JP2007046035A - Encapsulant for organic electroluminescent device, method for producing organic electroluminescent display and organic electroluminescent display - Google Patents
Encapsulant for organic electroluminescent device, method for producing organic electroluminescent display and organic electroluminescent display Download PDFInfo
- Publication number
- JP2007046035A JP2007046035A JP2005378504A JP2005378504A JP2007046035A JP 2007046035 A JP2007046035 A JP 2007046035A JP 2005378504 A JP2005378504 A JP 2005378504A JP 2005378504 A JP2005378504 A JP 2005378504A JP 2007046035 A JP2007046035 A JP 2007046035A
- Authority
- JP
- Japan
- Prior art keywords
- organic
- sealing agent
- organic electroluminescent
- epoxy resin
- compound
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000008393 encapsulating agent Substances 0.000 title abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 86
- 239000004593 Epoxy Substances 0.000 claims abstract description 28
- 125000003118 aryl group Chemical group 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 110
- 238000007789 sealing Methods 0.000 claims description 106
- 239000000758 substrate Substances 0.000 claims description 47
- 229920000647 polyepoxide Polymers 0.000 claims description 23
- 239000003822 epoxy resin Substances 0.000 claims description 20
- 238000005401 electroluminescence Methods 0.000 claims description 17
- -1 polyoxypropylene bisphenol Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 11
- 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 10
- 230000001678 irradiating effect Effects 0.000 claims description 9
- 239000000565 sealant Substances 0.000 claims description 9
- 239000004843 novolac epoxy resin Substances 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 5
- 238000012663 cationic photopolymerization Methods 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 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 4
- 239000011248 coating agent Substances 0.000 claims description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 4
- 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 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 3
- 229930003836 cresol Natural products 0.000 claims description 3
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 2
- WOCGGVRGNIEDSZ-UHFFFAOYSA-N 4-[2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical compound C=1C=C(O)C(CC=C)=CC=1C(C)(C)C1=CC=C(O)C(CC=C)=C1 WOCGGVRGNIEDSZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000010290 biphenyl Nutrition 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 150000002430 hydrocarbons Chemical group 0.000 claims description 2
- 125000003367 polycyclic group Chemical group 0.000 claims description 2
- 238000004020 luminiscence type Methods 0.000 claims 1
- 239000003505 polymerization initiator Substances 0.000 abstract description 28
- 238000004040 coloring Methods 0.000 abstract description 7
- 238000010538 cationic polymerization reaction Methods 0.000 abstract description 3
- 238000001723 curing Methods 0.000 description 30
- 238000000034 method Methods 0.000 description 22
- 239000000853 adhesive Substances 0.000 description 19
- 230000001070 adhesive effect Effects 0.000 description 17
- 150000001450 anions Chemical class 0.000 description 14
- 239000011521 glass Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- 229910052796 boron Inorganic materials 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000035699 permeability Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 7
- 229910052753 mercury Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 150000003983 crown ethers Chemical class 0.000 description 6
- 230000002093 peripheral effect Effects 0.000 description 6
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229920003986 novolac Polymers 0.000 description 5
- 239000003504 photosensitizing agent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 239000002033 PVDF binder Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 239000011324 bead Substances 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 150000002367 halogens Chemical group 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 4
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 4
- 238000000016 photochemical curing Methods 0.000 description 4
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 4
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 125000001931 aliphatic group Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 235000010216 calcium carbonate Nutrition 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 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 3
- 125000001624 naphthyl group Chemical group 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 238000001771 vacuum deposition Methods 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- NJWGQARXZDRHCD-UHFFFAOYSA-N 2-methylanthraquinone Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC=C3C(=O)C2=C1 NJWGQARXZDRHCD-UHFFFAOYSA-N 0.000 description 2
- VVBLNCFGVYUYGU-UHFFFAOYSA-N 4,4'-Bis(dimethylamino)benzophenone Chemical compound C1=CC(N(C)C)=CC=C1C(=O)C1=CC=C(N(C)C)C=C1 VVBLNCFGVYUYGU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000012965 benzophenone Substances 0.000 description 2
- ZFVMWEVVKGLCIJ-UHFFFAOYSA-N bisphenol AF Chemical compound C1=CC(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C=C1 ZFVMWEVVKGLCIJ-UHFFFAOYSA-N 0.000 description 2
- 239000004842 bisphenol F epoxy resin Substances 0.000 description 2
- ZADPBFCGQRWHPN-UHFFFAOYSA-N boronic acid Chemical compound OBO ZADPBFCGQRWHPN-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000013007 heat curing Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 229910052752 metalloid Inorganic materials 0.000 description 2
- 150000002738 metalloids Chemical class 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 2
- VLTYTTRXESKBKI-UHFFFAOYSA-N (2,4-dichlorophenyl)-phenylmethanone Chemical compound ClC1=CC(Cl)=CC=C1C(=O)C1=CC=CC=C1 VLTYTTRXESKBKI-UHFFFAOYSA-N 0.000 description 1
- 125000004642 (C1-C12) alkoxy group Chemical group 0.000 description 1
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 description 1
- MSAHTMIQULFMRG-UHFFFAOYSA-N 1,2-diphenyl-2-propan-2-yloxyethanone Chemical compound C=1C=CC=CC=1C(OC(C)C)C(=O)C1=CC=CC=C1 MSAHTMIQULFMRG-UHFFFAOYSA-N 0.000 description 1
- XQQZRZQVBFHBHL-UHFFFAOYSA-N 12-crown-4 Chemical compound C1COCCOCCOCCO1 XQQZRZQVBFHBHL-UHFFFAOYSA-N 0.000 description 1
- VFTFKUDGYRBSAL-UHFFFAOYSA-N 15-crown-5 Chemical compound C1COCCOCCOCCOCCO1 VFTFKUDGYRBSAL-UHFFFAOYSA-N 0.000 description 1
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- BTJPUDCSZVCXFQ-UHFFFAOYSA-N 2,4-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(CC)=CC(CC)=C3SC2=C1 BTJPUDCSZVCXFQ-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- HIGURUTWFKYJCH-UHFFFAOYSA-N 2-[[1-(oxiran-2-ylmethoxymethyl)cyclohexyl]methoxymethyl]oxirane Chemical compound C1OC1COCC1(COCC2OC2)CCCCC1 HIGURUTWFKYJCH-UHFFFAOYSA-N 0.000 description 1
- FPKCTSIVDAWGFA-UHFFFAOYSA-N 2-chloroanthracene-9,10-dione Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3C(=O)C2=C1 FPKCTSIVDAWGFA-UHFFFAOYSA-N 0.000 description 1
- ZCDADJXRUCOCJE-UHFFFAOYSA-N 2-chlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(Cl)=CC=C3SC2=C1 ZCDADJXRUCOCJE-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- KTALPKYXQZGAEG-UHFFFAOYSA-N 2-propan-2-ylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C(C)C)=CC=C3SC2=C1 KTALPKYXQZGAEG-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 description 1
- 125000006539 C12 alkyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- NQSMEZJWJJVYOI-UHFFFAOYSA-N Methyl 2-benzoylbenzoate Chemical compound COC(=O)C1=CC=CC=C1C(=O)C1=CC=CC=C1 NQSMEZJWJJVYOI-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 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
- 238000005349 anion exchange Methods 0.000 description 1
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- LUAKDNCXFXZOEC-UHFFFAOYSA-N antimony(3+);triphenylsulfanium Chemical compound [Sb+3].C1=CC=CC=C1[S+](C=1C=CC=CC=1)C1=CC=CC=C1 LUAKDNCXFXZOEC-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical class C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- 150000008366 benzophenones Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- NKWPZUCBCARRDP-UHFFFAOYSA-L calcium bicarbonate Chemical compound [Ca+2].OC([O-])=O.OC([O-])=O NKWPZUCBCARRDP-UHFFFAOYSA-L 0.000 description 1
- 229910000020 calcium bicarbonate Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001728 carbonyl compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical compound [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 150000008049 diazo compounds Chemical class 0.000 description 1
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 description 1
- 239000012954 diazonium Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000009545 invasion Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000010445 mica Substances 0.000 description 1
- 229910052618 mica group Inorganic materials 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229940044654 phenolsulfonic acid Drugs 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000012744 reinforcing agent Substances 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003458 sulfonic acid derivatives Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 239000004034 viscosity adjusting agent Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Abstract
Description
本発明は、優れた耐光性と耐湿性を有し、使用条件下での着色が非常に少なく、更に低粘度であり大面積の有機エレクトロルミネッセンス表示装置の製造にも好適に用いることができる有機エレクトロルミネッセンス素子用封止剤、該有機エレクトロルミネッセンス素子用封止剤を用いた有機エレクトロルミネッセンス表示装置の製造方法、及び、有機エレクトロルミネッセンス表示装置に関する。 The present invention has excellent light resistance and moisture resistance, has very little coloration under use conditions, and has a low viscosity and can be suitably used for the production of a large area organic electroluminescence display device. The present invention relates to a sealing agent for electroluminescence elements, a method for producing an organic electroluminescence display device using the sealing agent for organic electroluminescence elements, and an organic electroluminescence display device.
有機エレクトロルミネッセンス素子（以下、有機ＥＬ素子ともいう）は、互いに対向する一対の電極間に有機発光材料層が挟持された積層体構造を有し、この有機発光材料層に一方の電極から電子が注入されるとともに他方の電極から正孔が注入されることにより有機発光材料層内で電子と正孔とが結合して発光する。このように有機ＥＬ素子は自己発光を行うことから、バックライトを必要とする液晶表示素子等と比較して視認性がよく、薄型化が可能であり、しかも直流低電圧駆動が可能であるという利点を有しており、次世代ディスプレイとして着目されている。 An organic electroluminescent element (hereinafter also referred to as an organic EL element) has a laminated structure in which an organic light emitting material layer is sandwiched between a pair of electrodes facing each other, and electrons are transmitted from one electrode to the organic light emitting material layer. By being injected and holes are injected from the other electrode, electrons and holes are combined in the organic light emitting material layer to emit light. As described above, since the organic EL element performs self-emission, it has better visibility than a liquid crystal display element that requires a backlight, can be reduced in thickness, and can be driven by a DC low voltage. It has advantages and is attracting attention as a next-generation display.
しかし、有機ＥＬ素子を構成する有機発光材料や電極は、活性が高く化学的に不安定であるため、水分等による酸化により特性が劣化しやすく、大気中で駆動させると、発光特性が急激に劣化し寿命が短いという問題があった。そこで、一般的な有機ＥＬ素子では、有機ＥＬ素子の上に乾燥剤が設置されたガラス又は金属からなる蓋を被せ、その周辺を接着剤（封止剤）で封止することにより水分の浸入を遮断する構造が採られていた。この方式では、有機ＥＬ素子から発せられた光は蓋の反対側、即ち、有機ＥＬ素子の底部側から取り出されることからボトムエミッション方式とも呼ばれている（例えば、特許文献１参照）。 However, the organic light-emitting materials and electrodes constituting the organic EL element are highly active and chemically unstable. Therefore, the characteristics are likely to deteriorate due to oxidation by moisture or the like. There was a problem of deterioration and short life. Therefore, in general organic EL elements, a glass or metal lid with a desiccant is placed on the organic EL element, and the periphery is sealed with an adhesive (sealing agent), so that moisture can enter. The structure which shuts off was taken. In this method, since light emitted from the organic EL element is taken out from the opposite side of the lid, that is, from the bottom side of the organic EL element, it is also called a bottom emission method (see, for example, Patent Document 1).
一方、近年、従来のボトムエミッション方式の有機ＥＬ素子に代わって、有機ＥＬ素子から発せられた光を上面側から取り出すトップエミッション方式の有機ＥＬ素子が注目されている。この方式は、開口率が高く、低電圧駆動となることから、長寿命化に有利であるという利点がある。このようなトップエミッション方式の有機ＥＬ素子では、通常、積層体を２枚のガラス等の透明材料からなる防湿性基材により挟み込み、該防湿性基材間を充填剤で充填することにより封止している（例えば、特許文献２参照）。しかしながら、このようなトップエミッション方式の有機ＥＬ素子では、光の取り出し方向を遮蔽してしまわないようにするために乾燥剤を配置するスペースがなく、充填剤で充填したとしても充分な防湿効果が得られにくく寿命が短くなるという問題があった。
有機ＥＬ素子用接着剤のみでの封止は、水分が時間とともに浸入するため、有機ＥＬ素子に防湿性の保護膜をコーティングして、有機ＥＬ素子を保護し、更にこの有機ＥＬ素子を接着剤で封止する方法も考案されている（例えば、特許文献３参照）。この方法は、より高い信頼性を有する素子となる。
On the other hand, in recent years, instead of the conventional bottom emission type organic EL element, attention has been paid to a top emission type organic EL element that extracts light emitted from the organic EL element from the upper surface side. This method has an advantage that it has a high aperture ratio and is driven at a low voltage, which is advantageous for extending the life. In such a top emission type organic EL element, usually, the laminate is sandwiched between two moisture-proof substrates made of a transparent material such as glass, and sealed between the moisture-proof substrates with a filler. (For example, refer to Patent Document 2). However, in such a top emission type organic EL element, there is no space for disposing a desiccant so as not to shield the light extraction direction, and even if it is filled with a filler, a sufficient moisture-proof effect is obtained. There was a problem that it was difficult to obtain and the life was shortened.
Sealing with only an adhesive for organic EL elements allows moisture to permeate over time, so that the organic EL element is coated with a moisture-proof protective film to protect the organic EL element, and this organic EL element is further bonded to the adhesive. (See, for example, Patent Document 3). This method results in an element having higher reliability.
しかしながら、保護膜は欠陥が発生しやすく、欠陥が存在すると生産の歩留まりの低下を招く。このため、より防湿性の高い接着剤で封止することが望まれていた。
そこで従来は、透湿度を指標として防湿性の高い接着剤が選択され用いられてきたが、このようにして選択された接着剤を用いて有機ＥＬ素子を封止しても期待されたほど高い防湿性は得られなかった。
However, the protective film is prone to defects, and the presence of defects causes a reduction in production yield. For this reason, it has been desired to seal with an adhesive having higher moisture resistance.
Therefore, conventionally, an adhesive having a high moisture-proof property has been selected and used by using moisture permeability as an index. However, even when an organic EL element is sealed using the adhesive selected in this way, it is as high as expected. Moisture resistance was not obtained.
また、トップエミッション方式の有機ＥＬ素子では、光の取り出し方向に封止剤を配置するため、着色がない封止剤が必要とされる。しかしながら、従来の封止剤は熱や紫外線に曝されることより封止剤が着色し、色の再現性や輝度が低下するという問題があった。 Further, in the top emission type organic EL element, since the sealant is arranged in the light extraction direction, a sealant without coloring is required. However, the conventional sealing agent has a problem that the sealing agent is colored by being exposed to heat and ultraviolet rays, and color reproducibility and luminance are lowered.
更に、ガラス等を用いて有機ＥＬ素子を封止する方法は、未硬化の接着剤を用いて有機ＥＬ素子を封止した後に、熱や光により接着剤を硬化させる方法が採られている。しかし、このような有機ＥＬ素子の封止方法では、接着剤を硬化させる際に、有機ＥＬ素子が直接熱や光に曝されるために有機ＥＬ素子の性能が低下しやすく、場合によっては有機ＥＬ素子が劣化してしまうという問題があった。
光硬化接着剤を用いた場合、光照射時に発生するガスが有機ＥＬ素子の劣化を促進しやすいという問題もあった。更に、基板によってはガラス上の金属配線やカラーフィルター・ブラックマトリックスの存在のため、未硬化の接着剤に光の当らない部分がある場合や、紫外線吸収剤を含み紫外線が遮断される基板を用いる場合、光硬化接着剤が硬化できないという問題があった。
Furthermore, the method of sealing an organic EL element using glass etc. has taken the method of hardening an adhesive agent with a heat | fever or light, after sealing an organic EL element using an unhardened adhesive agent. However, in such an organic EL element sealing method, when the adhesive is cured, the organic EL element is directly exposed to heat or light, so that the performance of the organic EL element is likely to be deteriorated. There was a problem that the EL element deteriorated.
When a photo-curing adhesive is used, there is a problem that the gas generated during light irradiation easily promotes deterioration of the organic EL element. In addition, depending on the substrate, due to the presence of metal wiring on the glass, color filter and black matrix, there are parts where the uncured adhesive is not exposed to light, or a substrate that contains an ultraviolet absorber and blocks ultraviolet rays is used. In such a case, there is a problem that the photo-curing adhesive cannot be cured.
また、近年、より大画面の有機ＥＬ表示装置の開発が要求されており、大面積の有機ＥＬ素子を均一かつ正確に封止できる有機ＥＬ素子用封止剤が求められている。そのため、有機ＥＬ素子用封止剤を低粘度とすることが必要となり、低粘度であり、かつ、耐湿性に優れた有機ＥＬ素子用封止剤が求められていた。
しかしながら、上述の従来技術においては、充分な耐光性と耐湿性を両立させることは困難であった。また、低粘度の要求を同時に満たすような接着剤も得られなかった。
However, in the above-described prior art, it has been difficult to achieve both sufficient light resistance and moisture resistance. Also, an adhesive that satisfies the low viscosity requirement at the same time was not obtained.
本発明は、上記現状に鑑み、優れた耐光性と耐湿性とを有し、使用条件下における着色が非常に少なく、更に低粘度であり大面積の有機エレクトロルミネッセンス表示装置の製造に好適に用いることができる有機エレクトロルミネッセンス素子用封止剤、該有機エレクトロルミネッセンス素子用封止剤を用いた有機エレクトロルミネッセンス表示装置の製造方法、及び、有機エレクトロルミネッセンス表示装置を提供することを目的とする。 In view of the above situation, the present invention has excellent light resistance and moisture resistance, has very little coloration under use conditions, and is suitably used for the production of an organic electroluminescence display device having a low viscosity and a large area. An object of the present invention is to provide a sealing agent for organic electroluminescence elements, a method for producing an organic electroluminescence display device using the sealing agent for organic electroluminescence elements, and an organic electroluminescence display device.
本発明は、光重合性化合物と光カチオン重合開始剤とを含有する有機エレクトロルミネッセンス素子用封止剤であって、前記光重合性化合物は、該光重合性化合物１００重量部に対して、脂肪族環状骨格を有するエポキシ化合物を２０〜８０重量部、及び、芳香族環を有するエポキシ化合物を８０〜２０重量部含有する有機エレクトロルミネッセンス素子用封止剤である。
以下に本発明を詳述する。
The present invention relates to an organic electroluminescent device sealing agent comprising a photopolymerizable compound and a photocationic polymerization initiator, wherein the photopolymerizable compound is a fat based on 100 parts by weight of the photopolymerizable compound. It is a sealing agent for organic electroluminescent elements containing 20 to 80 parts by weight of an epoxy compound having an aromatic ring skeleton and 80 to 20 parts by weight of an epoxy compound having an aromatic ring.
The present invention is described in detail below.
本発明者らは、鋭意検討した結果、光硬化性樹脂を含有する有機ＥＬ素子用封止剤であって、該光硬化性樹脂が特定の構造を有するエポキシ化合物を特定の配合量で含有するものは、優れた耐光性を有し紫外線等の光照射によって着色することがなく、かつ、耐湿性にも優れ、更に、低粘度とすることができるため、大面積の有機ＥＬ表示装置の製造に好適に用いることかできることを見出し、本発明を完成させるに至った。 As a result of intensive studies, the inventors of the present invention are sealing agents for organic EL elements containing a photocurable resin, and the photocurable resin contains an epoxy compound having a specific structure in a specific blending amount. Since it has excellent light resistance, is not colored by irradiation with light such as ultraviolet rays, is excellent in moisture resistance, and can be made to have a low viscosity, it can produce a large area organic EL display device. As a result, the present invention has been completed.
本発明の有機ＥＬ素子用封止剤は、光重合性化合物を含有する。
上記光重合性化合物は、脂肪族環状骨格を有するエポキシ化合物と芳香族環を有するエポキシ化合物とを含有する。
The sealing agent for organic EL elements of this invention contains a photopolymerizable compound.
The photopolymerizable compound contains an epoxy compound having an aliphatic cyclic skeleton and an epoxy compound having an aromatic ring.
上記脂肪族環状骨格を有するエポキシ化合物としては、その構造中に脂肪族環状骨格とエポキシ基とを有するものであれば特に限定されず、構造中、又は、繰り返し単位内に上記脂肪族環状骨格を１つだけ有する化合物であってもよく、繰り返し単位内に２個以上の脂肪族環状骨格を有する化合物であってもよいが、繰り返し単位内に２個以上の脂肪族環状骨格を有する化合物がより好適に用いられる。上記脂肪族環状骨格を有するエポキシ化合物が繰り返し単位内に２個以上の脂肪族環状骨格を有する化合物である場合、本発明の有機ＥＬ素子用封止剤は、より耐光性、耐湿性等に優れたものとなる。 The epoxy compound having an aliphatic cyclic skeleton is not particularly limited as long as it has an aliphatic cyclic skeleton and an epoxy group in the structure, and the aliphatic cyclic skeleton is included in the structure or in a repeating unit. It may be a compound having only one or a compound having two or more aliphatic cyclic skeletons in a repeating unit, but a compound having two or more aliphatic cyclic skeletons in a repeating unit is more preferable. Preferably used. When the epoxy compound having an aliphatic cyclic skeleton is a compound having two or more aliphatic cyclic skeletons in a repeating unit, the organic EL device sealing agent of the present invention is more excellent in light resistance, moisture resistance and the like. It will be.
上記構造中、又は、繰り返し単位内に上記脂肪族環状骨格を１つだけ有する化合物としては特に限定されないが、例えば、下記化学式（１）、（２）で表される化合物、及び、下記一般式（３）で表される化合物からなる群より選択される少なくとも１種が好適に用いられる。 Although it does not specifically limit as a compound which has only one said aliphatic cyclic skeleton in the said structure or a repeating unit, For example, the compound represented by following Chemical formula (1), (2), and the following general formula At least one selected from the group consisting of compounds represented by (3) is preferably used.
上記化学式（１）で表される化合物のうち、市販されているものとしては、例えば、新日本理化工業社製「ＤＭＥ−１００」、旭電化工業社製「ＥＰ−４０８５」等が挙げられる。
上記化学式（２）で表される化合物のうち、市販されているものとしては、例えば、ダイセル化学工業社製「セロキサイド３０００」等が挙げられる。
上記一般式（３）で表される化合物のうち、市販されているものとしては、例えば、ダイセル化学工業社製「ＥＨＰＥ３１５０」等が挙げられる。
Among the compounds represented by the chemical formula (1), examples of commercially available compounds include “DME-100” manufactured by Shin Nippon Rika Kogyo Co., Ltd. and “EP-4085” manufactured by Asahi Denka Kogyo Co., Ltd.
Among the compounds represented by the chemical formula (2), examples of commercially available compounds include “Celoxide 3000” manufactured by Daicel Chemical Industries, Ltd.
Among the compounds represented by the general formula (3), examples of commercially available compounds include “EHPE3150” manufactured by Daicel Chemical Industries, Ltd.
また、上記繰り返し単位内に２個以上の脂肪族環状骨格を有する化合物としては特に限定されないが、繰り返し単位内に２個以上のシクロヘキシル基、又は、多環状炭化水素基を有する化合物であることが好ましく、このような化合物としては、例えば、下記一般式（４）、（５）又は（６）からなる群より選択される少なくとも１種であることが好ましい。これらの化合物は、耐光性に優れるとともに、耐湿性にも優れるからである。 The compound having two or more aliphatic cyclic skeletons in the repeating unit is not particularly limited, but may be a compound having two or more cyclohexyl groups or polycyclic hydrocarbon groups in the repeating unit. Preferably, such a compound is preferably at least one selected from the group consisting of the following general formula (4), (5) or (6). This is because these compounds are excellent in light resistance and moisture resistance.
上記一般式（４）で表される化合物のうち、市販されているものとしては、例えば、ジャパンエポキシレジン社製「エピコートＹＸ８０００」（Ｒ１＝Ｒ２＝ＣＨ３の場合）、「エピコートＹＬ６７５３」（Ｒ＝Ｈの場合）等が挙げられる。
上記一般式（５）で表される化合物のうち、市販されているものとしては、例えば、「エピコートＹＬ７０４０」（Ｒ１、Ｒ３、Ｒ６、Ｒ８＝ＣＨ３、Ｒ２、Ｒ４、Ｒ５、Ｒ７＝Ｈの場合）等が挙げられる。
上記一般式（６）で表される化合物のうち、市販されているものとしては、例えば、旭電化社製「ＥＰ−４０８８」等が挙げられる。
Among the compounds represented by the general formula (4), commercially available compounds include, for example, “Epicoat YX8000” (in the case of R 1 = R 2 = CH 3 ), “Epicoat YL6753” manufactured by Japan Epoxy Resin Co., Ltd. (When R = H).
Among the compounds represented by the general formula (5), commercially available compounds include, for example, “Epicoat YL7040” (R 1 , R 3 , R 6 , R 8 = CH 3 , R 2 , R 4 , And R 5 and R 7 = H).
Among the compounds represented by the general formula (6), examples of commercially available compounds include “EP-4088” manufactured by Asahi Denka Co., Ltd.
上記一般式（４）で表される化合物の中でも、Ｒ１及びＲ２は、水素又はメチル基であることがより好ましい。これらを用いることで、本発明の有機ＥＬ素子用封止剤は、優れた耐光性と耐湿性とを兼ね備えたものとなる。なかでも、Ｒ１及びＲ２は、水素であることが特に好ましい。 Among the compounds represented by the general formula (4), R 1 and R 2 are more preferably hydrogen or a methyl group. By using these, the sealing agent for organic EL elements of the present invention has both excellent light resistance and moisture resistance. Of these, R 1 and R 2 are particularly preferably hydrogen.
本発明の有機ＥＬ素子用封止剤において、上記脂肪族環状骨格を有するエポキシ化合物の配合量は、上記光重合性化合物１００重量部に対して、下限が２０重量部、上限が８０重量部である。２０重量部未満であると、本発明の有機ＥＬ素子用封止剤の耐光性が不充分となり、８０重量部を超えると、本発明の有機ＥＬ素子用封止剤の耐湿性が不充分となる。
なかでも、上記脂肪族環状骨格を有するエポキシ化合物が上記化学式（１）、（２）及び一般式（３）からなる群より選択される少なくとも１種である場合、本発明の有機ＥＬ素子用封止剤の透湿度が上がることがあるため、その配合量の好ましい上限は、上記光重合性化合物１００重量部に対して５０重量部である。
上記脂肪族環状骨格を有するエポキシ化合物が上記一般式（４）、（５）又は（６）からなる群より選択される少なくとも１種である場合、より高い耐光性と耐湿性を両立させ得る場合があることから、好ましい下限は３０重量部、好ましい上限は７０重量部である。
In the encapsulant for organic EL devices of the present invention, the amount of the epoxy compound having an aliphatic cyclic skeleton is 20 parts by weight for the lower limit and 80 parts by weight for the upper part of the photopolymerizable compound. is there. If it is less than 20 parts by weight, the light resistance of the organic EL device sealing agent of the present invention will be insufficient, and if it exceeds 80 parts by weight, the organic EL device sealing agent of the present invention will have insufficient moisture resistance. Become.
In particular, when the epoxy compound having an aliphatic cyclic skeleton is at least one selected from the group consisting of the chemical formulas (1), (2), and the general formula (3), the organic EL device seal of the present invention is used. Since the moisture permeability of the stopper may increase, the preferable upper limit of the blending amount is 50 parts by weight with respect to 100 parts by weight of the photopolymerizable compound.
When the epoxy compound having an aliphatic cyclic skeleton is at least one selected from the group consisting of the above general formulas (4), (5), or (6), when both higher light resistance and moisture resistance can be achieved Therefore, the preferable lower limit is 30 parts by weight, and the preferable upper limit is 70 parts by weight.
本発明の有機ＥＬ素子用封止剤は、上記光重合性化合物が脂肪族環状骨格を有するエポキシ化合物を上記範囲で含有するため、耐光性が優れたものとなると同時に、高い耐湿性も有するものとなる。このような高い耐光性が得られる理由としては、芳香族骨格のエポキシ化合物のみからなる有機ＥＬ素子用封止剤は、紫外線により、芳香族骨格が変化し、共役系が発達したり、芳香環と開始剤とが電荷移動錯体を形成し、黄変や着色の原因となるものと推察される。脂肪族骨格を有するエポキシ化合物を含有させることにより、共役系の発達や電荷移動錯体の形成が緩和又は希釈されるため、着色を低減することができると推察される。
また、本発明の有機ＥＬ素子用封止剤の光硬化時の反応性が向上するため、後述する光カチオン重合開始剤の添加量を少なくすることができる。このため、後述する光カチオン重合開始剤に起因する着色が少なくなり、耐光性が向上する。また、光硬化時に上記光カチオン重合開始剤に起因するアウトガスの発生を抑制することができ、有機ＥＬ素子を封止した本発明の有機ＥＬ素子用封止剤を光硬化させた際に、有機ＥＬ素子の上記アウトガスによる劣化を好適に防止することができる。
更に、本発明の有機ＥＬ素子用封止剤は、常温において低粘度となるため、大面積の有機ＥＬ素子の製造時に、均一でかつ短時間に有機ＥＬ素子用封止剤を流延することができる。
The encapsulant for organic EL devices of the present invention contains an epoxy compound having an aliphatic cyclic skeleton in the above range, so that it has excellent light resistance and at the same time has high moisture resistance. It becomes. The reason why such high light resistance can be obtained is that the sealing agent for organic EL elements composed only of an epoxy compound having an aromatic skeleton changes its aromatic skeleton due to ultraviolet rays, a conjugated system develops, an aromatic ring It is presumed that the initiator and the initiator form a charge transfer complex and cause yellowing or coloring. By including an epoxy compound having an aliphatic skeleton, the development of the conjugated system and the formation of the charge transfer complex are alleviated or diluted, and it is assumed that coloring can be reduced.
Moreover, since the reactivity at the time of photocuring of the sealing agent for organic EL elements of this invention improves, the addition amount of the photocationic polymerization initiator mentioned later can be decreased. For this reason, the coloring resulting from the photocationic polymerization initiator described later is reduced, and the light resistance is improved. Moreover, the generation of outgas resulting from the above-mentioned photocationic polymerization initiator during photocuring can be suppressed, and when the organic EL device sealing agent of the present invention in which the organic EL device is sealed is photocured, The deterioration of the EL element due to the outgas can be suitably prevented.
Furthermore, since the organic EL element sealing agent of the present invention has a low viscosity at room temperature, the organic EL element sealing agent can be cast uniformly and in a short time during the production of a large-area organic EL element. Can do.
上記芳香族環を有するエポキシ化合物としては、その構造中に芳香族環とエポキシ基とを有する化合物であれば特に限定されず、例えば、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、ビフェニルノボラック型エポキシ樹脂、トリスフェノールノボラック型エポキシ樹脂、ジシクロペンタジエンノボラック型エポキシ樹脂等のノボラック型エポキシ樹脂；ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、２、２’−ジアリルビスフェノールＡ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ポリオキシプロピレンビスフェノールＡ型エポキシ等のビスフェノール型エポキシ樹脂等が挙げられる。なかでも、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂が好適に用いられる。
これらの芳香族環を有するエポキシ化合物は、単独で用いられてもよく、２種以上が併用されてもよい。
The epoxy compound having an aromatic ring is not particularly limited as long as it is a compound having an aromatic ring and an epoxy group in its structure. For example, a phenol novolac type epoxy resin, a cresol novolac type epoxy resin, a biphenyl novolac type Epoxy resin, trisphenol novolac epoxy resin, novolac epoxy resin such as dicyclopentadiene novolac epoxy resin; bisphenol A epoxy resin, bisphenol F epoxy resin, 2,2′-diallylbisphenol A epoxy resin, bisphenol S Bisphenol type epoxy resins such as epoxy resin and polyoxypropylene bisphenol A type epoxy. Among these, bisphenol A type epoxy resins and bisphenol F type epoxy resins are preferably used.
The epoxy compound which has these aromatic rings may be used independently, and 2 or more types may be used together.
上記エポキシ樹脂の原料のうち、市販されているものとしては、フェノールノボラック型のものとしては、例えば、「エピクロンＮ−７４０」、「エピクロンＮ−７７０」、「エピクロンＮ−７７５」（いずれも、大日本インキ化学社製）、「エピコート１５２」、「エピコート１５４」（いずれも、ジャパンエポキシレジン社製）等が挙げられ、クレゾールノボラック型のものとしては、例えば、「エピクロンＮ−６６０」、「エピクロンＮ−６６５」、「エピクロンＮ−６７０」、「エピクロンＮ−６７３」、「エピクロンＮ−６８０」、「エピクロンＮ−６９５」、「エピクロンＮ−６６５−ＥＸＰ」、「エピクロンＮ−６７２−ＥＸＰ」（いずれも、大日本インキ化学社製）等が挙げられる。また、ビスフェノール型のものとしては、例えば、「エピコート８２８」、「エピコート１００１」、「エピコート１００２」（いずれも、ジャパンエポキシレジン社製）等が挙げられる。 Among the raw materials for the epoxy resin, commercially available phenol novolac types include, for example, “Epicron N-740”, “Epicron N-770”, “Epicron N-775” (both Dainippon Ink Chemical Co., Ltd.), “Epicoat 152”, “Epicoat 154” (all manufactured by Japan Epoxy Resin Co., Ltd.) and the like. Examples of the cresol novolak type include “Epicron N-660”, “ "Epicron N-665", "Epicron N-670", "Epicron N-673", "Epicron N-680", "Epicron N-695", "Epicron N-665-EXP", "Epicron N-672-EXP" (Both manufactured by Dainippon Ink & Chemicals, Inc.). Examples of the bisphenol type include “Epicoat 828”, “Epicoat 1001”, and “Epicoat 1002” (all manufactured by Japan Epoxy Resin Co., Ltd.).
本発明の有機ＥＬ素子用封止剤において、上記芳香族環を有するエポキシ化合物の配合量は、上記光重合性化合物１００重量部に対して、下限が２０重量部、上限が８０重量部である。２０重量部未満であると、本発明の有機ＥＬ素子用封止剤を光硬化させた際の硬化性に劣るとともに、耐湿性にも劣り、封止剤として充分に機能しなくなり、８０重量部を超えると、相対的に上述した脂肪族環状骨格を有するエポキシ化合物の配合量が少なくなり、本発明の有機ＥＬ素子用封止剤の耐光性、耐湿性等が不充分となる。 In the organic EL device sealing agent of the present invention, the amount of the epoxy compound having an aromatic ring is 20 parts by weight at the lower limit and 80 parts by weight at the upper limit with respect to 100 parts by weight of the photopolymerizable compound. . When the amount is less than 20 parts by weight, it is inferior in curability when the organic EL element sealing agent of the present invention is photocured, inferior in moisture resistance, and does not sufficiently function as a sealing agent. If it exceeds 1, the blending amount of the epoxy compound having an aliphatic cyclic skeleton described above becomes relatively small, and the light resistance, moisture resistance, etc. of the organic EL device sealing agent of the present invention become insufficient.
本発明の有機ＥＬ素子用封止剤は、光カチオン重合開始剤を含有する。
上記光カチオン重合開始剤としては特に限定されず、イオン性光酸発生タイプであってもよいし、非イオン性光酸発生タイプであってもよいが、なかでも、重合効率が高いことから下記式（７）で表されるようなボロン酸を対アニオンとするボロン酸塩からなる光カチオン重合開始剤が好適に用いられ、具体的には、「Ｐｈｏｔｏｉｎｉｔｉａｔｏｒ ２０７４」（ローディア社製）等の市販品が挙げられる。
The sealing agent for organic EL elements of this invention contains a photocationic polymerization initiator.
The photo-cationic polymerization initiator is not particularly limited, and may be an ionic photoacid generation type or a nonionic photoacid generation type. A photocationic polymerization initiator composed of a boronate having a boronic acid as a counter anion as represented by the formula (7) is preferably used. Specifically, “Photoinitiator 2074” (manufactured by Rhodia) or the like is commercially available. Goods.
上記イオン性光酸発生タイプの光カチオン重合開始剤としては特に限定されず、例えば、芳香族ジアゾニウム塩、芳香族ハロニウム塩、芳香族スルホニウム塩等のオニウム塩類や、鉄−アレン錯体、チタノセン錯体、アリールシラノール−アルミニウム錯体等の有機金属錯体類等が挙げられる。これらの光カチオン重合開始剤は単独で用いられてもよいし、２種以上が併用されてもよい。 The cationic photopolymerization initiator of the ionic photoacid generation type is not particularly limited, for example, onium salts such as aromatic diazonium salt, aromatic halonium salt, aromatic sulfonium salt, iron-allene complex, titanocene complex, And organometallic complexes such as arylsilanol-aluminum complexes. These photocationic polymerization initiators may be used independently and 2 or more types may be used together.
上記イオン性光酸発生タイプの光カチオン重合開始剤の具体例としては、例えば、「アデカオプトマーＳＰ１５０」、「アデカオプトマーＳＰ１７０」（いずれも旭電化工業社製）、「ＵＶＥ−１０１４」（ゼネラルエレクトロニクス社製）、「ＣＤ−１０１２」（サートマー社製）、「ＲＤ−２０７４」（ローディア社製）等が挙げられる。 Specific examples of the ionic photoacid generation type photocationic polymerization initiator include, for example, “Adekaoptomer SP150”, “Adekaoptomer SP170” (all manufactured by Asahi Denka Kogyo Co., Ltd.), “UVE-1014” ( General Electronics Co., Ltd.), “CD-1012” (Sartomer Co.), “RD-2074” (Rhodia Co., Ltd.), and the like.
また、上記イオン性光酸発生タイプの光カチオン重合開始剤は、下記一般式（８）又は下記一般式（９）で表されるスルホニウムカチオン部分を有することが好ましい。 Moreover, it is preferable that the said ionic photoacid generation type photocationic polymerization initiator has a sulfonium cation part represented by the following general formula (8) or the following general formula (9).
上記一般式（８）及び一般式（９）中、Ｒ９〜Ｒ１４は、互いに同一であってもよいし、異なっていてもよく、それぞれ１価若しくは２価のフェニル基又はナフチル基を表し、これらフェニル基又はナフチル基は、直鎖状又は分枝鎖状Ｃ１〜Ｃ１２アルキル基、直鎖状又は分枝鎖状Ｃ１〜Ｃ１２アルコキシル基、ハロゲン原子、−ＯＨ基、−ＣＯＯＨ基及び−ＣＯＯ−アルキルエステル基（ここで、アルキル部分は直鎖状又は分枝鎖状Ｃ１〜Ｃ１２残基である）からなる群より選択される少なくとも１個の基で随意に置換されていてもよい。 In the general formula (8) and the general formula (9), R 9 to R 14 may be the same as or different from each other, and each represents a monovalent or divalent phenyl group or naphthyl group. These phenyl groups or naphthyl groups are linear or branched C 1 -C 12 alkyl groups, linear or branched C 1 -C 12 alkoxyl groups, halogen atoms, —OH groups, —COOH. (wherein the alkyl moiety is linear or branched C 1 -C 12 residues) groups and -COO- alkyl ester group is optionally substituted with at least one group selected from the group consisting of It may be.
また、上記イオン性光酸発生タイプの光カチオン重合開始剤は、下記一般式（１０）で表されるホウ素中心アニオン部分を有することが好ましい。 Moreover, it is preferable that the said ionic photoacid generation type photocationic polymerization initiator has a boron center anion part represented by following General formula (10).
上記一般式（１０）中、Ｂは、３価のホウ素を表し、Ｒ１５〜Ｒ１８の少なくとも１個は、炭素数６〜３０のハロゲン置換芳香族基を表す。このように中心アニオンがホウ素であると、光カチオン重合開始剤の酸強度が強くなるため、この光カチオン重合開始剤を用いた有機ＥＬ素子用封止剤の硬化性が向上し、高いガラス転移温度を有する硬化物を得ることができる。その結果、本発明の有機ＥＬ素子用封止剤の透湿性（透湿度）が低下するため、この有機ＥＬ素子用封止剤を用いて作製した有機ＥＬ表示装置の有機ＥＬ素子の寿命を長くすることができ、信頼性を高めることができる。 In the general formula (10), B represents trivalent boron, and at least one of R 15 to R 18 represents a halogen-substituted aromatic group having 6 to 30 carbon atoms. When the central anion is boron as described above, the acid strength of the photocationic polymerization initiator is increased, so that the curability of the organic EL device sealing agent using this photocationic polymerization initiator is improved and the glass transition is high. A cured product having a temperature can be obtained. As a result, the moisture permeability (moisture permeability) of the sealing agent for organic EL elements of the present invention is lowered, so the life of the organic EL element of the organic EL display device produced using this sealing agent for organic EL elements is extended. Can improve reliability.
上記一般式（１０）中、Ｒ１５〜Ｒ１８の少なくとも１個は、炭素数６〜３０のハロゲン置換芳香族基である。上記芳香族基としては特に限定されず、例えば、フェニル基、ナフチル基、アントラセニル基等が挙げられる。また、ハロゲン置換基としては特に限定されず、例えば、塩素、フッ素等が挙げられ、なかでも、フッ素が好適に用いられる。上記ハロゲン置換基は、芳香族基の芳香族環に直接結合したハロゲン基であってもよいし、例えば、ハロ−ヒドロカルビル置換基の場合のように他の置換基の一部として導入されたものであってもよく、なかでも、フルオロ−ヒドロカルビル置換基が好ましい。 In the general formula (10), at least one of R 15 to R 18 is a halogen-substituted aromatic group having 6 to 30 carbon atoms. It does not specifically limit as said aromatic group, For example, a phenyl group, a naphthyl group, an anthracenyl group etc. are mentioned. Moreover, it does not specifically limit as a halogen substituent, For example, chlorine, a fluorine, etc. are mentioned, Especially, a fluorine is used suitably. The halogen substituent may be a halogen group directly bonded to an aromatic ring of an aromatic group, or, for example, one introduced as part of another substituent as in the case of a halo-hydrocarbyl substituent Of these, fluoro-hydrocarbyl substituents are preferred.
上記光カチオン重合開始剤において、有用なホウ素中心アニオンとしては特に限定されず、例えば、［３，５−（ＣＦ３）２Ｃ６Ｈ５］４Ｂ−、（Ｃ６Ｆ５）４Ｂ−、（Ｃ６Ｈ４−ｐ−ＣＦ３）４Ｂ−、（Ｃ６Ｈ４−ｍ−ＣＦ３）４Ｂ−、（Ｃ６Ｈ４−ｐ−Ｆ）４Ｂ−、（Ｃ６Ｆ５）３（ＣＨ３）Ｂ−、（Ｃ６Ｆ５）３（ｎ−Ｃ４Ｈ９）Ｂ−、（Ｃ６Ｈ４−ｐ−ＣＨ３）３（Ｃ６Ｆ５）Ｂ−、（Ｃ６Ｆ５）３ＦＢ−、（Ｃ６Ｈ５）３（Ｃ６Ｆ５）Ｂ−、（ＣＨ３）２（Ｃ６Ｈ４−ｐ−ＣＦ３）２Ｂ−、（Ｃ６Ｆ５）３（ｎ−Ｃ１８Ｈ３７Ｏ）Ｂ−等が挙げられる。 In the above photo cationic polymerization initiator is not particularly restricted but useful boron-centered anions, for example, [3,5- (CF 3) 2 C 6 H 5] 4 B -, (C 6 F 5) 4 B - , (C 6 H 4 -p- CF 3) 4 B -, (C 6 H 4 -m-CF 3) 4 B -, (C 6 H 4 -p-F) 4 B -, (C 6 F 5 ) 3 (CH 3 ) B − , (C 6 F 5 ) 3 (nC 4 H 9 ) B − , (C 6 H 4 -p-CH 3 ) 3 (C 6 F 5 ) B − , (C 6 F 5) 3 FB -, (C 6 H 5) 3 (C 6 F 5) B -, (CH 3) 2 (C 6 H 4 -p-CF 3) 2 B -, (C 6 F 5) 3 (n-C 18 H 37 O) B - , and the like.
上記好ましいホウ素中心アニオンは、一般的に、ホウ素に結合した３個以上のハロゲン置換芳香族基を含有しており、そのハロゲン置換基としては、フッ素が最も好ましい。最も好ましいホウ素中心アニオンとしては特に限定されず、例えば、［３，５−（ＣＦ３）２Ｃ６Ｈ３］４Ｂ−、（Ｃ６Ｆ５）４Ｂ−、（Ｃ６Ｆ５）３（ＣＨ３）Ｂ−、（Ｃ６Ｆ５）３（ｎ−Ｃ４Ｈ９）Ｂ−、（Ｃ６Ｆ５）３ＦＢ−等が挙げられる。 The preferred boron center anion generally contains three or more halogen-substituted aromatic groups bonded to boron, and the halogen substituent is most preferably fluorine. The most preferable boron center anion is not particularly limited, and for example, [3,5- (CF 3 ) 2 C 6 H 3 ] 4 B − , (C 6 F 5 ) 4 B − , (C 6 F 5 ) 3 (CH 3) B -, ( C 6 F 5) 3 (n-C 4 H 9) B -, (C 6 F 5) 3 FB - , and the like.
また、有用な他の金属中心又は半金属中心を含有する適当なアニオンも使用可能であり、そのようなアニオンとしては特に限定されず、例えば、［３，５−（ＣＦ３）２Ｃ６Ｈ３］４Ａｌ−、（Ｃ６Ｆ５）４Ａｌ−、（Ｃ６Ｆ５）２Ｆ４Ｐ−、（Ｃ６Ｆ５）Ｆ５Ｓｂ−、（Ｃ６Ｆ５）Ｆ５Ｐ−等が挙げられる。更に、有用であると考えられる他のホウ素中心非求核的塩や、他の金属や半金属を含有している他の有用なアニオン等も使用可能である。 In addition, suitable anions containing other useful metal centers or metalloid centers can also be used, and such anions are not particularly limited. For example, [3,5- (CF 3 ) 2 C 6 H 3] 4 Al -, (C 6 F 5) 4 Al -, (C 6 F 5) 2 F 4 P -, (C 6 F 5) F 5 Sb -, (C 6 F 5) F 5 P - , etc. Is mentioned. In addition, other boron-centered non-nucleophilic salts that may be useful, other useful anions containing other metals and metalloids, and the like can be used.
上記光カチオン重合開始剤としては特に限定されないが、上記一般式（１０）で表されるホウ素中心アニオン部分の分子量が４００以上であり、かつ、波長３００ｎｍ以上の光を吸収することが好ましく、波長３００〜４００ｎｍの光を吸収することがより好ましい。 Although it does not specifically limit as said photocationic polymerization initiator, It is preferable that the molecular weight of the boron center anion part represented by the said General formula (10) is 400 or more, and absorbs light with a wavelength of 300 nm or more, More preferably, it absorbs light of 300 to 400 nm.
上記光カチオン重合開始剤は、上記一般式（８）又は一般式（９）で表されるカチオン部分と、上記一般式（１０）で表されるホウ素中心アニオン部分とを有することが好ましく、より好ましくは、上記ホウ素中心アニオン部分の分子量が４００以上であり、かつ、波長３００ｎｍ以上の光、より好ましくは波長３００〜４００ｎｍの光を吸収するものである。なかでも、上記光カチオン重合開始剤を用いた接着剤組成物の硬化進行過程における着色防止効果や硬化物のガラス転移温度上昇効果等に優れることから、下記一般式（１１）又は一般式（１２）で表される光カチオン重合開始剤であることが好ましい。これらの光カチオン重合開始剤を用いることにより、硬化物の着色を防止することができる。また、上述の光カチオン重合性化合物に対して用いることにより、本発明の有機ＥＬ素子用封止剤は、耐光性及び耐湿性に優れたものとなる。
これらの光カチオン重合開始剤は、単独で用いられてもよいし、２種以上が併用されてもよい。
The photocationic polymerization initiator preferably has a cation moiety represented by the general formula (8) or the general formula (9) and a boron center anion moiety represented by the general formula (10). Preferably, the molecular weight of the boron center anion portion is 400 or more and absorbs light having a wavelength of 300 nm or more, more preferably light having a wavelength of 300 to 400 nm. Especially, since it is excellent in the coloring prevention effect in the hardening progress process of the adhesive composition using the said photocationic polymerization initiator, the glass transition temperature rise effect of hardened | cured material, etc., following General formula (11) or General formula (12) It is preferable that it is a photocationic polymerization initiator represented by this. By using these photocationic polymerization initiators, coloring of the cured product can be prevented. Moreover, the organic electroluminescent element sealing agent of this invention becomes the thing excellent in light resistance and moisture resistance by using with respect to the above-mentioned photocationic polymerizable compound.
These cationic photopolymerization initiators may be used alone or in combination of two or more.
上記非イオン性光酸発生タイプの光カチオン重合開始剤としては特に限定されず、例えば、ニトロベンジルエステル、スルホン酸誘導体、リン酸エステル、フェノールスルホン酸エステル、ジアゾナフトキノン、Ｎ−ヒドロキシイミドスホナート等が挙げられる。 The nonionic photoacid generation type photocationic polymerization initiator is not particularly limited, and examples thereof include nitrobenzyl ester, sulfonic acid derivative, phosphoric acid ester, phenolsulfonic acid ester, diazonaphthoquinone, N-hydroxyimidosulfonate, and the like. Is mentioned.
上述したように、本発明の有機ＥＬ素子用封止剤は、上記光重合性化合物が上述した脂肪族環状骨格を有するエポキシ化合物を含有するため、上記光カチオン重合開始剤の配合量を少なくすることができ、本発明の有機ＥＬ素子用封止剤を光硬化させた際に、上記光重合開始剤に起因するアウトガスの発生を抑制することができる。従って、本発明の有機ＥＬ素子用封止剤を用いて有機ＥＬ素子の封止を行うと、上記アウトガスによる有機ＥＬ素子の劣化を好適に防止することができる。 As mentioned above, since the sealing agent for organic EL elements of the present invention contains the epoxy compound having the above-mentioned aliphatic cyclic skeleton, the amount of the photocationic polymerization initiator is reduced. When the sealing agent for organic EL elements of this invention is photocured, generation | occurrence | production of the outgas resulting from the said photoinitiator can be suppressed. Therefore, when the organic EL element is sealed using the organic EL element sealing agent of the present invention, the deterioration of the organic EL element due to the outgas can be suitably prevented.
上記光カチオン重合開始剤の量としては特に限定されないが、上記光重合性化合物１００重量部に対して好ましい下限は０．１重量部、好ましい上限は１０重量部である。０．１重量部未満であると、光カチオン重合が充分に進行しなかったり、反応が遅くなりすぎたりすることがある。また、１０重量部を超えると、反応が速くなりすぎて、作業性が低下したり、反応が不均一になりやすくなったりすることがある。より好ましい上限は５重量部である。 The amount of the photocationic polymerization initiator is not particularly limited, but a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 10 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. If it is less than 0.1 part by weight, photocationic polymerization may not proceed sufficiently or the reaction may become too slow. On the other hand, when the amount exceeds 10 parts by weight, the reaction may become too fast, and workability may be deteriorated or the reaction may become uneven easily. A more preferred upper limit is 5 parts by weight.
本発明の有機ＥＬ素子用封止剤は、更に、硬化制御剤を含有することが好ましい。硬化制御剤を含有することにより、光照射から一定時間経過後に硬化する光後硬化性樹脂組成物とすることができる。
上記硬化制御剤としては特に限定されないが、例えば、ポリエチレングリコール、ポリプロピレングリコール、ポリオキシテトラメチレングリコール等のポリアルキレンオキサイド；クラウンエーテル等のエーテル結合を有する化合物が好適である。また、脂肪族水酸基含有化合物及び／又はフッ素系化合物も好適に用いられる。
It is preferable that the sealing agent for organic EL elements of this invention contains a hardening control agent further. By containing a curing control agent, it can be set as the post-light-curing resin composition which hardens | cures after progress for a fixed time from light irradiation.
Although it does not specifically limit as said hardening control agent, For example, the compound which has ether bonds, such as polyalkylene oxides, such as polyethyleneglycol, polypropylene glycol, polyoxytetramethylene glycol, and crown ether. In addition, an aliphatic hydroxyl group-containing compound and / or a fluorine-based compound is also preferably used.
上記硬化制御剤のなかでも、クラウンエーテルを用いることが特に好ましい。硬化制御剤としてクラウンエーテルを用いることにより、硬化制御剤の添加量に対して有機ＥＬ表示装置の製造に好適な、優れた後硬化性を達成することができる。
また、光カチオン重合開始剤として上述の化学式（７）で表されるアニオン部を有する化合物を用いる場合、上記硬化制御剤としてクラウンエーテルを用いる場合ことがより好ましい。
Among the curing control agents, it is particularly preferable to use crown ether. By using crown ether as the curing control agent, it is possible to achieve excellent post-curing property suitable for manufacturing an organic EL display device with respect to the addition amount of the curing control agent.
Moreover, when using the compound which has an anion part represented by the above-mentioned chemical formula (7) as a photocationic polymerization initiator, it is more preferable to use crown ether as the curing controller.
上記硬化制御剤としてポリアルキレンオキサイドを用いる場合、上記ポリアルキレンオキサイドの末端としては特に限定されず、水酸基でもよいし、他の化合物によりエーテル化、エステル化されていてもよいし、エポキシ基等の官能基となっていてもよい。なかでも、水酸基、エポキシ基等は上記光重合性化合物と反応するので好適である。 When polyalkylene oxide is used as the curing controller, the terminal of the polyalkylene oxide is not particularly limited, and may be a hydroxyl group, may be etherified or esterified with another compound, and may be an epoxy group or the like. It may be a functional group. Of these, a hydroxyl group, an epoxy group, and the like are preferable because they react with the photopolymerizable compound.
更に、上記ポリアルキレンオキサイドとしては、ポリアルキレンオキサイド付加ビスフェノール誘導体も好適に用いられ、特に末端が水酸基又はエポキシ基を有する化合物がより好適に用いられる。 Furthermore, as the polyalkylene oxide, a polyalkylene oxide-added bisphenol derivative is also preferably used, and particularly a compound having a terminal hydroxyl group or epoxy group is more preferably used.
上記硬化制御剤は、ポリエチレングリコール及び／又はポリプロピレングリコールを分子内に２つ以上有することが好ましい。 The curing controller preferably has two or more polyethylene glycols and / or polypropylene glycols in the molecule.
上記硬化制御剤のなかでも、ポリエチレングリコールを分子内に２つ以上有する硬化制御剤の市販品としては、例えば、「リカレジンＢＥＯ−６０Ｅ」、「リカレジンＥＯ−２０」（いずれも新日本理化社製）等が挙げられる。
また、ポリプロピレングリコールを分子内に２つ以上有する硬化制御剤の市販品としては、例えば、「リカレジンＢＰＯ−２０Ｅ」、「リカレジンＰＯ−２０」（いずれも新日本理化社製）等が挙げられる。
Among the above curing control agents, commercially available curing control agents having two or more polyethylene glycols in the molecule include, for example, “Likaresin BEO-60E” and “Likaresin EO-20” (both manufactured by Shin Nippon Rika Co., Ltd.). ) And the like.
Moreover, as a commercial item of the hardening control agent which has two or more polypropylene glycols in a molecule | numerator, "Lika Resin BPO-20E", "Lika Resin PO-20" (all are made by Shin Nippon Rika Co., Ltd.) etc. are mentioned, for example.
上記クラウンエーテルとしては特に限定されず、例えば、１２−クラウン−４、１５−クラウン−５、１８−クラウン−６等が挙げられる。 The crown ether is not particularly limited, and examples thereof include 12-crown-4, 15-crown-5, and 18-crown-6.
本発明の有機ＥＬ素子用封止剤において、上記硬化制御剤の配合量としては特に限定されないが、上記光重合性化合物１００重量部に対して好ましい下限は０．１重量部、好ましい上限は５０重量部である。０．１重量部未満であると、本発明の有機ＥＬ素子用封止剤に光を照射した後に充分な可使時間が得られないことがあり、５０重量部を超えると、上記光重合性化合物の光カチオン重合が充分に進行しなかったり、反応が遅くなりすぎたりすることがある。より好ましい下限は０．５重量部、好ましい上限は２０重量部であり、更に好ましい上限は１０重量部である。 In the organic EL device sealing agent of the present invention, the amount of the curing control agent is not particularly limited, but a preferable lower limit is 0.1 parts by weight and a preferable upper limit is 50 with respect to 100 parts by weight of the photopolymerizable compound. Parts by weight. If the amount is less than 0.1 parts by weight, sufficient pot life may not be obtained after irradiating the organic EL device sealing agent of the present invention with light. If the amount exceeds 50 parts by weight, the photopolymerizability described above may be obtained. The photocationic polymerization of the compound may not proceed sufficiently or the reaction may become too slow. A more preferred lower limit is 0.5 parts by weight, a preferred upper limit is 20 parts by weight, and a more preferred upper limit is 10 parts by weight.
更に、上記硬化制御剤の配合量は、上記クラウンエーテルを用いる場合、上記光カチオン重合開始剤１００重量部に対して好ましい下限は２０重量部、好ましい上限は３００重量部である。上記硬化制御剤をこのような配合量で含有することにより、本発明の有機ＥＬ用封止剤は、有機ＥＬ表示装置を製造する際に有機ＥＬ素子にダメージを与えることを防止でき、また、有機ＥＬ素子を保護するに充分な耐湿性を有するものになる。上記配合量が２０重量部未満であると硬化反応を適度に遅延させることができないことがあり、３００重量部を超えると硬化反応が充分に進行しなかったり、反応が遅くなりすぎたりすることがある。 Further, the blending amount of the curing control agent, when using the crown ether, is preferably 20 parts by weight and preferably 300 parts by weight with respect to 100 parts by weight of the cationic photopolymerization initiator. By containing the curing control agent in such a blending amount, the organic EL sealing agent of the present invention can prevent the organic EL element from being damaged when the organic EL display device is produced, It has sufficient moisture resistance to protect the organic EL element. If the blending amount is less than 20 parts by weight, the curing reaction may not be delayed moderately, and if it exceeds 300 parts by weight, the curing reaction may not proceed sufficiently or the reaction may become too slow. is there.
本発明の有機ＥＬ素子用封止剤は、光を照射した後硬化反応が進行し、接着ができなくなるまでの可使時間が１分以上であることが好ましい。可使時間が１分未満であると、基板等を貼り合わせる前に硬化進行してしまい、充分な接着強度を得られなくなることがある。このような本発明の有機ＥＬ素子用封止剤の可使時間は、上述した硬化制御剤を添加することで好適に調整することができる。 The sealant for an organic EL device of the present invention preferably has a pot life of 1 minute or more until a curing reaction proceeds after irradiation with light and adhesion cannot be performed. If the pot life is less than 1 minute, curing proceeds before the substrates are bonded together, and sufficient adhesive strength may not be obtained. The pot life of the sealing agent for organic EL elements of the present invention can be suitably adjusted by adding the above-described curing control agent.
本発明の有機ＥＬ素子用封止剤は、透湿性、接着強度、硬化収縮、熱膨張率等を改良するため、充填剤としてコロイダルシリカ、タルク、マイカ、炭酸カルシウム、酸化チタン、クレー等の粉体、ガラスバルーン、アルミナバルーン、セラミックバルーン等の無機中空体；ナイロンビーズ、アクリルビーズ、シリコンビーズ、フッ素系樹脂ビーズ等の有機球状体、塩化ビニリデンバルーン、アクリルバルーン等の有機中空体；ガラス、ポリエステル、レーヨン、ナイロン、セルロース等の単繊維等が添加されていてもよい。
また、本発明の有機ＥＬ素子用封止剤は、セル内への水分の浸入を防ぐため、吸水剤等が添加されていてもよい。吸水材の具体例としては特に限定されず、例えば、シリカゲル、モレキュラーシーブ、酸化カルシウム、酸化バリウム、酸化ストロンチウム等アルカリ土類金属の酸化物等が挙げられる。
The sealing agent for organic EL elements of the present invention is a powder of colloidal silica, talc, mica, calcium carbonate, titanium oxide, clay or the like as a filler in order to improve moisture permeability, adhesive strength, curing shrinkage, thermal expansion coefficient, etc. Bodies, inorganic hollow bodies such as glass balloons, alumina balloons and ceramic balloons; organic spherical bodies such as nylon beads, acrylic beads, silicon beads and fluororesin beads; organic hollow bodies such as vinylidene chloride balloons and acrylic balloons; glass, polyester Monofilaments such as rayon, nylon, and cellulose may be added.
Moreover, in order to prevent the penetration | invasion of the water | moisture content in a cell, the water absorbing agent etc. may be added to the sealing agent for organic EL elements of this invention. Specific examples of the water absorbing material are not particularly limited, and examples thereof include oxides of alkaline earth metals such as silica gel, molecular sieve, calcium oxide, barium oxide, and strontium oxide.
更に、本発明の有機ＥＬ素子用封止剤には、密着性向上剤、光増感剤、補強剤、軟化剤、可塑剤、粘度調整剤、紫外線吸収剤、酸化防止剤等の各種添加物が含有されていてもよい。
なお、本発明の有機ＥＬ素子用封止剤が上記添加剤を含有する場合、該添加剤は、上記光重合性化合物との２５℃において測定した平均屈折率の差が０．０５以下であることが好ましい。０．０５を超えると、本発明の有機ＥＬ素子用封止剤の硬化物の透明性が不充分となることがある。
Furthermore, the organic EL device sealing agent of the present invention has various additives such as an adhesion improver, a photosensitizer, a reinforcing agent, a softener, a plasticizer, a viscosity modifier, an ultraviolet absorber, and an antioxidant. May be contained.
In addition, when the sealing agent for organic EL elements of this invention contains the said additive, this additive is 0.05 or less of the difference of the average refractive index measured at 25 degreeC with the said photopolymerizable compound. It is preferable. If it exceeds 0.05, the transparency of the cured product of the sealing agent for organic EL elements of the present invention may be insufficient.
上記光増感剤は、上記光カチオン重合開始剤の効率をより向上させて、上記光重合性化合物の光カチオン重合をより促進させるものである。
上記光増感剤としては特に限定されず、例えば、カルボニル化合物、有機硫黄化合物、過硫化物、レドックス系化合物、アゾ化合物、ジアゾ化合物、ハロゲン化合物、光還元性色素等が挙げられる。具体例には、例えば、ベンゾインメチルエーテル、ベンゾインイソプロピルエーテル等のベンゾイン誘導体；ベンゾフェノン、２，４−ジクロルベンゾフェノン、ｏ−ベンゾイル安息香酸メチル、４，４’−ビス（ジメチルアミノ）ベンゾフェノン等のベンゾフェノン誘導体；２−クロルチオキサントン、２−イソプロピルチオキサントン等のチオキサントン誘導体；２−クロルアントラキノン、２−メチルアントラキノン等のアントラキノン誘導体等が挙げられる。これらの光増感剤は、単独で用いられてもよいし、２種類以上が併用されてもよい。
The photosensitizer further improves the efficiency of the photocationic polymerization initiator and further promotes the photocationic polymerization of the photopolymerizable compound.
The photosensitizer is not particularly limited, and examples thereof include carbonyl compounds, organic sulfur compounds, persulfides, redox compounds, azo compounds, diazo compounds, halogen compounds, and photoreductive dyes. Specific examples include, for example, benzoin derivatives such as benzoin methyl ether and benzoin isopropyl ether; benzophenones such as benzophenone, 2,4-dichlorobenzophenone, methyl o-benzoylbenzoate, and 4,4′-bis (dimethylamino) benzophenone. Derivatives; thioxanthone derivatives such as 2-chlorothioxanthone and 2-isopropylthioxanthone; anthraquinone derivatives such as 2-chloroanthraquinone and 2-methylanthraquinone. These photosensitizers may be used independently and 2 or more types may be used together.
本発明の有機ＥＬ素子用封止剤は、硬化物の透明性を阻害しない範囲で、素子電極の耐久性を向上させるために、組成物に発生した酸と反応する化合物又はイオン交換樹脂を含有してもよい。 The sealing agent for organic EL elements of the present invention contains a compound that reacts with an acid generated in the composition or an ion exchange resin in order to improve the durability of the element electrode within a range that does not impair the transparency of the cured product. May be.
上記発生した酸と反応する化合物としては、酸と中和する物質、例えば、アルカリ金属又はアルカリ土類金属の炭酸塩又は炭酸水素塩等が挙げられる。具体的には、炭酸カルシウム、炭酸水素カルシウム、炭酸ナトリウム、炭酸水素ナトリウム等が用いられる。 Examples of the compound that reacts with the generated acid include substances that neutralize the acid, such as carbonates or bicarbonates of alkali metals or alkaline earth metals. Specifically, calcium carbonate, calcium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate or the like is used.
上記イオン交換樹脂としては、陽イオン交換型、陰イオン交換型、両イオン交換型のいずれも使用することができるが、特に塩化物イオンを吸着することのできる陽イオン交換型又は両イオン交換型が好適である。 As the ion exchange resin, any of a cation exchange type, an anion exchange type, and a both ion exchange type can be used, and in particular, a cation exchange type or a both ion exchange type capable of adsorbing chloride ions. Is preferred.
本発明の有機ＥＬ素子用封止剤の粘度としては、本発明の有機ＥＬ素子用封止剤を用いて有機ＥＬ素子の封止を行う際に用いる塗布方法により適宜決定され、特に限定されないが、２５℃、５ｒｐｍにおいて、好ましい下限が１００ｍＰａ・ｓ、好ましい上限が１万ｍＰａ・ｓである。１００ｍＰａ・ｓ未満であると、有機ＥＬ素子を封止できないことがあり、１万ｍＰａを超えると、本発明の有機ＥＬ素子用封止剤を用いた有機ＥＬ素子の封止をスクリーン印刷により行う場合に、均一かつ正確に有機ＥＬ素子の封止ができないことがある。また、本発明の有機ＥＬ素子用封止剤をディスペンサー等で基板に塗布し、もう一方の基板を貼り合わすことにより有機ＥＬ素子を封止する場合、本発明の有機ＥＬ素子用封止剤の粘度の好ましい上限は３０００ｍＰａ・ｓである。３０００ｍＰａ・ｓを超えると、基板同士の貼り合わせ時に泡がかみ気泡が混入するおそれがあり、端部まで本発明の有機ＥＬ素子用封止剤が押し広げられない可能性がある。より好ましい上限は１０００ｍＰａである。
なお、本明細書において、上記粘度は、Ｅ型粘度計（東機産業社製、ＴＶ−２２型）を用いて上記条件下で測定した場合に得られる値である。
The viscosity of the organic EL device sealing agent of the present invention is appropriately determined by the coating method used when sealing the organic EL device using the organic EL device sealing agent of the present invention, and is not particularly limited. The preferable lower limit is 100 mPa · s and the preferable upper limit is 10,000 mPa · s at 25 ° C. and 5 rpm. If it is less than 100 mPa · s, the organic EL element may not be sealed. If it exceeds 10,000 mPa, the organic EL element is sealed by screen printing using the organic EL element sealant of the present invention. In some cases, the organic EL element cannot be sealed uniformly and accurately. In addition, when the organic EL element is sealed by applying the organic EL element sealant of the present invention to a substrate with a dispenser or the like and bonding the other substrate together, The upper limit with a preferable viscosity is 3000 mPa * s. When it exceeds 3000 mPa · s, there is a possibility that bubbles are formed and bubbles are mixed when the substrates are bonded together, and the sealing agent for organic EL elements of the present invention may not be spread to the end. A more preferable upper limit is 1000 mPa.
In addition, in this specification, the said viscosity is a value obtained when it measures on the said conditions using an E-type viscosity meter (the Toki Sangyo company make, TV-22 type | mold).
また、本発明の有機ＥＬ素子用封止剤は、硬化物の２０℃から８０℃までにおける引張貯蔵弾性率の好ましい下限が５×１０７Ｐａ、好ましい上限が５×１０８Ｐａである。引張貯蔵弾性率が上記範囲にある本発明の有機ＥＬ素子用封止剤は、加熱硬化時から常温までの弾性率が低弾性域でほぼ一定となっているため、有機ＥＬ表示装置の製造に用いた際に、加熱硬化時から常温まで冷却したときに硬化収縮が起こっても応力が緩和され、有機ＥＬ素子に対するダメージが低減される。 Moreover, the preferable lower limit of the tensile storage elastic modulus in 20 to 80 degreeC of the hardened | cured material of the sealing agent for organic EL elements of this invention is 5 * 10 < 7 > Pa, and a preferable upper limit is 5 * 10 < 8 > Pa. The sealing agent for organic EL elements of the present invention having a tensile storage elastic modulus in the above range has a substantially constant elastic modulus from the time of heat curing to room temperature in a low elastic region. When used, even if curing shrinkage occurs when cooled from room temperature to room temperature, the stress is relieved and damage to the organic EL element is reduced.
本発明の有機ＥＬ素子用封止剤の硬化物の波長３８０〜８００ｎｍにおける光の全光線透過率の好ましい下限は８０％である。８０％未満であると、本発明の有機ＥＬ素子用封止剤を用いて有機ＥＬ表示装置を製造した場合に、充分な光学特性を得られないことがある。より好ましい下限は８５％である。 The preferable minimum of the total light transmittance of the light in the wavelength of 380-800 nm of the hardened | cured material of the sealing agent for organic EL elements of this invention is 80%. If it is less than 80%, sufficient optical properties may not be obtained when an organic EL display device is produced using the organic EL element sealing agent of the present invention. A more preferred lower limit is 85%.
上記全光線透過率を測定する方法としては特に限定はされず、例えば東京電色社製「ＡＵＴＯＭＡＴＩＣ ＨＡＺＥ ＭＡＴＥＲ ＭＯＤＥＬ ＴＣ＝ＩＩＩ ＤＰＫ」等の分光計を用いて測定することができる。 The method for measuring the total light transmittance is not particularly limited, and can be measured using a spectrometer such as “AUTOMATIC HAZE MATER MODEL TC = III DPK” manufactured by Tokyo Denshoku Co., Ltd.
本発明の有機ＥＬ素子封止剤は、硬化物に紫外線を１００時間照射した後の４００ｎｍにおける透過率の下限が２０μｍの光路長にて８５％であることが好ましい。８５％未満であると、耐光性が低く、発光の損失が大きくなり、かつ、色再現性が悪くなることがある。より好ましい下限は９０％、更に好ましい下限は９５％である。 In the organic EL device sealing agent of the present invention, the lower limit of the transmittance at 400 nm after irradiating the cured product with ultraviolet rays for 100 hours is preferably 85% at an optical path length of 20 μm. If it is less than 85%, the light resistance is low, the light emission loss increases, and the color reproducibility may deteriorate. A more preferred lower limit is 90%, and a still more preferred lower limit is 95%.
上記紫外線を照射する方法としては特に限定はされず、キセノンランプ、カーボンアークランプ等、従来公知の光源を用いることができる。 The method of irradiating the ultraviolet rays is not particularly limited, and a conventionally known light source such as a xenon lamp or a carbon arc lamp can be used.
本発明の有機ＥＬ素子封止剤は、硬化物をＪＩＳ Ｚ ０２０８に従い、８５℃−８５％ＲＨに２４時間暴露して測定した１００μｍ厚での透湿度の値が１００ｇ／ｍ２以下であることが好ましい。１００ｇ／ｍ２を超えると、素子に水分が到達し発光部でのダークスポット発生の原因となる。 The organic EL device sealant of the present invention has a moisture permeability value of 100 g / m 2 or less at a thickness of 100 μm measured by exposing the cured product to 85 ° C.-85% RH for 24 hours according to JIS Z 0208. Is preferred. If it exceeds 100 g / m 2 , moisture will reach the element and cause dark spots in the light emitting part.
更に、本発明の有機ＥＬ素子封止剤は、硬化物を８５℃−８５％ＲＨの条件下、２４時間暴露したときに、上記硬化物の含水率が０．５％未満であることが好ましい。０．５％以上であると、硬化物中の水分による有機ＥＬ素子の劣化が起こる。より好ましい含水率の上限は０．３％である。 Furthermore, the organic EL device sealing agent of the present invention preferably has a moisture content of less than 0.5% when the cured product is exposed for 24 hours at 85 ° C. to 85% RH. . When it is 0.5% or more, the organic EL device is deteriorated due to moisture in the cured product. A more preferable upper limit of the moisture content is 0.3%.
上記含水率の測定方法としては特に限定されず、例えば、ＪＩＳ Ｋ−７２５１に準拠してカールフィッシャー法により求める方法や、ＪＩＳ Ｋ−７２０９−２に準拠して吸水後の重量増分を求める等の方法が挙げられる。 The method for measuring the moisture content is not particularly limited. For example, the method for obtaining by the Karl Fischer method in accordance with JIS K-7251, or the weight increment after water absorption in accordance with JIS K-7209-2. A method is mentioned.
上記のような低い透湿度と低い含水率を両方有することにより、本発明の有機ＥＬ素子封止剤は優れた耐湿性を有するものとなる。 By having both the low moisture permeability and the low moisture content as described above, the organic EL device sealing agent of the present invention has excellent moisture resistance.
本発明の有機ＥＬ素子封止剤は、硬化させた後の硬化物のガラス転移点が８５℃以上であることが好ましい。８５℃未満であると、有機ＥＬ素子が高温多湿の状態に曝されたときに、接着剤硬化物が軟化するため、水蒸気が硬化物を透過しやすくなり、有機ＥＬ素子劣化の原因となる。より好ましくは１００℃以上である。 It is preferable that the glass transition point of the hardened | cured material after hardening the organic EL element sealing agent of this invention is 85 degreeC or more. When the temperature is lower than 85 ° C., the cured adhesive is softened when the organic EL element is exposed to a high-temperature and high-humidity state, so that water vapor easily passes through the cured product, causing deterioration of the organic EL element. More preferably, it is 100 ° C. or higher.
本発明の有機ＥＬ素子用封止剤の製造方法としては特に限定されず、例えば、ホモディスパー、ホモミキサー、万能ミキサー、プラネタリウムミキサー、ニーダー、三本ロール等の混合機を用いて、常温又は加温下で、光重合性化合物、光カチオン重合開始剤及び硬化制御剤、充填剤、添加剤等の各所定量を混合する方法等が挙げられる。なお、製造する際は、光を遮断した状態で行われることが好ましい。 The method for producing the sealing agent for organic EL elements of the present invention is not particularly limited. For example, using a mixer such as a homodisper, a homomixer, a universal mixer, a planetarium mixer, a kneader, or a three-roller, Examples thereof include a method of mixing predetermined amounts of a photopolymerizable compound, a cationic photopolymerization initiator, a curing controller, a filler, an additive, and the like under temperature. In addition, when manufacturing, it is preferable to carry out in the state which interrupted | blocked light.
本発明の有機ＥＬ素子用封止剤は、光を照射することにより硬化する。
すなわち、本発明の有機ＥＬ素子用封止剤を用いて有機ＥＬ素子を封止し、光を照射して硬化させることで有機ＥＬ表示装置を製造することができる。
The sealing agent for organic EL elements of this invention hardens | cures by irradiating light.
That is, an organic EL display device can be produced by sealing an organic EL element using the organic EL element sealing agent of the present invention and curing it by irradiating light.
本発明の有機ＥＬ素子用封止剤を用いて有機ＥＬ表示装置を製造する方法としては、例えば、一方の基板上本発明の有機ＥＬ素子用封止剤を塗布し、本発明の有機ＥＬ素子用封止剤を介して他方の基板を貼り合わせ、本発明の有機ＥＬ素子用封止剤に光を照射する方法が挙げられる。 As a method for producing an organic EL display device using the organic EL element sealing agent of the present invention, for example, the organic EL element sealing agent of the present invention is applied on one substrate and the organic EL element of the present invention is applied. The other board | substrate is bonded through the sealing agent for water, and the method of irradiating light to the sealing agent for organic EL elements of this invention is mentioned.
上記一方の基板に本発明の有機ＥＬ素子用封止剤を塗布する方法としては特に限定はされず、例えば、スクリーン印刷、ディスペンサー塗布、フレキソ印刷、グラビア印刷等の方法を用いることができる。また、本発明の有機ＥＬ素子用封止剤を上記一方の基板の全面に塗布してもよく、基板の一部に塗布してもよい。 The method for applying the organic EL element sealing agent of the present invention to the one substrate is not particularly limited, and for example, methods such as screen printing, dispenser application, flexographic printing, and gravure printing can be used. Moreover, the sealing agent for organic EL elements of this invention may be apply | coated to the whole surface of said one board | substrate, and may be apply | coated to a part of board | substrate.
塗布により形成される本発明の有機ＥＬ素子用封止剤の封止部の形状としては、有機ＥＬ素子を外気から保護しうる形状であれば特に限定されず、有機ＥＬ素子を完全に被覆する形状であってもよいし、有機ＥＬ素子の周辺部に閉じたパターンを形成してもよい。更に、有機ＥＬ素子の周辺部に一部開口部を設けた形状のパターンを形成してもよい。
なお、本発明の有機ＥＬ素子用封止剤は、上述のように常温において低粘度とすることができることから、有機ＥＬ素子を完全に被覆する形状に塗布する方法を好適に行うことができる。
The shape of the sealing portion of the sealing agent for organic EL elements of the present invention formed by coating is not particularly limited as long as it can protect the organic EL elements from the outside air, and completely covers the organic EL elements. The shape may be sufficient and the closed pattern may be formed in the peripheral part of an organic EL element. Furthermore, you may form the pattern of the shape which provided the one part opening part in the peripheral part of the organic EL element.
In addition, since the sealing agent for organic EL elements of this invention can be made low viscosity at normal temperature as mentioned above, the method of apply | coating to the shape which coat | covers an organic EL element completely can be performed suitably.
上記一方の基板としては特に限定されず、例えば、有機ＥＬ素子の形成されている基板であってもよく、有機ＥＬ素子の形成されていない基板であってもよい。上記一方の基板に有機ＥＬ素子が形成されていない場合、他方の基板を貼り合わせた際に、上記有機ＥＬ素子を外気から保護できるように上記一方の基板に本発明の有機ＥＬ素子用封止剤を塗布すればよい。すなわち、他方の基板を貼り合わせた際に有機ＥＬ表示素子の位置となる場所に全面的に塗布するか、又は、他方の基板を貼り合わせた際に有機ＥＬ表示素子の位置となる場所が完全に収まる形状に、閉じたパターンの封止剤部を形成してもよい。 The one substrate is not particularly limited, and may be, for example, a substrate on which an organic EL element is formed or a substrate on which no organic EL element is formed. When the organic EL element is not formed on the one substrate, the organic EL element of the present invention is sealed on the one substrate so that the organic EL element can be protected from the outside air when the other substrate is bonded. What is necessary is just to apply | coat an agent. That is, it is applied over the entire surface where the organic EL display element is positioned when the other substrate is bonded, or the organic EL display element is completely positioned when the other substrate is bonded. The sealing agent portion having a closed pattern may be formed in a shape that fits in the shape.
また、上記基板としては特に限定されないが、防湿性基材であることが好ましい。具体例としては、例えば、ソーダガラス、無アルカリガラス等のガラス基材、ステンレス・アルミニウム等の金属基材、三フッ化ポリエチレン、ポリ三フッ化塩化エチレン（ＰＣＴＦＥ）、ポリビニリデンフルオライド（ＰＶＤＦ）、ＰＶＤＦとＰＣＴＦＥとの共重合体、ＰＶＤＦとポリフッ化塩化エチレンとの共重合体等のポリフッ化エチレン系ポリマー、ポリイミド、ポリカーボネート、ジシクロペンタジエン等のシクロオレフィン系樹脂、ポリエチレンテレフタレート等のポリエステル、ポリエチレン、ポリスチレン等の樹脂基材が挙げられる。 The substrate is not particularly limited, but is preferably a moisture-proof substrate. Specific examples include, for example, glass substrates such as soda glass and alkali-free glass, metal substrates such as stainless steel and aluminum, polyethylene trifluoride, polytrifluoroethylene chloride (PCTFE), and polyvinylidene fluoride (PVDF). , Copolymers of PVDF and PCTFE, polyfluorinated ethylene polymers such as PVDF and polyfluoroethylene chloride, cycloolefin resins such as polyimide, polycarbonate and dicyclopentadiene, polyesters such as polyethylene terephthalate, polyethylene And resin base materials such as polystyrene.
また、上記有機ＥＬ表示素子は、無機防湿膜で被覆されていてもよい。本発明の有機ＥＬ素子用封止剤は、硬化物の引張貯蔵弾性率が２０℃から８０℃の間で一定の低弾性率領域内を示すため、上記有機ＥＬ表示素子が無機防湿膜で被覆されている場合にも、該防湿膜を傷つけることなく、好適に用いることができる。上記無機防湿膜としては特に限定されず、例えば、従来公知のものと同様のものが挙げられる。 The organic EL display element may be covered with an inorganic moisture-proof film. Since the sealing agent for organic EL elements of the present invention exhibits a constant low elastic modulus region between 20 ° C. and 80 ° C. of the cured product, the organic EL display element is covered with an inorganic moisture-proof film. Even when it is used, it can be used suitably without damaging the moisture-proof film. The inorganic moisture barrier film is not particularly limited, and examples thereof include those conventionally known.
上記他方の基板を貼り合わせる方法としては特に限定はされないが、減圧雰囲気下で貼り合わせることが好ましい。上記減圧雰囲気下の真空度の好ましい下限は０．０１ｋＰａ、好ましい上限は１０ｋＰａである。０．０１ｋＰａ未満であると、真空装置の気密性や真空ポンプの能力から真空状態を達成するのに時間がかかるため現実的でなく、１０ｋＰａを超えると、上記他方の基板を貼り合わせる際の本発明の有機ＥＬ素子用封止剤中の気泡の除去が不充分となることがある。 The method of bonding the other substrate is not particularly limited, but it is preferable to bond the substrates in a reduced pressure atmosphere. The preferable lower limit of the degree of vacuum in the reduced-pressure atmosphere is 0.01 kPa, and the preferable upper limit is 10 kPa. If it is less than 0.01 kPa, it takes time to achieve a vacuum state due to the airtightness of the vacuum device and the ability of the vacuum pump, so it is not practical, and if it exceeds 10 kPa, this is a book for bonding the other substrate. Removal of bubbles in the sealing agent for organic EL elements of the invention may be insufficient.
上記光を照射するための光源としては特に限定されず、例えば、低圧水銀灯、中圧水銀灯、高圧水銀灯、超高圧水銀灯、エキシマレーザ、ケミカルランプ、ブラックライト、マイクロウェーブ励起水銀灯、メタルハライドランプ、ナトリウムランプ、ハロゲンランプ、キセノンランプ、蛍光灯、太陽光、電子線照射装置等が挙げられる。これらの光源は、単独で用いられてもよく、２種以上が併用されてもよい。 The light source for irradiating the light is not particularly limited. For example, a low pressure mercury lamp, a medium pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, an excimer laser, a chemical lamp, a black light, a microwave excitation mercury lamp, a metal halide lamp, a sodium lamp. Halogen lamps, xenon lamps, fluorescent lamps, sunlight, electron beam irradiation devices, and the like. These light sources may be used independently and 2 or more types may be used together.
これらの光源の使用に際しては、例えば、光カットフィルター等を用いて、熱線や波長３００ｎｍ未満の光を除去することが好ましい。また、上記光源の接着剤組成物への照射手順としては、例えば、各種光源の同時照射、時間差をおいての逐次照射、同時照射と逐次照射との組み合わせ照射等が挙げられ、いずれの照射手段を採ってもよい。
本発明の有機ＥＬ素子用封止剤の硬化に際しては、光重合性化合物等の光カチオン重合をより促進して、硬化時間をより短縮するために、光照射と同時に加熱を行ってもよい。上記加熱硬化を併用する場合の加熱温度としては特に限定されないが、５０〜１００℃程度であることが好ましい。
When using these light sources, it is preferable to remove heat rays or light having a wavelength of less than 300 nm using, for example, a light cut filter or the like. Examples of the irradiation procedure of the light source to the adhesive composition include simultaneous irradiation of various light sources, sequential irradiation with a time difference, combined irradiation of simultaneous irradiation and sequential irradiation, etc., and any irradiation means May be taken.
In curing the organic EL device sealing agent of the present invention, in order to further accelerate the photocationic polymerization of a photopolymerizable compound or the like and further shorten the curing time, heating may be performed simultaneously with light irradiation. Although it does not specifically limit as heating temperature in the case of using the said heat curing together, It is preferable that it is about 50-100 degreeC.
本発明の有機ＥＬ素子用封止剤が硬化制御剤を含有する場合、光照射後、光を遮断した後にも反応が進行し、硬化が完了するものとなる。このため、例えば、硬化制御剤を含有する本発明の有機ＥＬ素子用封止剤により有機ＥＬ素子を封止する場合、背面板に本発明の有機ＥＬ素子用封止剤を塗布し、該封止剤に光を照射して活性化させた後に、光を遮断し、背面板と素子を形成した基板を貼り合わせることにより、有機ＥＬ素子を光や熱に晒すことなく封止を行うことができる。このような方法により有機ＥＬ素子を封止して有機ＥＬ表示装置を製造する有機ＥＬ表示装置の製造方法もまた、本発明の１つである。 When the sealing agent for organic EL elements of the present invention contains a curing control agent, the reaction proceeds after light irradiation and light is blocked, and curing is completed. For this reason, for example, when sealing an organic EL element with the sealing agent for organic EL elements of the present invention containing a curing controller, the sealing agent for organic EL elements of the present invention is applied to the back plate and the sealing is performed. After activating the stopper by irradiating with light, the organic EL element can be sealed without being exposed to light or heat by blocking the light and bonding the back plate and the substrate on which the element is formed. it can. An organic EL display device manufacturing method in which an organic EL display device is manufactured by sealing an organic EL element by such a method is also one aspect of the present invention.
すなわち、本発明の有機ＥＬ表示装置の製造方法は、上記硬化制御剤を含有する本発明の有機ＥＬ素子用封止剤を防湿性基材の全面又は一部に塗布した後、光を照射し、前記有機ＥＬ素子用封止剤が硬化するまでの間に、前記防湿性基材と有機ＥＬ素子とを貼合して封止するものである。 That is, in the method for producing an organic EL display device of the present invention, the sealing agent for organic EL elements of the present invention containing the above curing controller is applied to the whole surface or a part of a moisture-proof substrate, and then irradiated with light. The moisture-proof substrate and the organic EL element are bonded and sealed until the organic EL element sealing agent is cured.
本発明の有機ＥＬ表示装置の製造方法においては、防湿性基材と有機ＥＬ素子とを貼合した後に加熱することが好ましい。
上記防湿性基材と有機ＥＬ素子とを貼合した後に加熱することにより、有機ＥＬ素子用封止剤の硬化速度を促進させることができる。
In the manufacturing method of the organic EL display device of the present invention, it is preferable to heat after bonding the moisture-proof substrate and the organic EL element.
By heating after bonding the moisture-proof substrate and the organic EL element, the curing rate of the organic EL element sealing agent can be accelerated.
このような本発明の有機ＥＬ表示装置の製造方法により封止されてなる有機ＥＬ素子もまた、本発明の１つである。 An organic EL element sealed by such a method for producing an organic EL display device of the present invention is also one aspect of the present invention.
本発明によると、光重合性化合物と光カチオン重合開始剤とを含有し、上記光重合性化合物が上記光重合性化合物１００重量部に対して２０〜８０重量部の範囲で脂肪族骨格を有するエポキシ化合物を含有するため、耐光性及び長期間耐湿性に優れるとともに、粘度を低くすることができ大面積の有機エレクトロルミネッセンス表示装置の製造に好適に用いることができる有機エレクトロルミネッセンス素子用封止剤、該有機エレクトロルミネッセンス素子用封止剤を用いた有機エレクトロルミネッセンス表示装置の製造方法、及び、有機エレクトロルミネッセンス表示装置を提供できる。 According to the present invention, it contains a photopolymerizable compound and a photocationic polymerization initiator, and the photopolymerizable compound has an aliphatic skeleton in the range of 20 to 80 parts by weight with respect to 100 parts by weight of the photopolymerizable compound. Since it contains an epoxy compound, it is excellent in light resistance and long-term moisture resistance, and can be used in the production of an organic electroluminescence display device having a large area because of its low viscosity. The manufacturing method of the organic electroluminescent display apparatus using this sealing agent for organic electroluminescent elements, and an organic electroluminescent display apparatus can be provided.
以下に実施例を掲げて本発明を更に詳しく説明するが、本発明はこれら実施例のみに限定されるものではない。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples.
（実施例１〜１３、比較例１〜９）
表１の組成に従って、下記に示す各材料を、ホモディスパー型撹拌混合機（ホモディスパーＬ型、特殊機化社製）を用い、撹拌速度３０００ｒｐｍで均一に撹拌混合して、有機ＥＬ素子用封止剤を製造した。
水素化ビスフェノールＡ型エポキシ樹脂（新日本理化社製、ＨＢＥ−１００）
ビスフェノールＡＦ型エポキシ樹脂（ダイキン工業社製、２，２−ビス（４−ヒドロキシフェニル）ヘキサフルオロプロパンのエピクロルヒドリン付加物）
ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン社製、エピコート８２８）
ビスフェノールＦ型エポキシ樹脂（ジャパンエポキシレジン社製、エピコート８０６）
水素化ビスフェノールＦ型エポキシ樹脂（ジャパンエポキシレジン社製、エピコートＹＬ６７５３）
ジシクロペンタジエン型エポキシ樹脂（旭電化社製、ＥＰ−４０８８）
シクロヘキサンジメタノールジグリシジルエーテル（旭電化社製、ＥＰ−４０８５）
光カチオン重合開始剤：トリフェニルスルホニウム−アンチモン系光カチオン性重合開始剤（旭電化工業社製、アデカオプトマーＳＰ１７０）
増感剤：チオキサントン系光増感剤（日本化薬社製、ＤＥＴＸ−Ｓ）
硬化制御剤：エチレンオキサイド付加ビスフェノールＡジグリシジルエーテル（新日本理化社製、ＢＥＯ−６０Ｅ）
(Examples 1-13, Comparative Examples 1-9)
According to the composition of Table 1, the materials shown below were uniformly stirred and mixed at a stirring speed of 3000 rpm using a homodisper type stirring mixer (Homodisper L type, manufactured by Tokushu Kika Co., Ltd.), and sealed for an organic EL device. A stop was produced.
Hydrogenated bisphenol A type epoxy resin (manufactured by Nippon Nippon Chemical Co., Ltd., HBE-100)
Bisphenol AF type epoxy resin (produced by Daikin Industries, Inc., epichlorohydrin adduct of 2,2-bis (4-hydroxyphenyl) hexafluoropropane)
Bisphenol A epoxy resin (Japan Epoxy Resin, Epicoat 828)
Bisphenol F epoxy resin (Japan Epoxy Resin, Epicoat 806)
Hydrogenated bisphenol F type epoxy resin (Japan Epoxy Resin, Epicoat YL6753)
Dicyclopentadiene type epoxy resin (Asahi Denka Co., EP-4088)
Cyclohexanedimethanol diglycidyl ether (Asahi Denka Co., EP-4085)
Photocationic polymerization initiator: Triphenylsulfonium-antimony photocationic polymerization initiator (Adeka Optomer SP170, manufactured by Asahi Denka Kogyo Co., Ltd.)
Sensitizer: Thioxanthone-based photosensitizer (manufactured by Nippon Kayaku Co., Ltd., DETX-S)
Curing control agent: Ethylene oxide-added bisphenol A diglycidyl ether (manufactured by Shin Nippon Rika Co., Ltd., BEO-60E)
（有機ＥＬ素子基板の製造）
ガラス基板（２５ｍｍ×２５ｍｍ×０．７ｍｍ）にＩＴＯ電極を１００ｎｍの厚さで成膜したものを透明支持基板とした。透明支持基板をアセトン、アルカリ水溶液、イオン交換水、イソプロピルアルコールにてそれぞれ１５分間超音波洗浄した後、煮沸させたイソプロピルアルコールにて１０分間洗浄し、更に、ＵＶ−オゾンクリーナ（ＮＬ−ＵＶ２５３、日本レーザー電子社製）にて直前処理を行った。
次に、この透明支持基板を真空蒸着装置の基板フォルダに固定し、素焼きの坩堝にＮ，Ｎ’−ジ（１−ナフチル）−Ｎ，Ｎ’−ジフェニルベンジジン（α−ＮＰＤ）を２００ｍｇ、他の異なる素焼き坩堝にトリス（８−ヒドロキシキノリラ）アルミニウム（Ａｌｑ３）を２００ｍｇ入れ、真空チャンバー内を、１×１０−４Ｐａまで減圧した。その後、α−ＮＰＤ入りの坩堝を加熱し、α−ＮＰＤを蒸着速度１５Å／ｓで基板に堆積させ、膜厚６００Åの正孔輸送層を成膜した。
次いでＡｌｑ３の坩堝を加熱し、１５Å／ｓの蒸着速度で（Ａｌｑ３）膜を形成した。その後、透明支持基板を別の真空蒸着装置に移し、この真空蒸着装置内のタングステン製抵抗加熱ボートにフッ化リチウム２００ｍｇ、別のタングステン製ボートにアルミニウム線１．０ｇを入れた。その後、真空槽を２×１０−４Ｐａまで減圧してフッ化リチウムを０．２Å／ｓの蒸着速度で５Å成膜した後、アルミニウムを２０Å／ｓの速度で２００Å成膜した。窒素により蒸着器内を常圧に戻し透明支持基板を取り出して透明支持基板上に作製した有機ＥＬ素子基板を得た。
(Manufacture of organic EL element substrate)
A glass substrate (25 mm × 25 mm × 0.7 mm) formed with an ITO electrode with a thickness of 100 nm was used as a transparent support substrate. The transparent support substrate was ultrasonically washed with acetone, an aqueous alkali solution, ion-exchanged water, and isopropyl alcohol for 15 minutes each, then washed with boiled isopropyl alcohol for 10 minutes, and further UV-ozone cleaner (NL-UV253, Japan). (Laser Electronics Co., Ltd.)
Next, this transparent support substrate is fixed to the substrate folder of the vacuum deposition apparatus, and 200 mg of N, N′-di (1-naphthyl) -N, N′-diphenylbenzidine (α-NPD) is put in an unglazed crucible. 200 mg of tris (8-hydroxyquinolina) aluminum (Alq 3 ) was put in an unglazed crucible having different pressures, and the pressure in the vacuum chamber was reduced to 1 × 10 −4 Pa. Thereafter, the crucible containing α-NPD was heated and α-NPD was deposited on the substrate at a deposition rate of 15 Å / s to form a 600 正 孔 hole transport layer.
Next, the Alq 3 crucible was heated to form an (Alq 3 ) film at a deposition rate of 15 Å / s. Thereafter, the transparent support substrate was transferred to another vacuum deposition apparatus, and 200 mg of lithium fluoride was placed in a tungsten resistance heating boat in the vacuum deposition apparatus, and 1.0 g of aluminum wire was placed in another tungsten boat. Thereafter, the pressure in the vacuum chamber was reduced to 2 × 10 −4 Pa, and 5 μm of lithium fluoride was formed at a deposition rate of 0.2 Å / s, and then 200 Å of aluminum was formed at a rate of 20 Å / s. The inside of the vapor deposition apparatus was returned to normal pressure with nitrogen, and the transparent support substrate was taken out to obtain an organic EL element substrate produced on the transparent support substrate.
（有機ＥＬ表示装置の製造）
実施例１〜１３及び比較例１〜９で得られた有機ＥＬ素子用封止剤をガラス製背面板に塗工装置にて５０μｍの厚さに全面塗布し、高圧水銀灯を用いて波長３６５ｎｍの紫外線を照射量が２０００ｍＪ／ｃｍ２となるように照射した。この基板を窒素中で、有機ＥＬ素子基板と貼合後、１０分間放置し有機ＥＬ素子用封止剤を硬化させて有機ＥＬ素子を封止した。
貼合後８０℃で３０分間加熱して有機ＥＬ素子用封止剤の硬化を行い、有機ＥＬ表示装置を製造した。
(Manufacture of organic EL display devices)
The sealing agent for organic EL elements obtained in Examples 1 to 13 and Comparative Examples 1 to 9 was applied to the entire surface of the glass back plate to a thickness of 50 μm with a coating apparatus, and a wavelength of 365 nm was applied using a high pressure mercury lamp. Ultraviolet rays were irradiated so that the irradiation amount was 2000 mJ / cm 2 . This substrate was bonded to the organic EL element substrate in nitrogen and allowed to stand for 10 minutes to cure the organic EL element sealing agent to seal the organic EL element.
After bonding, the organic EL display device was manufactured by heating at 80 ° C. for 30 minutes to cure the organic EL element sealant.
（評価）
実施例１〜１３及び比較例１〜９で製造した有機ＥＬ素子用封止剤及び有機ＥＬ表示装置について以下の評価を行った。結果を表１に示した。
(Evaluation)
The following evaluation was performed about the sealing agent for organic EL elements and organic EL display which were manufactured in Examples 1-13 and Comparative Examples 1-9. The results are shown in Table 1.
（粘度）
Ｅ型回転粘度計（ＴＶ−２２型：東機産業社製）により、２５℃、５ｒｐｍにて測定した。
(viscosity)
It measured at 25 degreeC and 5 rpm with the E-type rotational viscometer (TV-22 type | mold: Toki Sangyo company make).
（含水率及び透湿度の測定）
実施例１〜１３及び比較例１〜９で製造した有機ＥＬ素子用封止剤を１００μｍ厚となるように、ベーカー式アプリケーターにて恒温プレート上に塗布した。その後高圧水銀灯にて１００ｍＷ／ｃｍ２（３６５ｎｍ）で２０秒間光を照射したのち、８０℃にて３０分加熱し接着剤組成物のフィルムを得た。
得られたフィルム１０ｇを８５℃−８５％ＲＨの恒温恒湿オーブンに２４時間投入し、量の増加より、含水率を求めた。
また得られたフィルムの透湿度をＪＩＳ Ｚ ０２０８に従い、８５℃−８５％ＲＨに２４時間暴露して測定した。
(Measurement of moisture content and moisture permeability)
The sealing agent for organic EL elements manufactured in Examples 1 to 13 and Comparative Examples 1 to 9 was applied on a thermostatic plate with a Baker type applicator so as to have a thickness of 100 μm. Thereafter, the film was irradiated with light at 100 mW / cm 2 (365 nm) for 20 seconds with a high-pressure mercury lamp, and then heated at 80 ° C. for 30 minutes to obtain a film of an adhesive composition.
10 g of the obtained film was put into a constant temperature and humidity oven at 85 ° C. to 85% RH for 24 hours, and the water content was determined from the increase in the amount.
Further, the moisture permeability of the obtained film was measured by exposing it to 85 ° C.-85% RH for 24 hours in accordance with JIS Z 0208.
（耐光性）
実施例１〜１３及び比較例１〜９で製造した有機ＥＬ素子用封止剤を１．１ｍｍの硝子板２枚の間に２０μｍの厚みに形成し、スーパーキセノンウエザーメーターＳＸ７５（スガ試験機社製）で紫外線を１００時間照射した後の４００ｎｍにおける透過率を測定し、表１に示した。
(Light resistance)
The sealing agent for organic EL elements produced in Examples 1 to 13 and Comparative Examples 1 to 9 was formed to a thickness of 20 μm between two 1.1 mm glass plates, and Super Xenon Weather Meter SX75 (Suga Test Instruments Co., Ltd.) The transmittance at 400 nm after irradiation with ultraviolet rays for 100 hours was measured, and the results are shown in Table 1.
（発光状態評価）
有機ＥＬ表示装置を温度６０℃、湿度９０％の条件下に１００時間暴露した後、６Ｖの電圧を印加し有機ＥＬ表示装置の発光状態（発光及びダークスポット、画素周辺消光の有無）を目視で観察し、下記の基準で評価を行った。
◎：ダークスポット・周辺消光無く均一に発光
○：輝度に僅かな低下が見られるが、ダークスポット、周辺消光は無く均一に発光
△：一部にダークスポット有り。または、わずかな周辺消光有り
×：全面にダークスポット有り。または、顕著な周辺消光有り
(Light emission state evaluation)
After the organic EL display device is exposed to a temperature of 60 ° C. and a humidity of 90% for 100 hours, a voltage of 6 V is applied to visually check the light emission state of the organic EL display device (light emission and dark spots, whether or not pixels are quenched). Observed and evaluated according to the following criteria.
◎: Uniform light emission without dark spot / peripheral quenching ○: Slight decrease in brightness is observed, but there is no dark spot / peripheral quenching, and uniform light emission Δ: Some dark spots exist. Or there is a slight peripheral quenching ×: There is a dark spot on the entire surface. Or there is significant peripheral quenching
本発明によれば、優れた耐光性を有し、長期間耐湿性に優れるとともに、粘度が低く大面積の有機エレクトロルミネッセンス表示装置の製造に好適に用いることができる有機エレクトロルミネッセンス素子用封止剤、該有機エレクトロルミネッセンス素子用封止剤を用いた有機エレクトロルミネッセンス表示装置の製造方法、及び、有機エレクトロルミネッセンス表示装置を提供することができる。 ADVANTAGE OF THE INVENTION According to this invention, it has the outstanding light resistance, it is excellent in moisture resistance for a long period of time, and the sealing agent for organic electroluminescent elements which can be used suitably for manufacture of an organic electroluminescent display apparatus with a low viscosity and a large area The manufacturing method of the organic electroluminescent display apparatus using this sealing agent for organic electroluminescent elements, and an organic electroluminescent display apparatus can be provided.
Claims (7)
前記光重合性化合物は、該光重合性化合物１００重量部に対して、脂肪族環状骨格を有するエポキシ化合物を２０〜８０重量部、及び、芳香族環を有するエポキシ化合物を８０〜２０重量部含有する
ことを特徴とする有機エレクトロルミネッセンス素子用封止剤。 A sealing agent for an organic electroluminescence device containing a photopolymerizable compound and a cationic photopolymerization initiator,
The photopolymerizable compound contains 20 to 80 parts by weight of an epoxy compound having an aliphatic cyclic skeleton and 80 to 20 parts by weight of an epoxy compound having an aromatic ring with respect to 100 parts by weight of the photopolymerizable compound. A sealing agent for organic electroluminescence elements characterized by comprising:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005378504A JP4452683B2 (en) | 2005-01-26 | 2005-12-28 | Sealant for organic electroluminescence element, method for producing organic electroluminescence display device, and organic electroluminescence display device |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2005018935 | 2005-01-26 | ||
| JP2005204786 | 2005-07-13 | ||
| JP2005378504A JP4452683B2 (en) | 2005-01-26 | 2005-12-28 | Sealant for organic electroluminescence element, method for producing organic electroluminescence display device, and organic electroluminescence display device |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008292313A Division JP4850231B2 (en) | 2005-01-26 | 2008-11-14 | Sealant for organic electroluminescence device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2007046035A true JP2007046035A (en) | 2007-02-22 |
| JP4452683B2 JP4452683B2 (en) | 2010-04-21 |
Family
ID=37849128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005378504A Active JP4452683B2 (en) | 2005-01-26 | 2005-12-28 | Sealant for organic electroluminescence element, method for producing organic electroluminescence display device, and organic electroluminescence display device |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP4452683B2 (en) |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008274260A (en) * | 2007-04-06 | 2008-11-13 | Nippon Shokubai Co Ltd | Resin composition and optical member |
| JP2008305580A (en) * | 2007-06-05 | 2008-12-18 | Sekisui Chem Co Ltd | Post-light curing composition, sealant for organic electroluminescent element, manufacturing method of organic electroluminescent display, and organic electroluminescent display |
| JP2009030058A (en) * | 2007-07-27 | 2009-02-12 | Dongjin Semichem Co Ltd | Sealing method of display element |
| JP2009051980A (en) * | 2007-08-28 | 2009-03-12 | Panasonic Electric Works Co Ltd | Epoxy resin composition and resin-sealed device |
| JP2011021183A (en) * | 2009-06-15 | 2011-02-03 | Sekisui Chem Co Ltd | Photocurable resin composition, sealing agent for organic electroluminescence display elements, and organic electroluminescence display element |
| JP2012001690A (en) * | 2010-06-21 | 2012-01-05 | Adeka Corp | Photocurable resin composition |
| JP2014001367A (en) * | 2012-05-24 | 2014-01-09 | Adeka Corp | Photocurable resin composition |
| WO2014083850A1 (en) * | 2012-11-28 | 2014-06-05 | 日本化薬株式会社 | Resin composition, and cured product (1) thereof |
| WO2014192839A1 (en) | 2013-05-28 | 2014-12-04 | 株式会社ダイセル | Curable composition for sealing optical semiconductor |
| JP2015050143A (en) * | 2013-09-04 | 2015-03-16 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| JP2015143290A (en) * | 2014-01-31 | 2015-08-06 | アイカ工業株式会社 | Photocationic-curable resin composition |
| WO2016063825A1 (en) * | 2014-10-24 | 2016-04-28 | 積水化学工業株式会社 | Sealing agent for display elements and cured product of sealing agent for display elements |
| JPWO2014017524A1 (en) * | 2012-07-26 | 2016-07-11 | デンカ株式会社 | Resin composition |
| JP2016146347A (en) * | 2014-05-20 | 2016-08-12 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| JP2017179090A (en) * | 2016-03-29 | 2017-10-05 | 株式会社Adeka | Curable composition |
| US9798174B2 (en) | 2013-07-26 | 2017-10-24 | Sharp Kabushiki Kaisha | Liquid crystal display apparatus |
| WO2018235824A1 (en) * | 2017-06-23 | 2018-12-27 | 三井化学株式会社 | Image display device sealing material and image display device sealing sheet |
| WO2020067046A1 (en) * | 2018-09-26 | 2020-04-02 | デンカ株式会社 | Sealing agent for organic electroluminescent display elements |
| JP2020518952A (en) * | 2017-04-28 | 2020-06-25 | エルジー・ケム・リミテッド | Sealing material composition |
| CN112673065A (en) * | 2019-08-08 | 2021-04-16 | 三井化学株式会社 | Sealing material for image display device |
| JP2023022040A (en) * | 2019-02-21 | 2023-02-14 | デンカ株式会社 | Composition |
| TWI839389B (en) | 2018-09-26 | 2024-04-21 | 日商電化股份有限公司 | Sealant for organic electroluminescent display element |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4850231B2 (en) * | 2005-01-26 | 2012-01-11 | 積水化学工業株式会社 | Sealant for organic electroluminescence device |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191751A (en) * | 1998-12-25 | 2000-07-11 | Sumitomo Bakelite Co Ltd | Ultraviolet light-curable type resin composition |
| JP2002194056A (en) * | 2000-12-27 | 2002-07-10 | Nippon Kayaku Co Ltd | Epoxy resin composition and its cured product |
| JP2002256058A (en) * | 2001-03-01 | 2002-09-11 | Ricoh Co Ltd | Photocuring type epoxy resin composition and photocuring type sealant for display element |
| JP2003160640A (en) * | 2001-09-14 | 2003-06-03 | Sumitomo Chem Co Ltd | Resin composition for sealing optical semiconductor |
| JP2003327951A (en) * | 2002-05-10 | 2003-11-19 | Mitsui Chemicals Inc | Photo-setting resin composition for sealing material |
| WO2003106582A1 (en) * | 2002-01-10 | 2003-12-24 | 積水化学工業株式会社 | Adhesive for sealing organic electroluminescent element and use thereof |
| JP2004231938A (en) * | 2002-09-13 | 2004-08-19 | Sekisui Chem Co Ltd | Photocurable adhesive composition for sealing organic el element, method for sealing organic el element and organic el element |
| JP2004265615A (en) * | 2003-02-04 | 2004-09-24 | Sanyo Electric Co Ltd | Organic electroluminescent device, and manufacturing method of the same |
| JP2004307701A (en) * | 2003-04-09 | 2004-11-04 | Shin Etsu Chem Co Ltd | Highly thixotropic ultraviolet curable resin composition |
| JP2006070152A (en) * | 2004-09-02 | 2006-03-16 | Three Bond Co Ltd | Photocurable composition |
-
2005
- 2005-12-28 JP JP2005378504A patent/JP4452683B2/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000191751A (en) * | 1998-12-25 | 2000-07-11 | Sumitomo Bakelite Co Ltd | Ultraviolet light-curable type resin composition |
| JP2002194056A (en) * | 2000-12-27 | 2002-07-10 | Nippon Kayaku Co Ltd | Epoxy resin composition and its cured product |
| JP2002256058A (en) * | 2001-03-01 | 2002-09-11 | Ricoh Co Ltd | Photocuring type epoxy resin composition and photocuring type sealant for display element |
| JP2003160640A (en) * | 2001-09-14 | 2003-06-03 | Sumitomo Chem Co Ltd | Resin composition for sealing optical semiconductor |
| WO2003106582A1 (en) * | 2002-01-10 | 2003-12-24 | 積水化学工業株式会社 | Adhesive for sealing organic electroluminescent element and use thereof |
| JP2003327951A (en) * | 2002-05-10 | 2003-11-19 | Mitsui Chemicals Inc | Photo-setting resin composition for sealing material |
| JP2004231938A (en) * | 2002-09-13 | 2004-08-19 | Sekisui Chem Co Ltd | Photocurable adhesive composition for sealing organic el element, method for sealing organic el element and organic el element |
| JP2004265615A (en) * | 2003-02-04 | 2004-09-24 | Sanyo Electric Co Ltd | Organic electroluminescent device, and manufacturing method of the same |
| JP2004307701A (en) * | 2003-04-09 | 2004-11-04 | Shin Etsu Chem Co Ltd | Highly thixotropic ultraviolet curable resin composition |
| JP2006070152A (en) * | 2004-09-02 | 2006-03-16 | Three Bond Co Ltd | Photocurable composition |
Cited By (36)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008274260A (en) * | 2007-04-06 | 2008-11-13 | Nippon Shokubai Co Ltd | Resin composition and optical member |
| JP2008305580A (en) * | 2007-06-05 | 2008-12-18 | Sekisui Chem Co Ltd | Post-light curing composition, sealant for organic electroluminescent element, manufacturing method of organic electroluminescent display, and organic electroluminescent display |
| JP2009030058A (en) * | 2007-07-27 | 2009-02-12 | Dongjin Semichem Co Ltd | Sealing method of display element |
| JP2009051980A (en) * | 2007-08-28 | 2009-03-12 | Panasonic Electric Works Co Ltd | Epoxy resin composition and resin-sealed device |
| JP2011021183A (en) * | 2009-06-15 | 2011-02-03 | Sekisui Chem Co Ltd | Photocurable resin composition, sealing agent for organic electroluminescence display elements, and organic electroluminescence display element |
| JP2012001690A (en) * | 2010-06-21 | 2012-01-05 | Adeka Corp | Photocurable resin composition |
| JP2014001367A (en) * | 2012-05-24 | 2014-01-09 | Adeka Corp | Photocurable resin composition |
| US10273389B2 (en) | 2012-07-26 | 2019-04-30 | Denka Company Limited | Resin composition |
| JPWO2014017524A1 (en) * | 2012-07-26 | 2016-07-11 | デンカ株式会社 | Resin composition |
| CN104813741A (en) * | 2012-11-28 | 2015-07-29 | 日本化药株式会社 | Resin composition, and cured product (1) thereof |
| JPWO2014083850A1 (en) * | 2012-11-28 | 2017-01-05 | 日本化薬株式会社 | Resin composition and cured product thereof (1) |
| WO2014083850A1 (en) * | 2012-11-28 | 2014-06-05 | 日本化薬株式会社 | Resin composition, and cured product (1) thereof |
| KR20160015226A (en) | 2013-05-28 | 2016-02-12 | 주식회사 다이셀 | Curable composition for sealing optical semiconductor |
| WO2014192839A1 (en) | 2013-05-28 | 2014-12-04 | 株式会社ダイセル | Curable composition for sealing optical semiconductor |
| US9685597B2 (en) | 2013-05-28 | 2017-06-20 | Daicel Corporation | Curable composition for sealing optical semiconductor |
| US9798174B2 (en) | 2013-07-26 | 2017-10-24 | Sharp Kabushiki Kaisha | Liquid crystal display apparatus |
| JP2015050143A (en) * | 2013-09-04 | 2015-03-16 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| JP2015143290A (en) * | 2014-01-31 | 2015-08-06 | アイカ工業株式会社 | Photocationic-curable resin composition |
| JP2016146347A (en) * | 2014-05-20 | 2016-08-12 | 積水化学工業株式会社 | Sealant for organic electroluminescent display element |
| WO2016063825A1 (en) * | 2014-10-24 | 2016-04-28 | 積水化学工業株式会社 | Sealing agent for display elements and cured product of sealing agent for display elements |
| JP2017179090A (en) * | 2016-03-29 | 2017-10-05 | 株式会社Adeka | Curable composition |
| JP2020518952A (en) * | 2017-04-28 | 2020-06-25 | エルジー・ケム・リミテッド | Sealing material composition |
| JP7020495B2 (en) | 2017-04-28 | 2022-02-16 | エルジー・ケム・リミテッド | Sealing material composition |
| US11264589B2 (en) | 2017-06-23 | 2022-03-01 | Mitsui Chemicals, Inc. | Image display device sealing material and image display device sealing sheet |
| KR102161444B1 (en) | 2017-06-23 | 2020-10-06 | 미쯔이가가꾸가부시끼가이샤 | Image display device sealing material and image display device sealing sheet |
| KR20190125509A (en) * | 2017-06-23 | 2019-11-06 | 미쯔이가가꾸가부시끼가이샤 | Image display device sealing material and image display device sealing sheet |
| WO2018235824A1 (en) * | 2017-06-23 | 2018-12-27 | 三井化学株式会社 | Image display device sealing material and image display device sealing sheet |
| WO2020067046A1 (en) * | 2018-09-26 | 2020-04-02 | デンカ株式会社 | Sealing agent for organic electroluminescent display elements |
| CN112470551A (en) * | 2018-09-26 | 2021-03-09 | 电化株式会社 | Sealing agent for organic electroluminescent display element |
| JPWO2020067046A1 (en) * | 2018-09-26 | 2021-10-07 | デンカ株式会社 | Encapsulant for organic electroluminescence display elements |
| JP7270635B2 (en) | 2018-09-26 | 2023-05-10 | デンカ株式会社 | Sealant for organic electroluminescence display elements |
| TWI839389B (en) | 2018-09-26 | 2024-04-21 | 日商電化股份有限公司 | Sealant for organic electroluminescent display element |
| CN112470551B (en) * | 2018-09-26 | 2024-05-14 | 电化株式会社 | Sealing agent for organic electroluminescent display element |
| JP2023022040A (en) * | 2019-02-21 | 2023-02-14 | デンカ株式会社 | Composition |
| JP7397151B2 (en) | 2019-02-21 | 2023-12-12 | デンカ株式会社 | Composition |
| CN112673065A (en) * | 2019-08-08 | 2021-04-16 | 三井化学株式会社 | Sealing material for image display device |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4452683B2 (en) | 2010-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4452683B2 (en) | Sealant for organic electroluminescence element, method for producing organic electroluminescence display device, and organic electroluminescence display device | |
| JP4850231B2 (en) | Sealant for organic electroluminescence device | |
| JP6200203B2 (en) | Sealant for organic electroluminescence display element and method for producing organic electroluminescence display element | |
| JP4933751B2 (en) | Organic electroluminescent device sealant and organic electroluminescent device | |
| JP4384509B2 (en) | Method for sealing organic electroluminescent element and organic electroluminescent element | |
| WO2016167347A1 (en) | Sealant for electronic device, and method for manufacturing electronic device | |
| TWI677530B (en) | Sealant for organic electroluminescent display element | |
| JP2004231938A (en) | Photocurable adhesive composition for sealing organic el element, method for sealing organic el element and organic el element | |
| JP6247125B2 (en) | Manufacturing method of organic optical device | |
| JP2006236987A (en) | Sealant for organic electroluminescent element, sealing method of organic electroluminescent element, and organic electroluminescent element | |
| JP2009098187A (en) | Adhesive for optical components | |
| JP2017228414A (en) | Sealant for organic electroluminescent display element | |
| JP2005314687A (en) | Photo-curable resin composition, cationic photopolymerization initiator, adhesive for display element and display element | |
| JP2020024938A (en) | Curable composition and sealant for organic electroluminescent display element | |
| JP2007299725A (en) | Organic electroluminescent device | |
| JPWO2020149384A1 (en) | Encapsulant, cured product, organic electroluminescence display device, and manufacturing method of the device | |
| JP6527390B2 (en) | Sealant for organic electroluminescent display device | |
| JP4991648B2 (en) | Organic electroluminescent device sealant | |
| WO2021201013A1 (en) | Sealant, cured body, organic electroluminescent display device, and organic electroluminescent display device manufacturing method | |
| JP2006127815A (en) | Organic electroluminescent element | |
| TW202109786A (en) | Sealant for organic EL display element | |
| JP2005336314A (en) | Photocurable resin composition | |
| JP2011021183A (en) | Photocurable resin composition, sealing agent for organic electroluminescence display elements, and organic electroluminescence display element | |
| JP2023012530A (en) | Composition | |
| JP4555611B2 (en) | Organic electroluminescence device sealant and top emission type organic electroluminescence device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20080616 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080624 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20080812 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20080924 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20081114 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20100105 |
|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20100201 |
|
| R151 | Written notification of patent or utility model registration |
Ref document number: 4452683 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R151 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20130205 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (event date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20140205 Year of fee payment: 4 |