JP4918975B2 - Dye-sensitized solar cell sealant - Google Patents
Dye-sensitized solar cell sealant Download PDFInfo
- Publication number
- JP4918975B2 JP4918975B2 JP2005273282A JP2005273282A JP4918975B2 JP 4918975 B2 JP4918975 B2 JP 4918975B2 JP 2005273282 A JP2005273282 A JP 2005273282A JP 2005273282 A JP2005273282 A JP 2005273282A JP 4918975 B2 JP4918975 B2 JP 4918975B2
- Authority
- JP
- Japan
- Prior art keywords
- epoxy resin
- dye
- sensitized solar
- type epoxy
- component
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000000565 sealant Substances 0.000 title claims description 22
- 229920000647 polyepoxide Polymers 0.000 claims description 63
- 239000003822 epoxy resin Substances 0.000 claims description 59
- 238000007789 sealing Methods 0.000 claims description 48
- 239000003795 chemical substances by application Substances 0.000 claims description 33
- 239000003505 polymerization initiator Substances 0.000 claims description 18
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 14
- 238000010538 cationic polymerization reaction Methods 0.000 claims description 11
- 229920003986 novolac Polymers 0.000 claims description 8
- 239000007870 radical polymerization initiator Substances 0.000 claims description 8
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 7
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 claims description 6
- 125000002091 cationic group Chemical group 0.000 claims description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- JRQJLSWAMYZFGP-UHFFFAOYSA-N 1,1'-biphenyl;phenol Chemical group OC1=CC=CC=C1.C1=CC=CC=C1C1=CC=CC=C1 JRQJLSWAMYZFGP-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- IYJMFNNRVITCDG-UHFFFAOYSA-N biphenylene;phenol Chemical group OC1=CC=CC=C1.C1=CC=C2C3=CC=CC=C3C2=C1 IYJMFNNRVITCDG-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
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- 238000000016 photochemical curing Methods 0.000 claims 1
- 239000008151 electrolyte solution Substances 0.000 description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 24
- 239000003792 electrolyte Substances 0.000 description 23
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 18
- 239000000758 substrate Substances 0.000 description 18
- 239000003566 sealing material Substances 0.000 description 16
- 125000003118 aryl group Chemical group 0.000 description 14
- -1 polyethylene Polymers 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
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- 238000010248 power generation Methods 0.000 description 9
- 229920005989 resin Polymers 0.000 description 9
- 239000011347 resin Substances 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
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- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 6
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- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 5
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- 125000006850 spacer group Chemical group 0.000 description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 5
- 229930185605 Bisphenol Natural products 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 239000004593 Epoxy Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
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- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 239000004844 aliphatic epoxy resin Substances 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
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- 239000007788 liquid Substances 0.000 description 3
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
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- FGTYTUFKXYPTML-UHFFFAOYSA-N 2-benzoylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 FGTYTUFKXYPTML-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
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- 229940009714 erythritol Drugs 0.000 description 1
- 238000005530 etching Methods 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
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- HOXINJBQVZWYGZ-UHFFFAOYSA-N fenbutatin oxide Chemical compound C=1C=CC=CC=1C(C)(C)C[Sn](O[Sn](CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C=1C=CC=CC=1)(CC(C)(C)C=1C=CC=CC=1)CC(C)(C)C1=CC=CC=C1 HOXINJBQVZWYGZ-UHFFFAOYSA-N 0.000 description 1
- YAGKRVSRTSUGEY-UHFFFAOYSA-N ferricyanide Chemical compound [Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] YAGKRVSRTSUGEY-UHFFFAOYSA-N 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- ZTOMUSMDRMJOTH-UHFFFAOYSA-N glutaronitrile Chemical compound N#CCCCC#N ZTOMUSMDRMJOTH-UHFFFAOYSA-N 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000004693 imidazolium salts Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 150000004694 iodide salts Chemical class 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- MGFYSGNNHQQTJW-UHFFFAOYSA-N iodonium Chemical compound [IH2+] MGFYSGNNHQQTJW-UHFFFAOYSA-N 0.000 description 1
- UETZVSHORCDDTH-UHFFFAOYSA-N iron(2+);hexacyanide Chemical compound [Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] UETZVSHORCDDTH-UHFFFAOYSA-N 0.000 description 1
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000006078 metal deactivator Substances 0.000 description 1
- POPACFLNWGUDSR-UHFFFAOYSA-N methoxy(trimethyl)silane Chemical compound CO[Si](C)(C)C POPACFLNWGUDSR-UHFFFAOYSA-N 0.000 description 1
- ZWXYOPPJTRVTST-UHFFFAOYSA-N methyl-tris(prop-1-en-2-yloxy)silane Chemical compound CC(=C)O[Si](C)(OC(C)=C)OC(C)=C ZWXYOPPJTRVTST-UHFFFAOYSA-N 0.000 description 1
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 description 1
- 150000004980 phosphorus peroxides Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- 150000003077 polyols Chemical class 0.000 description 1
- 238000004382 potting Methods 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
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- 150000004756 silanes Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 235000009518 sodium iodide Nutrition 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
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- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- OPQYOFWUFGEMRZ-UHFFFAOYSA-N tert-butyl 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOC(=O)C(C)(C)C OPQYOFWUFGEMRZ-UHFFFAOYSA-N 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 1
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
Description
本発明は色素増感型太陽電池に関するものであり、特に電解液に対する耐性に優れた色素増感型太陽電池のシール剤に関する。 The present invention relates to a dye-sensitized solar cell, and more particularly to a sealant for a dye-sensitized solar cell excellent in resistance to an electrolytic solution.
１９９１年にグレッツェルらが発表した色素増感型太陽電池はシリコン半導体のｐｎ接合型の太陽電池とは異なるメカニズムによって作動し、変換効率が高く、しかも製造コストが安いという利点がある。この太陽電池は、内部に電解液を封入してあることから湿式太陽電池とも呼ばれる。 The dye-sensitized solar cell announced by Gretzell et al. In 1991 operates by a mechanism different from that of a silicon semiconductor pn junction solar cell, and has an advantage of high conversion efficiency and low manufacturing cost. This solar cell is also called a wet solar cell because an electrolyte is sealed inside.
以下その構造を簡単に説明すると、まず、一枚の透明基板の片方の面に透明導電膜を形成し、その上に色素などの光増感材を吸着させた酸化チタンの粒子を主成分とする多孔質膜を設ける。一方、もう一枚の透明基板に透明導電膜を形成し、さらにその上に白金触媒層を形成して導電性基板とする。ついで両基板を封止剤を介して対向させて、両基板と封止剤によって形成された隙間に電解液を注入して色素増感型太陽電池セルを製造する。 The structure will be briefly described below. First, a transparent conductive film is formed on one surface of a single transparent substrate, and titanium oxide particles adsorbed with a photosensitizer such as a dye are formed as a main component. A porous membrane is provided. On the other hand, a transparent conductive film is formed on another transparent substrate, and a platinum catalyst layer is further formed thereon to form a conductive substrate. Next, both substrates are made to face each other via a sealant, and an electrolyte is injected into a gap formed by both the substrates and the sealant to manufacture a dye-sensitized solar cell.
この太陽電池が電気を発生する仕組みは以下のとおりである。透明基板に光が当たると色素が光を吸収し電子を放出する。電子は酸化チタン膜に移動し電極に伝わる。さらに電子は対極に移動し電解液中のイオンを還元する。還元されたイオンは色素上で再び酸化される。これを繰り返して電気が発生する。 The mechanism by which this solar cell generates electricity is as follows. When light strikes the transparent substrate, the dye absorbs the light and emits electrons. Electrons move to the titanium oxide film and are transmitted to the electrode. Further, the electrons move to the counter electrode and reduce ions in the electrolyte. The reduced ions are oxidized again on the dye. This is repeated to generate electricity.
このような太陽電池において、長期間の信頼性を確保するためには封止セル中の電解液が漏洩することを防止することが求められている。なお、電解液を半固形状又は固体化する方法もあるが、このようにしても電解質が漏洩することを防止する必要がある。また、屋外条件で数年にわたる長期の使用を想定すると、紫外線による劣化等が抑制され、耐久性を有するものが求められている。このような特性は、太陽電池の他の構成要素においても要求されることになり、例えば、導電性支持体等の基材の周縁部を補強する封止材や大面積化で必要になる金属線（集電配線）の封止材（導線被覆材）の他、ギャップ保持やモジュールの形態保持のための形態保持材においても耐久性等が求められることになる。 In such a solar cell, in order to ensure long-term reliability, it is required to prevent leakage of the electrolyte in the sealed cell. In addition, there is a method of making the electrolytic solution semi-solid or solid, but even in this way, it is necessary to prevent the electrolyte from leaking. In addition, assuming long-term use over several years under outdoor conditions, there is a demand for a material that is resistant to deterioration due to ultraviolet rays and has durability. Such characteristics are also required for other components of the solar cell. For example, a sealing material that reinforces the peripheral portion of a base material such as a conductive support or a metal that is required for increasing the area. In addition to the wire (current collection wiring) sealing material (conductive wire coating material), durability and the like are also required in the shape holding material for holding the gap and holding the shape of the module.
色素増感型太陽電池における電解液の封止については、これまでに幾つかの発明事例が存在する。下記の特許文献１〜６にはアイオノマー等の熱可塑性樹脂をシール材として使用した例が示されているが、この樹脂材料は耐熱性や耐湿性が悪く、長期間にわたって十分なシール性能を発揮することができない。
下記の特許文献７〜１３にはポリエチレン製のスペーサーを使用し、外周部をエポキシ樹脂接着剤でシールした例が示されている。特許文献１４〜１８にはポリフッ化エチレン製のシートをスペーサーとして使用し、外周部をエポキシ樹脂接着剤でシールした例が示されている。特許文献１９〜２４にはポリフッ化エチレン、シリカ、アイオノマーシート、ガラス等をスペーサーとして使用し、外周部をエポキシ樹脂接着剤でシールした例が示されている。しかしながら、ここで示されているエポキシ樹脂は高極性の有機溶剤を主成分とする電解液に対する耐性が悪く、長期間にわたって十分なシール性能を発揮することができない。
下記の特許文献２５にはポリイソブチレン系樹脂をシール剤として使用する技術が開示されている。
下記参考文献２６には、導電膜が形成された透明基板にエッチングで凹部を作り、電解液を注入してなる色素増感型太陽電池に関して、封止材の形成には、シリカ微粉末を含むエポキシ樹脂等の絶縁微粒子を含む樹脂を用いることが開示されている。
下記参考文献２７〜３０には透明基板の形成と電解液の注入及び封止工程等を有する色素増感型太陽電池の製造方法に関し、封止材の形成にはシリコンゴム成形体を外周枠として電解液の周辺に置き、貼り合わせ後の電極外周をエポキシ樹脂で硬化させる封止方法が開示されている。
下記参考文献３１〜３２には増感色素溶液と電解液とを予め封止されている領域に導入する工程等を有する色素増感型太陽電池の製造方法に関し、封止材の形成には、ガラスフリットのペ−スト等の無機系のシール剤によることが開示されている。しかし、ガラスフリットを用いる場合には、基板に融着させるために通常４００℃以上の作業温度が必要となり、酸化チタンに吸着された色素へのダメージが懸念される。
また直接電解液を疑似固体化させることで信頼性を向上させる技術もある。下記参考文献３３〜３４には疑似固体電解質を構成する高分子化合物として、ポリ（メタ）アクリレート類、イソシアネート基を有する化合物とエポキシ樹脂類等を用いた技術が開示されている。特にポリ（メタ）アクリレート類において、繰り返し単位に長鎖アルキレンジオール部位を有するものは、電解液との親和性も高く、疑似固体化した後も電解液の漏洩が少ないことが報告されている。
また、本願出願人等は色素増感型太陽電池の製造上の作業工程を短縮化する目的で、特願２００４−１１７８５６号、特願２００４−１２３７０９号、特願２００４−１８７３６０号、特願２００４−２５５０５１号、特願２００４−３７５４５６号において電解液性に優れる種々の光硬化性組成物について提案してきた。 In addition, the applicants of the present application and the like have the purpose of shortening the work steps in the production of the dye-sensitized solar cell, such as Japanese Patent Application Nos. 2004-117856, 2004-123709, 2004-187360, and 2004. No. 255051 and Japanese Patent Application No. 2004-375456 have proposed various photocurable compositions having excellent electrolyte properties.
そして、電解液の漏洩を防止するためにはシール幅やシール厚みを適切に管理する必要があり、特願２００４−３７５４５６号では、特許文献２５で示されるポリイソブチレン系樹脂や上述した光硬化性組成物を使用する場合、シール幅は２ｍｍ以上、より高い信頼性を得るためには５ｍｍ以上のシール幅をとることが好ましいことを見いだした。 In order to prevent leakage of the electrolytic solution, it is necessary to appropriately manage the seal width and the seal thickness. In Japanese Patent Application No. 2004-375456, the polyisobutylene resin disclosed in Patent Document 25 and the above-described photocurability are used. When using the composition, it has been found that the seal width is preferably 2 mm or more, and it is preferable to take a seal width of 5 mm or more in order to obtain higher reliability.
一般に太陽電池においては受光面積が大きいほど単位面積あたりの発電量が大きくなることから、発電に関与しないシール部の面積をなるべく小さくし、受光面積を広くすることが好ましい。そこで、本発明は前述した発明をさらに改良し、色素増感型太陽電池に由来する特殊な電解液の漏洩を防止すること、より詳細にはシール材層の幅を細くし、シール部の面積が小さくても電解液の漏洩を防止できる色素増感型太陽電池用シール剤組成物を提供することを目的とする。 In general, in a solar cell, the larger the light receiving area, the larger the amount of power generation per unit area. Therefore, it is preferable to make the area of the seal portion not involved in power generation as small as possible and widen the light receiving area. Therefore, the present invention further improves the above-described invention to prevent leakage of a special electrolytic solution derived from the dye-sensitized solar cell, more specifically, the width of the sealing material layer is reduced, and the area of the sealing portion is reduced. An object of the present invention is to provide a dye-sensitized solar cell sealant composition that can prevent leakage of an electrolyte even when the electrolyte is small.
本願発明者らは、色素増感型太陽電池の長期信頼性を確保するために、封止セル中の電解液漏洩を防止するための樹脂組成物について鋭意検討を行った結果、水添（水素化）されたエポキシ樹脂を主成分としたシール剤として用いることで従来よりもシール幅を細くし、シール部の面積を小さくしても色素増感型太陽電池に由来する特殊な電解液の漏洩を防止できることを見いだし本発明に至った。すなわち、本発明の請求項１では、
（Ａ）ビスフェノールＡ型エポキシ樹脂及び／またはビスフェノールＦ型エポキシ樹脂を水素化して得られたエポキシ樹脂
（Ｂ）光重合開始剤
の（Ａ）及び（Ｂ）を主成分とする色素増感型太陽電池用シール剤組成物により前記課題を解決するに至った。
また、請求項６では、上記組成物にさらに（Ｃ）側鎖にグリシジル基を有する多官能エポキシ樹脂を配合することにより、高温時の耐湿性向上を図った。
In order to ensure long-term reliability of the dye-sensitized solar cell, the inventors of the present application have conducted intensive studies on a resin composition for preventing leakage of an electrolyte in a sealed cell. Leakage of a special electrolyte derived from a dye-sensitized solar cell even if the seal width is narrower than before and the area of the seal is reduced. The inventors have found that this can be prevented and have arrived at the present invention. That is, in claim 1 of the present invention,
(A) Epoxy resin obtained by hydrogenating bisphenol A-type epoxy resin and / or bisphenol F-type epoxy resin (B) Dye-sensitized sun mainly composed of (A) and (B) of photopolymerization initiator The battery sealing agent composition has solved the above problems.
Further, in claim 6, the moisture resistance at high temperature is improved by further blending (C) a polyfunctional epoxy resin having a glycidyl group in the side chain with the above composition.
以下本発明をより詳細に説明する。まず、本発明における色素増感型太陽電池の構造は次のようなものがある。図２は通称グレッツェルセルと呼ばれる色素増感型太陽電池で、透明基板２ａに透明電極６ａおよび光増感材（色素）が吸着された多孔質金属酸化物半導体膜４（酸化チタン粒子を多孔質状に形成した膜）を順次積層した積層基板１ａと、基板２ｂに電極６ｂおよび白金触媒３を順次積層形成した積層基板１ｂとを積層面を内側にしてシール材５により封止するとともに、積層基板１ａ、１ｂおよびシール材５により形成された空間に電解液７を封入してある。また、図３では、電極６と多孔質金属酸化物半導体膜４とを積層した部材と電極６と白金触媒３とを積層した部材とを一方の基板１ｂに交互に積層させて、積層面を内側にして他方の透明基板１ａとの間をシール材５により封止している。また、これにより生じた空間に電解液７が封入されている。 Hereinafter, the present invention will be described in more detail. First, the structure of the dye-sensitized solar cell in the present invention is as follows. FIG. 2 shows a dye-sensitized solar cell commonly called a Gretzel cell, which is a porous metal oxide semiconductor film 4 in which a transparent electrode 2a and a photosensitizer (dye) are adsorbed on a transparent substrate 2a. And a laminated substrate 1b in which an electrode 6b and a platinum catalyst 3 are sequentially laminated on a substrate 2b are sealed with a sealing material 5 with a laminated surface inside, and laminated. An electrolytic solution 7 is sealed in a space formed by the substrates 1a and 1b and the sealing material 5. Further, in FIG. 3, a member in which the electrode 6 and the porous metal oxide semiconductor film 4 are laminated and a member in which the electrode 6 and the platinum catalyst 3 are laminated are alternately laminated on one substrate 1b, and the laminated surface is formed. The inside and the other transparent substrate 1a are sealed with a sealing material 5. Moreover, the electrolyte solution 7 is enclosed in the space produced by this.
本発明における封止電解液は色素増感型太陽電池において電荷移動媒体として作用される成分であり、光電変換作用には不可欠な成分である。一般的な光電変換作用はグレッツェルらの文献Ｊ．Ａｍ．Ｃｈｅｍ．Ｓｏｃ．，１１５，６３８２（１９９３）に記されているが、その成分は高極性の有機溶剤と酸化還元剤からなっている。この高極性有機溶媒と酸化還元剤との組合せは、酸化還元過程における再生型の電解液として光電変換作用を得ると言う点では酸化チタン半導体部に含浸しやすいこと、光電変換過程において劣化しにくいこと、光・熱作用において電解液成分中に副反応が生じないこと等の特徴を有することが望ましいとされている。これらを満たす好ましい組み合わせとして、高極性有機溶剤としては、電気化学反応における反応媒体として公知のものが望ましく、特にリチウムイオン電池に使用される様な誘電率が高く塩の溶解も可能なものが好ましい。その具体例としては、エチレンカーボネート、プロピレンカーボネート、ブチレンカーボネート等の環状カーボネート類、ジメチルカーボネート、ジエチルカーボネート、メチルエチルカーボネート等の非環状カーボネート類、ジオキサン、テトラヒドロフラン、２−メチルテトラヒドロフラン、エチレングリコールジアルキルエーテル、プロピレングリコールジアルキルエーテル、ポリエチレングリコールモノアルキルエーテル、ポリエチレングリコールジアルキルエーテル等のエーテル類、アセトニトリル、グルタロジニトリル、メトキシアセトニトリル、プロピオニトリル、ベンゾニトリル等のニトリル類、ジメチルスフホキシド、スルホラン等のスルホキシド類、γ−ブチロラクトンプロピレンカーボネート、エチレングリコールモノアルキルエーテル類、ジメチルスルホキシドなどの非プロトン正極性溶媒類、γ−ブチロラクトン、等のラクトン類、ジメチルホルムアミド、ジメチルアセトアミド、Ｎ−メチルピロリドン等のアミド類、３−メチル−２−オキサゾリノン等の複素環類等を用いることが可能である。またこれらの有機溶剤は電解液の粘度や用いる電池の性能にあわせて任意で選択が可能であり、必要に応じて混合もできる。 The sealing electrolyte in the present invention is a component that acts as a charge transfer medium in a dye-sensitized solar cell, and is an indispensable component for a photoelectric conversion effect. The general photoelectric conversion action is described in Gletzel et al. Am. Chem. Soc. 115, 6382 (1993), the components are composed of a highly polar organic solvent and a redox agent. This combination of a highly polar organic solvent and a redox agent is easy to impregnate the titanium oxide semiconductor part in terms of obtaining a photoelectric conversion action as a regenerative electrolyte in the redox process, and hardly deteriorates in the photoelectric conversion process. In addition, it is desirable to have characteristics such that no side reaction occurs in the electrolyte component in the light and heat action. As a preferable combination satisfying these conditions, the highly polar organic solvent is preferably a known solvent as a reaction medium in an electrochemical reaction, and particularly preferably one having a high dielectric constant and capable of dissolving a salt as used in a lithium ion battery. . Specific examples thereof include cyclic carbonates such as ethylene carbonate, propylene carbonate, butylene carbonate, acyclic carbonates such as dimethyl carbonate, diethyl carbonate, and methyl ethyl carbonate, dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, ethylene glycol dialkyl ether, Ethers such as propylene glycol dialkyl ether, polyethylene glycol monoalkyl ether, polyethylene glycol dialkyl ether, nitriles such as acetonitrile, glutarodinitrile, methoxyacetonitrile, propionitrile, benzonitrile, sulfoxides such as dimethyl sulfoxide and sulfolane , Γ-butyrolactone propylene carbonate, ethylene glycol Aprotic positive solvents such as alkyl ethers, dimethyl sulfoxide, lactones such as γ-butyrolactone, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and heterocyclic rings such as 3-methyl-2-oxazolinone Etc. can be used. These organic solvents can be arbitrarily selected according to the viscosity of the electrolytic solution and the performance of the battery to be used, and can be mixed as necessary.
酸化還元剤成分としてはヨウ素と金属ヨウ素化合物が好ましい。金属ヨウ素化合物の例としては、ヨウ化リチウム、ヨウ化ナトリウム、ヨウ化カリウム、ヨウ化セシウム等がある。またヨウ素と組み合わせる酸化還元剤は上記金属ヨウ素化合物だけでなく、四級ピリジニウム塩や四級イミダゾリウム塩のヨウ化物塩も挙げられる。さらにアミン類やチオール類などのヘテロ化合物も還元助剤として使用することができ、フェロシアン酸塩、フェリシアン酸塩、フェロセン、フェロシアニウムイオン塩等のレドックス系触媒の添加も可能である。これらの酸化還元剤および酸化還元助剤の組み合わせとして、特に好ましくはヨウ素とヨウ化物塩系であり、電解液に対する濃度は０．０１〜２ｍｏｌ／Ｌであり、特に０．０１〜０．０５ｍｏｌ／Ｌの範囲が好ましい。電解質として添加するこれら酸化還元剤成分は添加する濃度に光電変換効率は大きく依存する。 As the redox agent component, iodine and a metal iodine compound are preferable. Examples of the metal iodine compound include lithium iodide, sodium iodide, potassium iodide, cesium iodide and the like. Examples of the redox agent combined with iodine include not only the above metal iodine compounds but also iodide salts of quaternary pyridinium salts and quaternary imidazolium salts. Furthermore, hetero compounds such as amines and thiols can also be used as reducing aids, and redox catalysts such as ferrocyanate, ferricyanate, ferrocene, and ferrocyanium ion salts can be added. As a combination of these redox agents and redox assistants, iodine and iodide salt systems are particularly preferable, and the concentration with respect to the electrolytic solution is 0.01 to 2 mol / L, particularly 0.01 to 0.05 mol / L. A range of L is preferred. The photoelectric conversion efficiency greatly depends on the concentration of these redox components added as an electrolyte.
上述した何れの構造を用いた色素増感型太陽電池においても、二枚のプレート間に発電要素を封じ込めた構造を有しているため、電解液など液状物が漏洩しないようシール材５で封止する必要がある。このシール材５は、常温で液状のシール剤をディスペンサ等により少なくとも一方のプレート上にビード状に塗布し、加熱やその他の手段により硬化もしくは固化させて形成する。このシール材５は二枚のプレート（基板）を貼合わす際に同時に硬化させてもよいし、一方もしくは双方のプレート（基板）上に任意の厚さと寸法で予め形成しておいてもよい。なお、シール材の厚みをなるべく薄くするには、シール剤を液状のままで貼合わせ押圧してシール剤層を所望の厚みとしてから、シール剤を反応硬化させてシール材層を形成するとよい。このとき、シール剤中にスペーサ材（粒径を整えた充填剤等）を混入してシール材５の厚みを制御することが望ましい。 Since the dye-sensitized solar cell using any of the structures described above has a structure in which the power generation element is enclosed between the two plates, it is sealed with a sealing material 5 so that a liquid material such as an electrolyte does not leak. It is necessary to stop. The sealing material 5 is formed by applying a liquid sealing agent at room temperature on at least one plate in a bead shape by a dispenser or the like, and curing or solidifying by heating or other means. The sealing material 5 may be cured at the same time when two plates (substrates) are bonded together, or may be previously formed on one or both plates (substrates) with an arbitrary thickness and size. In order to reduce the thickness of the sealing material as much as possible, it is preferable to form the sealing material layer by reacting and curing the sealing agent after the sealing agent is bonded and pressed in a liquid state to obtain a desired thickness. At this time, it is desirable to control the thickness of the sealing material 5 by mixing a spacer material (such as a filler with a adjusted particle size) into the sealing material.
上述のようにして製造された発電要素を内包した二枚のプレート間に、電解液を注入して封入孔をシール剤等で封孔して色素増感型太陽電池を製造する。電解液の封入は、シール材５に一部切り欠き部を設けここから電解液を注入したり、あるいはプレートの一部に孔を２箇所開けてここから電解液を注入する方法（図１参照）があるが、特に制限はない。このようにして得られた色素増感型太陽電池セルの大きさ（表面積）は約１〜５００ｃｍ２程度であり、このセルを複数連結して所望の電圧を作り出す。 A dye-sensitized solar cell is manufactured by injecting an electrolyte solution between two plates enclosing the power generation element manufactured as described above and sealing the sealing hole with a sealant or the like. The electrolytic solution can be sealed by injecting the electrolytic solution from a part of the sealing member 5 provided with a notch, or by injecting the electrolytic solution from two holes in a part of the plate (see FIG. 1). ), But there are no particular restrictions. The size (surface area) of the dye-sensitized solar cell thus obtained is about 1 to 500 cm 2 , and a plurality of cells are connected to create a desired voltage.
本発明における（Ａ）成分芳香族部位が水素化されたビスフェノールＡ型のエポキシ樹脂とビスフェノールＦ型エポキシ樹脂は、特許文献４０〜４２に示されるような不飽和芳香族骨格を水素添加した脂環式エポキシ構造を有する化合物が挙げられる。参考文献にも記されているが液状封止剤には芳香族部位を水素化されていないビスフェノールＡ型およびビスフェノールＦ型エポキシ樹脂が多く用いられている。しかしこれらを硬化させたものは弾性率が低いため、急激な熱衝撃によりクラックが発生し、封止剤としての性能を低下させてしまう欠点がある。参考文献では、この欠点を緩和させるために本化学構造を主骨格として用いている。一方、本発明においては熱衝撃によるクラックよりも電解系の封止性能に本骨格が有効であることを見いだした。芳香族部位が水素化されていないエポキシ樹脂を色素増感型太陽電池用封止剤として使用した場合、電解液との親和性によって封止が完全に出来ない場合が多い。そこでエポキシ樹脂の持つ信頼性を維持しつつ電解液と相溶性を低くするために本骨格が有効である。これらの芳香族部位を水素化したビスフェノールＡ型のエポキシ樹脂とビスフェノールＦ型エポキシ樹脂は、一種類単独でも複数種を併用してもよい。なお、複数種を併用する場合は、それらが共に芳香族部位を水素化されており、かつそれぞれが相溶可能であれば本発明の効果範囲内である。
本発明における（Ａ）成分の水素化エポキシ樹脂の製造方法は、芳香族エポキシ樹脂を無溶剤又はテトラヒドロフラン、ジオキサン等のエーテル系の有機溶剤を用いて、ロジウム又はルテニウムをグラファイト（六方晶結晶の黒鉛）に担持した触媒の存在下で、芳香環を選択的に水素化反応し脂環式エポキシ樹脂を得る方法が、芳香環の水素化の選択率が良いという点で好ましい。水素化率は全芳香族１００％の水素添加が好ましい。水素添加率が低い場合、先に口述した熱衝撃性による封止性能の低下が見られ、本発明の効果を十分に発揮されない可能性がある。 The method for producing the hydrogenated epoxy resin of component (A) in the present invention uses an aromatic epoxy resin as a solvent-free or ether-based organic solvent such as tetrahydrofuran and dioxane, and rhodium or ruthenium as graphite (hexagonal crystal graphite). The method of selectively hydrogenating an aromatic ring to obtain an alicyclic epoxy resin in the presence of a catalyst supported on (3) is preferable in terms of good selectivity for hydrogenation of the aromatic ring. The hydrogenation rate is preferably 100% wholly aromatic. When the hydrogenation rate is low, the sealing performance is lowered due to the thermal shock property described above, and the effects of the present invention may not be sufficiently exhibited.
上述した（Ａ）成分に関して、より好ましくは下式で示される１分子中に２個以上のエポキシ基を有し、かつ主鎖中の芳香族部位が水素添加され、飽和された構造を有するエポキシ化合物を示す。
（Ａ）成分の具体例としては、ジャパンエポキシレジン社製のＹＸ８０３４（ビスフェノールＡ型エポキシ樹脂系）、大日本インキ社製のＵＸＡ７０１５、東都化成社製のＳＴ３０００等が挙げられる。 Specific examples of the component (A) include YX8034 (bisphenol A type epoxy resin) manufactured by Japan Epoxy Resin, UXA7015 manufactured by Dainippon Ink, ST3000 manufactured by Tohto Kasei Co., Ltd., and the like.
さらには、本発明は必要に応じて他の環状エーテル類の添加も可能である。例えば、脂肪族エポキシ樹脂、オキセタン化合物、スピロオルソエステル、ビシクロオルソエステル、スピロオルソカーボネート等が挙げられる。 Furthermore, the present invention can add other cyclic ethers as required. Examples include aliphatic epoxy resins, oxetane compounds, spiro orthoesters, bicycloorthoesters, spiroorthocarbonates, and the like.
添加が可能なエポキシ樹脂の中でも脂肪族エポキシ樹脂は、成分（Ａ）との相溶性に関して長けている。脂肪族エポキシ樹脂は脂環式エポキシ樹脂と脂鎖式エポキシ樹脂に分類される。脂環式エポキシ樹脂は、脂環構造を有するエポキシ化合物であり、その具体例としては、３，４−エポキシシクロヘキシルメチル−３，４−エポキシシクロヘキサンカルボキシレート、ビス（３，４−エポキシシクロヘキシルメチル）アジペート、２−（３，４−エポキシシクロヘキシル−５，５−スピロ−３，４−エポキシ）シクロヘキサノン−ｍ−ジオキサン、ビス（２，３−エポキシシクロペンチル）エーテル等が挙げられる。 Among the epoxy resins that can be added, the aliphatic epoxy resin is excellent in compatibility with the component (A). Aliphatic epoxy resins are classified into alicyclic epoxy resins and alicyclic epoxy resins. The alicyclic epoxy resin is an epoxy compound having an alicyclic structure, and specific examples thereof include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexylmethyl). Examples include adipate, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexanone-m-dioxane, bis (2,3-epoxycyclopentyl) ether, and the like.
脂鎖式エポキシ樹脂は、脂肪族多価アルコールまたはそのアルキレンオキサイド付加物のポリグリシジルエーテルやまたはそのアルキレンオキサイド付加体のポリグリシジルエーテルであり、その具体例としては、１，４−ブタンジオールジグリシジルエーテル、１，６−ヘキサンジオールジグリシジルエーテル、グリセリントリグリシジルエーテル、トリメチロールプロパントリグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、エチレングリコール、プロピレングリコール、グリセリン等の多価アルコールに１種または２種以上のアルキレンオキサイドを付加されることによって合成されるポリエーテルポリオールのポリグリシジルエーテル等が挙げられる。 The alicyclic epoxy resin is a polyglycidyl ether of an aliphatic polyhydric alcohol or an alkylene oxide adduct thereof or a polyglycidyl ether of an alkylene oxide adduct thereof. Specific examples thereof include 1,4-butanediol diglycidyl. 1 for polyhydric alcohols such as ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, ethylene glycol, propylene glycol, glycerin Examples thereof include polyglycidyl ethers of polyether polyols synthesized by adding seeds or two or more alkylene oxides.
オキセタン化合物の具体例としては、３−（メタ）アリルオキシメチル−３−エチルオキセタン、イソボルニルオキシエチル（３−エチル−３−キセタニルメチル）エーテル、イソボルニル（３−エチル−３−キセタニルメチル）エーテル、２−エチルヘキシル（３−エチル−３−キセタニルメチル）エーテル、ジシクロペンタジエン（３−エチル−３−キセタニルメチル）エーテル等の１官能オキセタン化合物、３，７−ビス（３−オキセタニル）−５−オキサ−ノナン、１，２−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］エタン、１，２−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］プロパン、ジシクロペンテニルビス（３−エチル−３−オキセタニルメチル）エーテル、１，４−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］ブタン、１，６−ビス［（３−エチル−３−オキセタニルメトキシ）メチル］ヘキサン等の２官能オキセタン化合物、トリメチロールプロパントリス（３−エチル−３−キセタニルメチル）エーテル、ペンタエリスリトールトリス（３−エチル−３−キセタニルメチル）エーテル、ペンタエリスリトールテトラキス（３−エチル−３−キセタニルメチル）エーテル、ジペンタエリスリトールヘキサキス（３−エチル−３−キセタニルメチル）エーテル等の多官能オキセタン化合物が挙げられる。 Specific examples of the oxetane compound include 3- (meth) allyloxymethyl-3-ethyloxetane, isobornyloxyethyl (3-ethyl-3-xetanylmethyl) ether, isobornyl (3-ethyl-3-xetanylmethyl) ether, Monofunctional oxetane compounds such as 2-ethylhexyl (3-ethyl-3-xetanylmethyl) ether, dicyclopentadiene (3-ethyl-3-xetanylmethyl) ether, 3,7-bis (3-oxetanyl) -5-oxa-nonane 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, dicyclopentenylbis (3-ethyl- 3-Oxetanylmethyl) ether, 1,4-bis [(3-ethyl- -Oxetanylmethoxy) methyl] butane, bifunctional oxetane compounds such as 1,6-bis [(3-ethyl-3-oxetanylmethoxy) methyl] hexane, trimethylolpropane tris (3-ethyl-3-xetanylmethyl) ether, penta Multifunctional oxetane compounds such as erythritol tris (3-ethyl-3-xetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-xetanylmethyl) ether, dipentaerythritol hexakis (3-ethyl-3-xetanylmethyl) ether It is done.
本発明の（Ｂ）重合開始剤は、紫外線などの活性エネルギー線又は熱によりカチオン種又はルイス酸を発生するカチオン重合開始剤（Ｂ１）が好ましく用いることができる。好ましいカチオン重合開始剤（Ｂ１）の中で紫外線などの活性エネルギー線によりカチオン種を発生する化合物としては、アリールスルホニウム錯塩、ハロゲン含有錯イオンの芳香族スルホニウム、ヨードニウム、ホウ素塩並びに芳香族オニウム塩が包含される。その具体例としては、テトラフルオロホウ酸トリフェニルフェナシルホスホニウム、ヘキサフルオロアンチモン酸トリフェニルスルホニウム、ビス−［４−（ジフェニルスルフォニオ）フェニル］スルフィドビスジヘキサフルオロアンチモネート、ビス−［４−（ジ４’−ヒドロキシエトキシフェニルスルフォニオ）フェニル］スルフィドビスジヘキサフルオロアンチモネート、ビス−［４−（ジフェニルスルフォニオ）フェニル］スルフィドビスジヘキサフルオロフォスフェート、テトラフルオロホウ酸ジフェニルヨードニウム等が挙げられる。これらの塩のいくつかは商品として入手が可能であり、ＦＸ−５１２（３Ｍ社製）、ＵＶＲ−６９９０及びＵＶＲ−６９７４（ユニオン・カーバイド社製）、ＵＶＥ−１０１４及びＵＶＥ−１０１６（ジェネラル・エレクトリック社製）、ＫＩ−８５（デグッサ社製）、ＳＰ−１５０及びＳＰ−１７０（旭電化社製）並びにサンエイドＳＩ−６０Ｌ、ＳＩ−８０Ｌ及びＳＩ−１００Ｌ（三新化学工業社製）の名称で上市されている。また、熱によりカチオン種を発生する化合物としては、アルキル基を少なくとも１個有するアンモニウム塩、スルホニウム塩、ヨウドニウム塩、ジアゾニウム塩、三フッ化ホウ素・トリエチルアミン錯体等が挙げられる。また一方、活性エネルギー線カチオン重合開始剤としても用いられる芳香族オニウム塩のうち、熱によりカチオン種を発生するものがあり、これらのカチオン重合開始剤を用いれば活性エネルギー線でも熱でも、またその両方を用いても本発明のシール剤を重合硬化させることができる。その具体例としては、サンエイドＳＩ−６０Ｌ、ＳＩ−８０Ｌ及びＳＩ−１００Ｌ（三新化学工業社製）がある。また、上記列記した多数のカチオン重合開始剤の中で、芳香族オニウム塩が、取り扱い性及び潜在性と硬化性のバランスに優れるという点で好ましい。なお、本発明では上記した多数のカチオン重合開始剤を複数併用することにより、光（紫外線や可視光）硬化性と熱硬化性の両方の特徴を合わせ持たせることもできる。 As the (B) polymerization initiator of the present invention, a cationic polymerization initiator (B1) that generates a cationic species or a Lewis acid by active energy rays such as ultraviolet rays or heat can be preferably used. Among the preferred cationic polymerization initiators (B1), examples of compounds that generate cationic species by active energy rays such as ultraviolet rays include arylsulfonium complex salts, halogen-containing complex ions of aromatic sulfonium, iodonium, boron salts, and aromatic onium salts. Is included. Specific examples thereof include triphenylphenacylphosphonium tetrafluoroborate, triphenylsulfonium hexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (Di4′-hydroxyethoxyphenylsulfonio) phenyl] sulfide bisdihexafluoroantimonate, bis- [4- (diphenylsulfonio) phenyl] sulfide bisdihexafluorophosphate, diphenyliodonium tetrafluoroborate, etc. Is mentioned. Some of these salts are commercially available, FX-512 (manufactured by 3M), UVR-6990 and UVR-6974 (manufactured by Union Carbide), UVE-1014 and UVE-1016 (general electric). KI-85 (manufactured by Degussa), SP-150 and SP-170 (manufactured by Asahi Denka) and Sun-Aid SI-60L, SI-80L and SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.) It is on the market. In addition, examples of the compound that generates a cationic species by heat include ammonium salts having at least one alkyl group, sulfonium salts, iodonium salts, diazonium salts, boron trifluoride / triethylamine complexes, and the like. On the other hand, among the aromatic onium salts used as active energy ray cationic polymerization initiators, there are those that generate cationic species by heat, and if these cationic polymerization initiators are used, both active energy rays and heat can be used. Even if both are used, the sealing agent of the present invention can be polymerized and cured. Specific examples thereof include Sun Aid SI-60L, SI-80L and SI-100L (manufactured by Sanshin Chemical Industry Co., Ltd.). Of the many cationic polymerization initiators listed above, aromatic onium salts are preferred because they are excellent in handleability and the balance between latency and curability. In the present invention, by combining a plurality of the above-described many cationic polymerization initiators, it is possible to have both light (ultraviolet light and visible light) curability and thermosetting characteristics.
また、本発明のシール剤は前述の（Ｂ１）カチオン重合開始剤のみでも硬化は可能であるが、（Ｂ２）ラジカル重合開始剤を併用すると硬化速度が著しく向上するため、これを重合開始助剤として用いることが有効である。この（Ｂ２）ラジカル重合開始剤は、（メタ）アクリレート化合物等のラジカル重合性化合物の重合開始剤として一般に良く知られている化合物が使用できる。この（Ｂ２）ラジカル重合開始剤もまた紫外線などの活性エネルギー線によりラジカルを発生するものや、熱を加えることによりラジカルを発生するものがあるが、（Ｂ１）カチオン重合開始剤の種類に合わせて任意に選択して使用すれば良い。例えば、紫外線により活性化するカチオン重合開始剤を選択した場合には、同じように紫外線によりラジカルを発生するラジカル重合開始剤を選択する方が、シール剤の硬化性に好ましい影響を与える場合が多い。 Further, the sealing agent of the present invention can be cured only by the above-mentioned (B1) cationic polymerization initiator, but (B2) when used together with the radical polymerization initiator, the curing rate is remarkably improved. It is effective to use as. As this (B2) radical polymerization initiator, a compound that is generally well known as a polymerization initiator of a radical polymerizable compound such as a (meth) acrylate compound can be used. This (B2) radical polymerization initiator also includes those that generate radicals by active energy rays such as ultraviolet rays and those that generate radicals by applying heat. (B1) Depending on the type of cationic polymerization initiator Any selection may be used. For example, when a cationic polymerization initiator that is activated by ultraviolet rays is selected, it is often the case that a radical polymerization initiator that generates radicals by ultraviolet rays similarly has a favorable effect on the curability of the sealant. .
ラジカル重合開始剤（Ｂ２）は、上記したように紫外線や可視光などの活性エネルギー線によりラジカルを生成する化合物と熱を与えることによりラジカルを生成する化合物と分けられるが、これらのうち活性エネルギー線によりラジカルを生成する光ラジカル重合開始剤は、さらに化学構造（分子結合エネルギー）の差により、分子内開裂型（Ｐ１型）と水素引き抜き型（Ｐ２型）に分類される。分子内開裂型（Ｐ１型）の具体例としては、４−フェノキシジクロロアセトフェノン、４−ｔ−ブチル−ジクロロアセトフェノン、４−ｔ−ブチル−トリクロロアセトフェノン、ジエトキシアセトフェノン、２−ヒドロキシ−２−メチル−１−フェニルプロパン−１−オン、１−（４−イソプロピルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、１−（４−ドデシルフェニル）−２−ヒドロキシ−２−メチルプロパン−１−オン、４−（２−ヒドロキシエトキシ）−フェニル（２−ヒドロキシ−２−プロピル）ケトン、１−ヒドロキシシクロヘキシルフェニルケトン等のアセトフェノン類、ベンゾイン、ベンゾインメチルーテル、ベンゾインエチルエーテル、ベンジルジメチルケタール等のベンゾイン類、アシルフォシフィンオキサイド類、チタノセン化合物等が挙げられる。 The radical polymerization initiator (B2) is classified into a compound that generates radicals by active energy rays such as ultraviolet rays and visible light and a compound that generates radicals by applying heat, as described above. The photo-radical polymerization initiators that generate radicals due to the above are further classified into an intramolecular cleavage type (P1 type) and a hydrogen abstraction type (P2 type) depending on the difference in chemical structure (molecular bond energy). Specific examples of the intramolecular cleavage type (P1 type) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2-methyl- 1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-1 -One, acetophenones such as 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzyldimethyl ketal, etc. Benzoins, acyl phosphiphy Oxides, titanocene compounds, and the like.
水素引き抜き型（Ｐ２型）の具体例としては、ベンゾフェノン、ベンゾイルベンゾイックアシッド、ベンゾイルベンゾイックアシッドメチルエーテル、４−フェニルベンゾフェノン、ヒドロキシベンゾフェノン、４−ベンゾイル−４’−メチルジフェニルサルファイド、３，３’−メチル−４−メトキシベンゾフェノン等のベンゾフェノン類、チオキサントン、２−クロロチオキサントン、２−メチルチオキサントン、２，４−ジメチルチオキサントン、イソプロピルチオキサントン等のチオキサントン類が挙げられる。さらに、熱によりラジカルを発生する化合物としては、過酸化ベンゾイル、ジイソプロピルパーオキシジカーボネート、ｔ − ブチルパーオキシ− ２ − エチルヘキサノエート、ｔ − ブチルパーオキシピバレート、ジ− ｔ − ブチルパーオキシド 、ｔ − ブチルパーオキシジイソブチレート、過酸化ラウロイル、２ ， ２ '− アゾビスイソ酪酸ジメチル等の有機パーオキサイド類やアゾビスイソブチロニトリルなどが挙げられる。また、上記ラジカル重合開始剤は１種または２種以上を用いることができ、Ｐ１型同士、Ｐ２型同士あるいはＰ１型とＰ２型を併用しても良いし、（Ｂ１）成分と同様に本発明のシール剤の硬化方法（光硬化性や熱硬化性）に合わせて選択して使用することができる。特にＰ１型開始剤は光カチオン重合速度を促進する効果が大きいため、本発明では光カチオン重合開始剤とＰ１型光ラジカル重合開始剤を併用すると極めて硬化性のよい光硬化性のシール剤を得ることが可能となる。
また、色素増感型太陽電池の発電要素に対する熱の影響を考慮すると、本発明のシール剤に光硬化性を付与するためにそれに適した重合開始剤を選択することがより好ましい。
Specific examples of the hydrogen abstraction type (P2 type) include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl ether, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, 3,3 ′. Examples include benzophenones such as -methyl-4-methoxybenzophenone, and thioxanthones such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, and isopropylthioxanthone. Further, as a compound that generates radicals by heat, benzoyl peroxide, diisopropyl peroxydicarbonate, t-butylperoxy-2-ethylhexanoate, t-butylperoxypivalate, di-t-butylperoxide , T-butylperoxydiisobutyrate, lauroyl peroxide, organic peroxides such as 2,2′-dimethyl azobisisobutyrate, and azobisisobutyronitrile. In addition, the radical polymerization initiator may be used alone or in combination of two or more, P1 types, P2 types or P1 type and P2 type may be used together, or the present invention as in the case of component (B1). The sealant can be selected and used in accordance with the curing method (photocurability and thermosetting). In particular, since the P1 type initiator has a great effect of accelerating the rate of photocationic polymerization, in the present invention, when a photocationic polymerization initiator and a P1 type photoradical polymerization initiator are used in combination, a photocurable sealant with extremely good curability is obtained. It becomes possible.
In consideration of the influence of heat on the power generation element of the dye-sensitized solar cell, it is more preferable to select a polymerization initiator suitable for imparting photocurability to the sealant of the present invention.
本発明のシール剤は、（Ａ）水素化エポキシ樹脂１００重量部に対し、（Ｂ）重合開始剤が０．５〜１０重量部配合することが望ましい。また、（Ｂ１）カチオン重合開始剤と（Ｂ２）ラジカル重合開始助剤を併用する場合にもその合計量で、（Ａ）水素化エポキシ樹脂１００重量部に対し、０. ５〜１０重量部配合することが望ましい。なお、（Ｂ１）成分及び（Ｂ２）成分を併用する場合は、その併用割合を重量比で（Ｂ１）：（Ｂ２）＝７：３〜３：７とすることがより好ましい。 As for the sealing agent of this invention, it is desirable to mix | blend 0.5-10 weight part of (B) polymerization initiator with respect to 100 weight part of (A) hydrogenated epoxy resins. Further, when (B1) cationic polymerization initiator and (B2) radical polymerization initiation assistant are used in combination, 0.5 to 10 parts by weight of 100 parts by weight of (A) hydrogenated epoxy resin is added in the total amount. It is desirable to do. In addition, when using together (B1) component and (B2) component, it is more preferable that the combined ratio is set to (B1) :( B2) = 7: 3-3: 7 by weight ratio.
本発明の（Ｃ）成分として用いられる側鎖にグリシジル基を有する多官能エポキシ樹脂は主鎖骨格に剛直な構造を有する樹脂の側鎖に反応性グリシジル基を有する多官能のエポキシ樹脂である。この（Ｃ）成分をさらに添加することにより、特に高温高湿時のシール効果を向上させることができる。この様なエポキシ樹脂の例としては、フェノールノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、トリスフェノールメタン型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂、ナフトールアラルキル型エポキシ樹脂、ナフォトールノボラック型エポキシ樹脂、４官能ナフタレン型エポキシ樹脂、フェノールビフェニル型エポキシ樹脂、フェノールビフェニレンノボラック型エポキシ樹脂等が挙げられる。 The polyfunctional epoxy resin having a glycidyl group in the side chain used as the component (C) of the present invention is a polyfunctional epoxy resin having a reactive glycidyl group in the side chain of a resin having a rigid structure in the main chain skeleton. By further adding the component (C), it is possible to improve the sealing effect particularly at high temperature and high humidity. Examples of such epoxy resins include phenol novolac type epoxy resins, cresol novolak type epoxy resins, trisphenol methane type epoxy resins, dicyclopentadiene type epoxy resins, naphthol aralkyl type epoxy resins, nafol novolak type epoxy resins, 4 Functional naphthalene type epoxy resins, phenol biphenyl type epoxy resins, phenol biphenylene novolac type epoxy resins and the like can be mentioned.
成分（Ｃ）の添加量は成分（Ａ）１００重量部に対して１０〜９０重量部が好ましく、より好ましくは３０〜７０重量部である。特に成分（Ｃ）の添加量は成分（Ａ）との相溶性に大きく影響を及ぼす。成分（Ｃ）の添加量が過剰量であると樹脂中で分離を起こし、十分な発明効果を発揮できない。また成分（Ｃ）の過剰添加は電解液中のヨウ素を吸着してしまうことから、封止性能を満足しても電池性能が低下する原因にも繋がる。 The amount of component (C) added is preferably 10 to 90 parts by weight, more preferably 30 to 70 parts by weight, based on 100 parts by weight of component (A). In particular, the amount of component (C) added greatly affects the compatibility with component (A). If the amount of component (C) added is excessive, separation occurs in the resin, and sufficient invention effects cannot be exhibited. Moreover, since excessive addition of a component (C) will adsorb | suck iodine in electrolyte solution, even if it satisfies sealing performance, it will also lead to the cause for battery performance to fall.
本発明のシール剤組成物には、物性を調整するために各種の添加剤、例えば難燃剤、老化防止剤、充填材、可塑剤、物性調整剤、接着性付与剤、貯蔵安定性改良剤、溶剤、ラジカル禁止剤、金属不活性剤、オゾン劣化防止剤、リン系過酸化物分解剤、滑剤、顔料、光硬化性樹脂などを必要に応じて適宜配合してもよい。これらの各種添加剤は単独で用いてもよく、２種類以上を併用してもよい。 The sealant composition of the present invention has various additives for adjusting physical properties, such as flame retardants, anti-aging agents, fillers, plasticizers, physical property modifiers, adhesion promoters, storage stability improvers, You may mix | blend a solvent, a radical inhibitor, a metal deactivator, an ozone degradation inhibitor, a phosphorus peroxide decomposer, a lubricant, a pigment, a photocurable resin, etc. as needed. These various additives may be used alone or in combination of two or more.
配合できる充填材としては特に限定されないが、強度などの物性を付与するために、例えば微粉末シリカ、炭酸カルシウム、タルク、酸化チタン、珪藻土、硫酸バリウム、カーボンブラック、表面処理微細炭酸カルシウム、焼成クレー等の補強性充填材などが挙げられる。補強性充填材は単独で用いてもよく、２種類以上を併用してもよい。これらの中でもシリカ微粉末が好ましく、湿式製造法等から得られる含水シリカ、乾式製造法等から得られる乾式シリカなどを用いることができる。これらの中で組成物中に水分が多く含まれると硬化反応時に副反応が起こる可能性があるため、無水シリカが特に好ましい。他に増量あるいは物性調整のために補強性のあまり強くない充填材も用いることができる。また、図２において多孔質金属酸化物半導体膜４と白金触媒３との隙間、あるいは図３において金属酸化物半導体膜４および／または白金触媒３と透明基板１ａとの隙間を一定に保つ目的で、ガラスや樹脂製のギャップ材を添加してもよい。 The filler that can be blended is not particularly limited, but in order to impart physical properties such as strength, for example, fine powder silica, calcium carbonate, talc, titanium oxide, diatomaceous earth, barium sulfate, carbon black, surface-treated fine calcium carbonate, calcined clay And reinforcing fillers such as The reinforcing filler may be used alone or in combination of two or more. Among these, silica fine powder is preferable, and hydrous silica obtained from a wet production method or the like, dry silica obtained from a dry production method or the like can be used. Among these, anhydrous silica is particularly preferable because a large amount of moisture in the composition may cause a side reaction during the curing reaction. In addition, in order to increase the amount or adjust the physical properties, a filler that is not so strong in reinforcement can be used. 2 for the purpose of keeping the gap between the porous metal oxide semiconductor film 4 and the platinum catalyst 3 or the gap between the metal oxide semiconductor film 4 and / or the platinum catalyst 3 and the transparent substrate 1a constant in FIG. A gap material made of glass or resin may be added.
配合できる接着性付与剤としては、シランカップリング剤が好ましい。例えばメチルトリメトキシシラン、ジメチルジメトキシシラン、トリメチルメトキシシラン、ｎ−プロピルトリメトキシシラン等のアルキルアルコキシシラン類、ジメチルジイソプロペノキシシラン、メチルトリイソプロペノキシシラン等のアルキルイソプロペノキシシラン類、ビニルトリメトキシシラン、ビニルトリエトキシシラン、γ−メタクリロイルオキシプロピルメチルジメトキシシラン、γ−アクリロイルオキシプロピルトリエトキシシラン等のビニル型不飽和基含有シラン類、シリコーンワニス類、ポリシロキサン類等が挙げられる。 As the adhesion-imparting agent that can be blended, a silane coupling agent is preferable. For example, alkyl alkoxysilanes such as methyltrimethoxysilane, dimethyldimethoxysilane, trimethylmethoxysilane, and n-propyltrimethoxysilane, alkylisopropenoxysilanes such as dimethyldiisopropenoxysilane, and methyltriisopropenoxysilane, vinyl Examples include vinyl unsaturated group-containing silanes such as trimethoxysilane, vinyltriethoxysilane, γ-methacryloyloxypropylmethyldimethoxysilane, and γ-acryloyloxypropyltriethoxysilane, silicone varnishes, and polysiloxanes.
本発明の色素増感型太陽電池用シール剤組成物を用いることにより、耐電解液特性の優れたシール材層を形成できるため、発電に関与しないシール部の面積を小さくして受光面積を大きくとることができることから、単位面積あたりの発電効率や発電量を大きくすることができる。特に、本発明のシール剤に紫外線などの活性エネルギー線硬化性を付与すると、色素増感型太陽電池の製造時に熱がかからないため、発電要素への悪影響をより小さくすることができる。 By using the dye-sensitized solar cell sealing agent composition of the present invention, a sealing material layer having excellent anti-electrolytic solution properties can be formed. Therefore, the area of the seal portion not involved in power generation is reduced and the light receiving area is increased. Therefore, power generation efficiency and power generation amount per unit area can be increased. In particular, when an active energy ray curability such as ultraviolet rays is imparted to the sealing agent of the present invention, no heat is applied during the production of the dye-sensitized solar cell, so that the adverse effect on the power generation element can be further reduced.
以下に実施例によって本発明について具体的に説明するが、本発明は以下の実施例により制約されるものではない。なお、表中の添加量は重量部を意味する。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited by the following examples. In addition, the addition amount in a table | surface means a weight part.
１．シール剤の調製
成分（Ａ）として水添ビスフェノールＡ型エポキシ樹脂ＹＸ８０３４（ジャパンエポキシレジン社製）、水添ビスフェノールＦ型エポキシ樹脂ＹＬ６７５３（ジャパンエポキシレジン社製）、成分（Ｃ）として側鎖にグリシジル基を有する多官能エポキシ樹脂ＥＰ１５２（ジャパンエポキシレジン社製）、比較例として水素化していないビスフェノールＡ型エポキシ樹脂ＥＰ８２８（ジャパンエポキシレジン社製）を用いた。光カチオン重合開始剤（Ｂ１）としてアデカオプトマーＳＰ−１７０（旭電化工業製）、光ラジカル重合開始助剤（Ｂ２）としてダロキュアー１１７３（チバ・スペシャルティ・ケミカルズ社製）を用いた。各シール剤の調整は表１に示した添加量（表中の添加量は特に説明のない限り重量基準である）で行い、ミキサーを用いて５０℃で１時間攪拌して各組成物を得た。その後、樹脂にギャップ材（スペーサー材）として粒径１５μｍのガラスファイバー（日本電気硝子社製）を３重量％それぞれ添加撹拌して各シール剤を得た。
1. Hydrogenated bisphenol A type epoxy resin YX8034 (manufactured by Japan Epoxy Resin Co., Ltd.), hydrogenated bisphenol F type epoxy resin YL6753 (manufactured by Japan Epoxy Resin Co., Ltd.) as the preparation component (A) of the sealant, and glycidyl in the side chain as component (C) Polyfunctional epoxy resin EP152 having a group (made by Japan Epoxy Resin Co., Ltd.) and a non-hydrogenated bisphenol A type epoxy resin EP828 (made by Japan Epoxy Resin Co., Ltd.) were used as comparative examples. Adekaoptomer SP-170 (Asahi Denka Kogyo Co., Ltd.) was used as the photocationic polymerization initiator (B1), and Darocur 1173 (Ciba Specialty Chemicals Co., Ltd.) was used as the photoradical polymerization initiation assistant (B2). Adjustment of each sealing agent is performed with the addition amount shown in Table 1 (addition amounts in the table are based on weight unless otherwise specified), and each composition is obtained by stirring at 50 ° C. for 1 hour using a mixer. It was. Thereafter, 3% by weight of glass fiber (manufactured by Nippon Electric Glass Co., Ltd.) having a particle diameter of 15 μm as a gap material (spacer material) was added to the resin and stirred to obtain each sealing agent.
２．電解液の調整
封止する電解液は以下の手順で調整した。有機溶剤にヨウ素０．０５モル／Ｌ、ヨウ化カリウム０．０３モル／Ｌ、１−メチル−３−プロピルイミダゾリウムヨージド０．０１モル／Ｌを添加し、それぞれを十分に溶解させた。有機溶剤に３−メトキシプロピオニトリルを使用した系を電解液Ａ、アセトニトリルを使用した系を電解液Ｂ、プロピレンカーボネートを使用した系を電解液Ｃ、γ−ブチロラクトンを使用した系を電解液Ｄとした。
2. Adjustment of electrolyte solution The electrolyte solution to be sealed was prepared by the following procedure. 0.05 mol / L of iodine, 0.03 mol / L of potassium iodide, and 0.01 mol / L of 1-methyl-3-propylimidazolium iodide were added to the organic solvent, and each was sufficiently dissolved. A system using 3-methoxypropionitrile as an organic solvent is electrolytic solution A, a system using acetonitrile is electrolytic solution B, a system using propylene carbonate is electrolytic solution C, and a system using γ-butyrolactone is electrolytic solution D. It was.
３．疑似セルの作成
３ｃｍ×３ｃｍのガラス板上に上記調整した各シール剤をシール幅２ｍｍで２．５ｃｍ×２．５ｃｍの四角形を描くように塗布した（塗布にはスリーボンドＴＲＣ１２０ロボットを使用）。塗布後、３ｃｍ×３ｃｍの別のガラス板上で１Φ（直径１ｍｍ）の孔が２つ開いたガラス板を張り合わせ、３０００ｍＪ／ｃｍ2の積作光量での光硬化させた。その後、孔から電解液を十分に注入し、それぞれの注入孔周辺にシール剤Ｅを塗布して、さらに３ｃｍ×３ｃｍの別のガラス板にて再度貼合わせ光照射を行った。（図１参照）
3. Preparation of Pseudo Cell Each of the prepared sealing agents was applied on a 3 cm × 3 cm glass plate so as to draw a 2.5 cm × 2.5 cm square with a seal width of 2 mm (a three-bond TRC120 robot was used for application). After the application, a glass plate having two holes of 1Φ (diameter 1 mm) was pasted on another 3 cm × 3 cm glass plate and photocured with a product light amount of 3000 mJ / cm 2 . Then, electrolyte solution was fully inject | poured from the hole, the sealing agent E was apply | coated to each injection hole periphery, and also bonding light irradiation was performed again with another 3 cm x 3 cm glass plate. (See Figure 1)
４．電解液漏洩性試験条件
先の手法により作成した疑似セルを用いて以下の試験を行い、電解液の漏洩性を確認することでシール性の優劣を判断した。電解液のシール性は封止した電解液の漏洩量を測定し、初期値との重量変化率（％）にて表中に示した。
耐熱性：８０℃の恒温状態で９６時間放置後の漏洩量を測定した。
耐湿性：６０℃×９５％ＲＨ（表中：耐湿６０℃）および８０℃×８５％ＲＨ（表中：耐湿８０℃）の状態で９６時間放置の漏洩量を測定した。
ヒートサイクル性：−４０℃〜９０℃を各３０分放置するヒートサイクル試験を２００回行った後の漏洩量を測定した。
耐光性：キセノンランプを用いて、疑似天候（日照時間：１０２分と降雨：１８分を１サイクルとする）を４８サイクル行った後の漏洩量を測定した。
4). Electrolyte leakage test conditions The following tests were performed using the pseudo cell created by the previous method, and the superiority or inferiority of the sealing performance was determined by confirming the leakage of the electrolyte. The sealing property of the electrolytic solution was shown in the table by measuring the leakage amount of the sealed electrolytic solution and the weight change rate (%) from the initial value.
Heat resistance: The amount of leakage after standing for 96 hours at a constant temperature of 80 ° C. was measured.
Moisture resistance: The amount of leakage after standing for 96 hours in a state of 60 ° C. × 95% RH (in the table: moisture resistance 60 ° C.) and 80 ° C. × 85% RH (in the table: moisture resistance 80 ° C.) was measured.
Heat cycle property: The amount of leakage after 200 cycles of a heat cycle test in which −40 ° C. to 90 ° C. was allowed to stand for 30 minutes each was measured.
Light resistance: Using a xenon lamp, the amount of leakage after 48 cycles of simulated weather (sunshine duration: 102 minutes and rainfall: 18 minutes as one cycle) was measured.
実施例３〜７、比較例１〜２、参考例１、２
上記各シール剤を用いて、また、上述の手法により電解液Ａを封入した疑似色素増感型太陽電池セルを製造し、各試験条件における電解液漏洩率を表２に示した。
Example 3-7, Comparative Examples 1-2, Reference Examples 1 and 2
A pseudo dye-sensitized solar cell in which the electrolytic solution A was encapsulated was manufactured using the above-described sealing agents by the above-described method, and the electrolytic solution leakage rate under each test condition is shown in Table 2.
本発明のシール剤（シール剤Ａ〜Ｇ）は、いずれも水添化されていないシール剤（シール剤Ｈ、Ｉ）よりも各条件（耐熱性、ヒートサイクル、耐光性）において優れた封止性能が見られた。 The sealing agents (sealing agents A to G) of the present invention are superior in sealing (heat resistance, heat cycle, light resistance) in each condition (sealing agents H and I) which are not hydrogenated. Performance was seen.
また、（Ｃ）側鎖にグリシジル基を有する多官能エポキシ樹脂を添加することで高温高湿条件下での封止性能が向上することが分かった。しかし実施例７の結果の通り、添加量が多くなることで耐光性、ヒートサイクル性が低下することが分かった。またこの際にシール剤はヨウ素によって茶色に変色していた。 Moreover, it turned out that the sealing performance under high-temperature, high-humidity conditions improves by adding the polyfunctional epoxy resin which has a glycidyl group in (C) side chain. However, as the result of Example 7, it turned out that light resistance and heat cycle property fall by the addition amount increasing. At this time, the sealant was turned brown by iodine.
次に、シール剤として表１に示すＡ，Ｅ，Ｈ，Ｉを用い、封入する電解液をＢ，Ｃ，Ｄと変化させたときのシール剤の封止性能を測定するため、実施例１と同様にして疑似色素増感型太陽電池セルを製造し、耐光性試験における電解液漏洩性試験行った。その結果を電解液漏洩率を表３に示した。 Next, Example 1 was used to measure the sealing performance of the sealing agent when A, E, H, and I shown in Table 1 were used as the sealing agent, and the sealed electrolyte was changed to B, C, and D. A pseudo dye-sensitized solar cell was manufactured in the same manner as described above, and an electrolyte leakage test in a light resistance test was performed. The results are shown in Table 3.
上記の結果から、いずれの電解液においても本発明のシール剤は未水添（非水素化）のものと比較して優れたシール性を示すことが分かった。 From the above results, it was found that the sealing agent of the present invention showed excellent sealing properties in any electrolytic solution compared to the non-hydrogenated (non-hydrogenated) one.
本発明における組成物は優れた耐電解液性、耐熱性、耐湿性を有しており、色素増感型太陽電池用シール剤として有用であるばかりでなく、集電グリッドの保護コーティング剤としても使用することができる。また、本発明のシール剤は優れた耐電解液性を有しているので、電解液を用いる一次電池や二次電池のシール剤・接着剤・コーティング剤として使用することも可能である。さらには、優れた耐湿性、耐熱性を有しているので、工業用、家庭用などの電子機器に用いられる電子デバイス部品のシール剤・接着剤・コーティング剤・モールディング剤・ポッティング剤としても使用することができる。 The composition of the present invention has excellent electrolytic solution resistance, heat resistance and moisture resistance, and is useful not only as a sealant for dye-sensitized solar cells but also as a protective coating agent for current collecting grids. Can be used. Moreover, since the sealing agent of this invention has the outstanding electrolyte solution resistance, it can also be used as a sealing agent, adhesive agent, and coating agent of the primary battery which uses electrolyte solution, or a secondary battery. In addition, because it has excellent moisture resistance and heat resistance, it can also be used as a sealing agent, adhesive, coating agent, molding agent, and potting agent for electronic device parts used in electronic equipment for industrial and household use. can do.
１０ 硬化前のシール剤
１２ ガラス板
１４ 注入孔が設けられたガラス板
１６ 電解液注入孔
DESCRIPTION OF SYMBOLS 10 Sealing agent before hardening 12 Glass plate 14 Glass plate provided with injection hole 16 Electrolyte injection hole
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| JP2009117308A (en) * | 2007-11-09 | 2009-05-28 | Shin Etsu Chem Co Ltd | Sealant for dye-sensitized solar cell |
| PT104282A (en) | 2008-12-05 | 2010-06-07 | Univ Do Porto | DSC SOLAR CELL GLASS SELECTION PROCESS |
| KR20110134407A (en) * | 2009-02-20 | 2011-12-14 | 세키스이가가쿠 고교가부시키가이샤 | Sealing agent for dye-sensitized solar cell and dye-sensitized solar cell |
| KR101017191B1 (en) | 2009-05-25 | 2011-02-25 | 도레이첨단소재 주식회사 | Encapsulation Film for Solar Cell Module |
| JP2011044357A (en) * | 2009-08-21 | 2011-03-03 | Sony Corp | Photocell module, and manufacturing method of photocell module |
| JP5649648B2 (en) | 2010-05-17 | 2015-01-07 | 日本化薬株式会社 | Photoelectric conversion element using sealant for thermosetting photoelectric conversion element |
| CN103283085B (en) | 2010-12-27 | 2015-12-09 | 三键精密化学有限公司 | Sealant composition for photoelectric conversion element |
| JP2012136614A (en) * | 2010-12-27 | 2012-07-19 | Three Bond Co Ltd | Gas-barrier photosetting resin composition |
| JP5812275B2 (en) * | 2011-10-24 | 2015-11-11 | スリーボンドファインケミカル株式会社 | Sealant composition for photoelectric conversion element |
| KR101349344B1 (en) * | 2011-12-06 | 2014-01-17 | 한국전기연구원 | organic-inorganic sealant for internal and external protection of photovoltaic cell |
| JP2014071951A (en) * | 2012-09-27 | 2014-04-21 | Fujikura Ltd | Electrode for photoelectric conversion element and photoelectric conversion element using the same |
| JP5878913B2 (en) * | 2013-12-17 | 2016-03-08 | 互応化学工業株式会社 | Photosensitive resin composition, composition for solder resist, printed wiring board, and method for producing photosensitive resin composition |
| JP5930248B2 (en) * | 2015-06-05 | 2016-06-08 | 株式会社スリーボンド | Gas barrier photocurable resin composition |
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