic light emitting layer.
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| JP2021526292A (en) * | 2018-05-29 | 2021-09-30 | ネーデルランツ オルガニサティー フォール トゥーゲパスト‐ナトゥールヴェテンシャッペリーク オンデルズーク テーエンオー | Foldable electronics protection |
| JP7329544B2 (en) | 2018-05-29 | 2023-08-18 | ネーデルランツ オルガニサティー フォール トゥーゲパスト‐ナトゥールヴェテンシャッペリーク オンデルズーク テーエンオー | Protection for foldable electronics |
| JP2022522341A (en) * | 2019-02-28 | 2022-04-18 | エルジー・ケム・リミテッド | Encapsulating film |
| JP7317133B2 (en) | 2019-02-28 | 2023-07-28 | エルジー・ケム・リミテッド | sealing film |
| WO2021006351A1 (en) * | 2019-07-10 | 2021-01-14 | 大日本印刷株式会社 | Adhesive film for metal terminals, metal terminal with adhesive film for metal terminals, electricity storage device using said adhesive film for metal terminals, and method for producing electricity storage device |
| JPWO2021006351A1 (en) * | 2019-07-10 | 2021-12-02 | 大日本印刷株式会社 | An adhesive film for metal terminals, a metal terminal with an adhesive film for metal terminals, a power storage device using the adhesive film for metal terminals, and a method for manufacturing the power storage device. |
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