JP2012031091A - EuIII COMPLEX SALT, LUMINESCENT ELEMENT USING THE SAME, AND LUMINESCENCE ENHANCER - Google Patents
EuIII COMPLEX SALT, LUMINESCENT ELEMENT USING THE SAME, AND LUMINESCENCE ENHANCER Download PDFInfo
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- JP2012031091A JP2012031091A JP2010171584A JP2010171584A JP2012031091A JP 2012031091 A JP2012031091 A JP 2012031091A JP 2010171584 A JP2010171584 A JP 2010171584A JP 2010171584 A JP2010171584 A JP 2010171584A JP 2012031091 A JP2012031091 A JP 2012031091A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 74
- 239000003623 enhancer Substances 0.000 title claims abstract description 18
- 238000004020 luminiscence type Methods 0.000 title claims abstract description 15
- -1 organic acid anion Chemical class 0.000 claims abstract description 97
- 125000001931 aliphatic group Chemical group 0.000 claims description 55
- 125000004432 carbon atom Chemical group C* 0.000 claims description 48
- 239000007983 Tris buffer Substances 0.000 claims description 38
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 26
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 6
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 125000001183 hydrocarbyl group Chemical group 0.000 claims 4
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 abstract description 10
- 239000012964 benzotriazole Substances 0.000 abstract description 2
- RZCXRDBYLLLRKH-UHFFFAOYSA-N 2-(2-ethylhexyl)-2-sulfobutanedioic acid Chemical compound CCCCC(CC)CC(S(O)(=O)=O)(C(O)=O)CC(O)=O RZCXRDBYLLLRKH-UHFFFAOYSA-N 0.000 abstract 1
- LJKDOMVGKKPJBH-UHFFFAOYSA-N 2-ethylhexyl dihydrogen phosphate Chemical compound CCCCC(CC)COP(O)(O)=O LJKDOMVGKKPJBH-UHFFFAOYSA-N 0.000 abstract 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 47
- 239000000243 solution Substances 0.000 description 47
- 230000000052 comparative effect Effects 0.000 description 36
- 229920005989 resin Polymers 0.000 description 36
- 239000011347 resin Substances 0.000 description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 30
- 150000002430 hydrocarbons Chemical group 0.000 description 23
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 23
- 238000000295 emission spectrum Methods 0.000 description 22
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 20
- SQNZLBOJCWQLGQ-UHFFFAOYSA-N 6,6,7,7,8,8,8-heptafluoro-2,2-dimethyloctane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(F)(F)C(F)(F)C(F)(F)F SQNZLBOJCWQLGQ-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000003446 ligand Substances 0.000 description 16
- 239000002904 solvent Substances 0.000 description 16
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 14
- 239000012071 phase Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003960 organic solvent Substances 0.000 description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 12
- 238000011156 evaluation Methods 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 238000000695 excitation spectrum Methods 0.000 description 11
- 230000007423 decrease Effects 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000002284 excitation--emission spectrum Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 8
- 239000008346 aqueous phase Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 229930195734 saturated hydrocarbon Natural products 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 6
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 6
- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 description 5
- 229910052693 Europium Inorganic materials 0.000 description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000002194 synthesizing effect Effects 0.000 description 4
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 3
- 125000006017 1-propenyl group Chemical group 0.000 description 3
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 3
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000003493 decenyl group Chemical group [H]C([*])=C([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])[H] 0.000 description 3
- 125000002704 decyl 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])* 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 229920005672 polyolefin resin Polymers 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 0 CC1(*)C2=N*N=C2C=CC=C1 Chemical compound CC1(*)C2=N*N=C2C=CC=C1 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- CYDRXTMLKJDRQH-UHFFFAOYSA-N benzododecinium Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 CYDRXTMLKJDRQH-UHFFFAOYSA-N 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- 125000004369 butenyl group Chemical group C(=CCC)* 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000003438 dodecyl 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 2
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000006038 hexenyl group Chemical group 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- ZUZLIXGTXQBUDC-UHFFFAOYSA-N methyltrioctylammonium Chemical compound CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC ZUZLIXGTXQBUDC-UHFFFAOYSA-N 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 125000001421 myristyl group Chemical group [H]C([*])([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])C([H])([H])[H] 0.000 description 2
- 125000005187 nonenyl group Chemical group C(=CCCCCCCC)* 0.000 description 2
- 125000001400 nonyl group Chemical group [H]C([*])([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])[H] 0.000 description 2
- 125000004365 octenyl group Chemical group C(=CCCCCCC)* 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 125000002255 pentenyl group Chemical group C(=CCCC)* 0.000 description 2
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 2
- 239000004014 plasticizer Substances 0.000 description 2
- 229920006122 polyamide resin Polymers 0.000 description 2
- 229920001225 polyester resin Polymers 0.000 description 2
- 239000004645 polyester resin Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
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- 238000001228 spectrum Methods 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- QBVXKDJEZKEASM-UHFFFAOYSA-M tetraoctylammonium bromide Chemical compound [Br-].CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC QBVXKDJEZKEASM-UHFFFAOYSA-M 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
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- 239000004711 α-olefin Substances 0.000 description 2
- YRAJNWYBUCUFBD-UHFFFAOYSA-N 2,2,6,6-tetramethylheptane-3,5-dione Chemical compound CC(C)(C)C(=O)CC(=O)C(C)(C)C YRAJNWYBUCUFBD-UHFFFAOYSA-N 0.000 description 1
- BMOKHTQIBPRXSL-UHFFFAOYSA-N 2h-benzotriazole;sodium Chemical compound [Na].C1=CC=CC2=NNN=C21 BMOKHTQIBPRXSL-UHFFFAOYSA-N 0.000 description 1
- NKOTXYPTXKUCDL-UHFFFAOYSA-N 4-(trifluoromethyl)pyrimidin-2-amine Chemical compound NC1=NC=CC(C(F)(F)F)=N1 NKOTXYPTXKUCDL-UHFFFAOYSA-N 0.000 description 1
- ZWTWLIOPZJFEOO-UHFFFAOYSA-N 5-ethyl-2h-benzotriazole Chemical compound C1=C(CC)C=CC2=NNN=C21 ZWTWLIOPZJFEOO-UHFFFAOYSA-N 0.000 description 1
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- JTUSTMIMVOUSLY-UHFFFAOYSA-M CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1.CCCCC(CC)COC(CC(C(OCC(CC)CCCC)=O)S([O-])(=O)=O)=O Chemical compound CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1.CCCCC(CC)COC(CC(C(OCC(CC)CCCC)=O)S([O-])(=O)=O)=O JTUSTMIMVOUSLY-UHFFFAOYSA-M 0.000 description 1
- 239000004593 Epoxy Substances 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
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 1
- OIYWGUYEHXENNZ-UHFFFAOYSA-N N1N=NC2=C1C=CC=C2.C(C2=CC=CC=C2)[N+](CCCCCCCCCCCC)(C)C Chemical compound N1N=NC2=C1C=CC=C2.C(C2=CC=CC=C2)[N+](CCCCCCCCCCCC)(C)C OIYWGUYEHXENNZ-UHFFFAOYSA-N 0.000 description 1
- CCTYWEKLRAGREM-UHFFFAOYSA-N N1N=NC2=C1C=CC=C2.C(CCCCCCC)[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC Chemical compound N1N=NC2=C1C=CC=C2.C(CCCCCCC)[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC CCTYWEKLRAGREM-UHFFFAOYSA-N 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 229930182556 Polyacetal Natural products 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- WNBGYVXHFTYOBY-UHFFFAOYSA-N benzyl-dimethyl-tetradecylazanium Chemical compound CCCCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 WNBGYVXHFTYOBY-UHFFFAOYSA-N 0.000 description 1
- RITXFZKCKDYJKE-UHFFFAOYSA-M benzyl-dodecyl-dimethylazanium bis(2-ethylhexyl) phosphate Chemical compound P(=O)(OCC(CCCC)CC)(OCC(CCCC)CC)[O-].C(C1=CC=CC=C1)[N+](CCCCCCCCCCCC)(C)C RITXFZKCKDYJKE-UHFFFAOYSA-M 0.000 description 1
- UQPFZWHFRYGUEJ-UHFFFAOYSA-M bis(2-ethylhexyl) phosphate;tetraoctylazanium Chemical compound CCCCC(CC)COP([O-])(=O)OCC(CC)CCCC.CCCCCCCC[N+](CCCCCCCC)(CCCCCCCC)CCCCCCCC UQPFZWHFRYGUEJ-UHFFFAOYSA-M 0.000 description 1
- BJQHLKABXJIVAM-UHFFFAOYSA-N bis(2-ethylhexyl) phthalate Chemical compound CCCCC(CC)COC(=O)C1=CC=CC=C1C(=O)OCC(CC)CCCC BJQHLKABXJIVAM-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- HTDKEJXHILZNPP-UHFFFAOYSA-N dioctyl hydrogen phosphate Chemical compound CCCCCCCCOP(O)(=O)OCCCCCCCC HTDKEJXHILZNPP-UHFFFAOYSA-N 0.000 description 1
- 125000005066 dodecenyl group Chemical group C(=CCCCCCCCCCC)* 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
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- SULCVUWEGVSCPF-UHFFFAOYSA-L europium(2+);carbonate Chemical compound [Eu+2].[O-]C([O-])=O SULCVUWEGVSCPF-UHFFFAOYSA-L 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- PVDYMOCCGHXJAK-UHFFFAOYSA-H europium(3+);oxalate Chemical compound [Eu+3].[Eu+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O PVDYMOCCGHXJAK-UHFFFAOYSA-H 0.000 description 1
- LNYNHRRKSYMFHF-UHFFFAOYSA-K europium(3+);triacetate Chemical compound [Eu+3].CC([O-])=O.CC([O-])=O.CC([O-])=O LNYNHRRKSYMFHF-UHFFFAOYSA-K 0.000 description 1
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 description 1
- GEIGXJHXQWKQAT-UHFFFAOYSA-N europium;nitric acid Chemical compound [Eu].O[N+]([O-])=O GEIGXJHXQWKQAT-UHFFFAOYSA-N 0.000 description 1
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 description 1
- 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 1
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 description 1
- 238000007602 hot air drying Methods 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QLPMKRZYJPNIRP-UHFFFAOYSA-M methyl(trioctyl)azanium;bromide Chemical compound [Br-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC QLPMKRZYJPNIRP-UHFFFAOYSA-M 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
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Abstract
Description
本発明は、ＥｕＩＩＩ錯塩及びそれを用いた発光素子、並びに発光増強剤に関する。 The present invention relates to an Eu III complex salt, a light emitting device using the same, and a light emission enhancer.
３価ユーロピウム（ＥｕＩＩＩ）化合物は赤色発光材料として自発型ディスプレイ、高演色性発光灯等に用いられている。ＥｕＩＩＩ化合物としては、例えば、酸化イットリウム等によって賦活化されたＥｕＩＩＩ等の無機化合物が従来から用いられているが、近年注目されている有機ＥＬ素子等においては発光層が樹脂等の有機媒体からなるため、このような無機化合物は発光層に対する相溶性が十分ではなかった。そこで、ＥｕＩＩＩに有機化合物が配位してなるＥｕＩＩＩ錯体が開発されており、例えば、ＥｕＩＩＩにβ−ジケトン（Ｌ）が配位してなるトリスβ−ジケトナトＥｕＩＩＩ錯体（［ＥｕＬ３］）が知られているが、［ＥｕＬ３］は発光強度が十分ではなかった。 Trivalent europium (Eu III ) compounds are used as red light emitting materials in spontaneous displays, high color rendering light emitting lamps and the like. As the Eu III compound, for example, an inorganic compound such as Eu III activated by yttrium oxide or the like has been conventionally used. However, in an organic EL element or the like that has recently attracted attention, the light emitting layer is an organic medium such as a resin. Therefore, such an inorganic compound is not sufficiently compatible with the light emitting layer. Therefore, Eu III and Eu III complex organic compound is coordinated have been developed, for example, the Eu III beta-diketones (L) is coordinated tris beta-diketonate Eu III complex ([EuL 3 ]) Is known, however, [EuL 3 ] has insufficient light emission intensity.
また、［ＥｕＬ３］にさらに配位子（Ｘ０）が配位してなる［ＥｕＬ３（Ｘ０）］（Ｘ０が二座配位子の場合)若しくは［ＥｕＬ３（Ｘ０）２］（Ｘ０が単座配位子の場合)についても開発がなされており、例えば、「Ｐｏｌｙｈｅｄｒｏｎ」、２００７年、２６、１２２９−１２３８頁（非特許文献１）には、［ＥｕＬ３］にさらに配位子として２，４，６−トリ（２−ピリジル）−１，３，５−トリアジン（ＴＰＴＺ）が配位してなるＥｕ（ＴＴＡ）３ＴＰＴＺ及びＥｕ（ＢＡ）３ＴＰＴＺが記載されており、「Ｍｏｌｅｃｕｌａｒ Ｐｈｙｓｉｃｓ」、２００３年、ｖｏｌ．１０１、ｎｏ．７、１０３７−１０４５頁（非特許文献２）には、［ＥｕＬ３］にさらに配位子としてジメチルスルホキシド（ＤＭＳＯ）が配位してなるＥｕ（ＮＴＡ）３ＤＭＳＯが記載されている。 In addition, [EuL 3 (X 0 )] (when X 0 is a bidentate ligand) or [EuL 3 (X 0 ) 2, wherein a ligand (X 0 ) is further coordinated to [EuL 3 ]. ] (When X 0 is a monodentate ligand) has also been developed. For example, “Polyhedron”, 2007, 26, 1229-1238 (Non-Patent Document 1) further includes [EuL 3 ]. Eu (TTA) 3 TPTZ and Eu (BA) 3 TPTZ formed by coordination of 2,4,6-tri (2-pyridyl) -1,3,5-triazine (TPTZ) as ligands are described. "Molecular Physics", 2003, vol. 101, no. 7, pages 1037-1045 (Non-Patent Document 2) describe Eu (NTA) 3 DMSO in which dimethyl sulfoxide (DMSO) is coordinated to [EuL 3 ] as a ligand.
しかしながら、非特許文献１に記載のＥｕ（ＴＴＡ）３ＴＰＴＺ、Ｅｕ（ＢＡ）３ＴＰＴＺ及び非特許文献２に記載のＥｕ（ＮＴＡ）３ＤＭＳＯにおいても、発光強度は未だ十分ではなく、さらに、樹脂や有機溶媒等の有機媒体に対する相溶性も十分ではないため、樹脂と混合して発光素子に用いると経時によってＥｕＩＩＩ錯体又は配位子である有機物が表面に析出するいわゆるブリードアウトが生じるという問題を有していた。 However, even in Eu (TTA) 3 TPTZ, Eu (BA) 3 TPTZ described in Non-Patent Document 1, and Eu (NTA) 3 DMSO described in Non-Patent Document 2, the emission intensity is still not sufficient, and further, resin The compatibility with organic media such as organic solvents and the like is not sufficient, so when mixed with a resin and used in a light-emitting device, a so-called bleedout occurs in which an organic substance as an Eu III complex or a ligand is deposited on the surface over time. Had.
本発明は、上記従来技術の有する課題に鑑みてなされたものであり、高い発光強度と優れた有機媒体への相溶性とを有する発光性ＥｕＩＩＩ錯塩及びそれを用いた発光素子、並びにトリスβ−ジケトナトＥｕＩＩＩ錯体に対する発光増強剤を提供することを目的とする。 The present invention has been made in view of the above-described problems of the prior art, and has a light-emitting Eu III complex salt having high light emission intensity and excellent compatibility with an organic medium, a light-emitting device using the same, and Tris β The object is to provide a luminescence enhancer for the diketonato Eu III complex.
本発明者らは、上記目的を達成すべく鋭意研究を重ねた結果、トリスβ−ジケトナトＥｕＩＩＩ錯体にさらに特定の有機酸アニオンを配位してなるＥｕＩＩＩ錯イオンと、該ＥｕＩＩＩ錯イオンの対カチオンとしての第４級アンモニウムカチオンとからなるＥｕＩＩＩ錯塩が高い発光強度及び優れた有機媒体への相溶性を有することを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventors have obtained a Eu III complex ion obtained by further coordinating a specific organic acid anion to a tris β-diketonato Eu III complex, and the Eu III complex ion. The present inventors have found that an Eu III complex salt composed of a quaternary ammonium cation as a counter cation has high emission intensity and excellent compatibility with an organic medium, thereby completing the present invention.
すなわち、本発明の発光性ＥｕＩＩＩ錯塩は、トリスβ−ジケトナトＥｕＩＩＩ錯体及び該錯体に配位している有機酸アニオンからなるＥｕＩＩＩ錯イオンと、第４級アンモニウムカチオンとからなり、且つ、前記有機酸アニオンが下記一般式（１）〜（３）： That is, the luminescent Eu III complex salt of the present invention comprises a tris β-diketonato Eu III complex and an Eu III complex ion composed of an organic acid anion coordinated with the complex, and a quaternary ammonium cation, and The organic acid anion is represented by the following general formulas (1) to (3):
［式（１）中、Ｒ１、Ｒ２は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (1), R 1 and R 2 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（２）中、Ｒ３、Ｒ４は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (2), R 3 and R 4 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（３）中、Ｒ５は、水素原子又は炭素数１〜４の炭化水素基を示す。］
で表わされる有機酸アニオンのうちの少なくとも１種であることを特徴とするものである。
[In formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
It is at least 1 sort (s) among the organic acid anions represented by these.
また、本発明の発光増強剤は、有機酸アニオンと第４級アンモニウムカチオンとを含有し、且つ、前記有機酸アニオンが下記一般式（１）〜（３）： The light emission enhancer of the present invention contains an organic acid anion and a quaternary ammonium cation, and the organic acid anion is represented by the following general formulas (1) to (3):
［式（１）中、Ｒ１、Ｒ２は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (1), R 1 and R 2 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（２）中、Ｒ３、Ｒ４は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (2), R 3 and R 4 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（３）中、Ｒ５は、水素原子又は炭素数１〜４の炭化水素基を示す。］
で表わされる有機酸アニオンのうちの少なくとも１種であることを特徴とするものである。
[In formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
It is at least 1 sort (s) among the organic acid anions represented by these.
さらに、本発明の発光素子は、前記本発明の発光性ＥｕＩＩＩ錯塩を含有する発光層を備えることを特徴とするものである。 Furthermore, the light emitting device of the present invention is characterized by comprising a light emitting layer containing the light emitting Eu III complex salt of the present invention.
本発明において、前記第４級アンモニウムカチオンとしては、下記一般式（４）〜（５）： In the present invention, as the quaternary ammonium cation, the following general formulas (4) to (5):
［式（４）中、Ｒ６は炭素数１〜１０の脂肪族炭化水素基を示し、Ｒ７、Ｒ８、Ｒ９は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In the formula (4), R 6 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 7 , R 8 and R 9 may be the same or different, and each represents an aliphatic group having 4 to 10 carbon atoms. Represents a hydrocarbon group. ]
［式（５）中、Ｒ１０、Ｒ１１は、同一でも異なっていてもよく、それぞれ炭素数１〜４の脂肪族炭化水素基を示し、Ｒ１２は炭素数１０〜１６の脂肪族炭化水素基を示す。］
で表わされる第４級アンモニウムカチオンのうち少なくとも１種を用いることが好ましい。
[In Formula (5), R 10 and R 11 may be the same or different and each represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms; R 12 is an aliphatic hydrocarbon having 10 to 16 carbon atoms; Indicates a group. ]
It is preferable to use at least one of quaternary ammonium cations represented by the formula:
前記トリスβ−ジケトナトＥｕＩＩＩ錯体におけるβ−ジケトンとしては、下記一般式（６）： As the β-diketone in the tris β-diketonato Eu III complex, the following general formula (6):
［式（６）中、Ｒ１３、Ｒ１４は、同一でも異なっていてもよく、それぞれ−Ｃ（ＣＨ３）３、−ＣＦ３、−ＣＦ２ＣＦ３及び−（ＣＦ２）２ＣＦ３からなる群から選択されるいずれか１種を示す。］
で表わされるβ−ジケトンを用いることが好ましい。
[In Formula (6), R 13 and R 14 may be the same or different, and are each represented by —C (CH 3 ) 3 , —CF 3 , —CF 2 CF 3, and — (CF 2 ) 2 CF 3. Any one selected from the group consisting of: ]
It is preferable to use a β-diketone represented by
なお、本発明によって高い発光強度が得られるようになる理由は必ずしも定かではないが、本発明者らは以下のように推察する。すなわち、本発明の発光性ＥｕＩＩＩ錯塩においては、電荷を有する特定の有機酸アニオンをトリスβ−ジケトナトＥｕＩＩＩ錯体にさらに配位させることによって錯体中の配位子場の非対称性が大きくなり高い発光強度を得ることが可能となるのに対して、従来の電荷を持たないＤＭＳＯ等の配位子をトリスβ−ジケトナトＥｕＩＩＩ錯体にさらに配位させてなるＥｕＩＩＩ錯体においては、錯体中の配位子場の非対称性が本発明に比べて小さいため、高い発光強度が得られないと本発明者らは推察する。 The reason why high emission intensity can be obtained by the present invention is not necessarily clear, but the present inventors infer as follows. That is, in the luminescent Eu III complex salt of the present invention, further coordination of a specific organic acid anion having a charge to the tris β-diketonato Eu III complex increases the asymmetry of the ligand field in the complex. whereas it is possible to obtain light emission intensity, in the conventional Eu III complex ligands such as DMSO composed by further coordinated to tris β- diketonate Eu III complex uncharged, in the complex Since the asymmetry of the ligand field is smaller than that of the present invention, the present inventors presume that high emission intensity cannot be obtained.
本発明によれば、高い発光強度と優れた有機媒体への相溶性とを有する発光性ＥｕＩＩＩ錯塩及びそれを用いた発光素子、並びにトリスβ−ジケトナトＥｕＩＩＩ錯体に対する発光増強剤を提供することが可能となる。 According to the present invention, there are provided a luminescent Eu III complex salt having high luminescence intensity and excellent compatibility with an organic medium, a light emitting device using the same, and a luminescence enhancer for a tris β-diketonato Eu III complex. Is possible.
以下、本発明をその好適な実施形態に即して詳細に説明する。 Hereinafter, the present invention will be described in detail with reference to preferred embodiments thereof.
先ず、本発明の発光性ＥｕＩＩＩ錯塩について説明する。本発明の発光性ＥｕＩＩＩ錯塩は、トリスβ−ジケトナトＥｕＩＩＩ錯体及び該錯体に配位している有機酸アニオンからなるＥｕＩＩＩ錯イオンと、第４級アンモニウムカチオンとからなり、且つ、前記有機酸アニオンが下記一般式（１）〜（３）： First, the luminescent Eu III complex salt of the present invention will be described. The luminescent Eu III complex salt of the present invention comprises a tris β-diketonato Eu III complex, an Eu III complex ion comprising an organic acid anion coordinated with the complex, a quaternary ammonium cation, and the organic The acid anion is represented by the following general formulas (1) to (3):
［式（１）中、Ｒ１、Ｒ２は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (1), R 1 and R 2 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（２）中、Ｒ３、Ｒ４は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (2), R 3 and R 4 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（３）中、Ｒ５は、水素原子又は炭素数１〜４の炭化水素基を示す。］
で表わされる有機酸アニオンのうちの少なくとも１種であることを特徴とするものである。
[In formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
It is at least 1 sort (s) among the organic acid anions represented by these.
本発明にかかるトリスβ−ジケトナトＥｕＩＩＩ錯体は、中心金属としての３価ユーロピウム（ＥｕＩＩＩ）１分子に対して、配位子としてのβ−ジケトンが３分子配位してなる錯体である。前記β−ジケトンとは、下記一般式（７）： The tris β-diketonato Eu III complex according to the present invention is a complex in which three molecules of β-diketone as a ligand are coordinated with one molecule of trivalent europium (Eu III ) as a central metal. The β-diketone is the following general formula (7):
で表わされるβ−ジケトン構造を分子中に少なくとも１つ有し、酸素原子を介してＥｕＩＩＩに２箇所で配位する二座配位子である。このようなβ−ジケトンとしては、発光性ＥｕＩＩＩ錯塩の発光強度がより向上する傾向にあるという観点から、下記一般式（６）： Is a bidentate ligand having at least one β-diketone structure represented by the formula (1) and coordinated to Eu III at two positions via an oxygen atom. As such β-diketone, from the viewpoint that the emission intensity of the luminescent Eu III complex salt tends to be further improved, the following general formula (6):
［式（６）中、Ｒ１３、Ｒ１４は、同一でも異なっていてもよく、それぞれ−Ｃ（ＣＨ３）３、−ＣＦ３、−ＣＦ２ＣＦ３及び−（ＣＦ２）２ＣＦ３からなる群から選択されるいずれか１種を示す。］
で表わされるβ−ジケトンであることが好ましい。このようなβ−ジケトンとしては、１，１，１，２，２，３，３−ヘプタフルオロ−７，７−ジメチル−４，６−オクタンジオン；１，１，１，５，５，５−ヘキサフルオロ−２，４−ペンタジオン；２，２，６，６−テトラメチル−３，５−ヘプタンジオン等が挙げられ、これらのβ−ジケトンの中でも、発光性ＥｕＩＩＩ錯塩の発光強度が特に向上する傾向にあるという観点から、下記式（８）；
[In Formula (6), R 13 and R 14 may be the same or different, and are each represented by —C (CH 3 ) 3 , —CF 3 , —CF 2 CF 3, and — (CF 2 ) 2 CF 3. Any one selected from the group consisting of: ]
It is preferable that it is (beta) -diketone represented by these. Examples of such β-diketone include 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione; 1,1,1,5,5,5 -Hexafluoro-2,4-pentadione; 2,2,6,6-tetramethyl-3,5-heptanedione and the like. Among these β-diketones, the emission intensity of the luminescent Eu III complex salt is particularly From the viewpoint that it tends to improve, the following formula (8);
で表わされる１，１，１，２，２，３，３−ヘプタフルオロ−７，７−ジメチル−４，６−オクタンジオンが特に好ましい。 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedione represented by the formula is particularly preferred.
本発明にかかる有機酸アニオンは、前記トリスβ−ジケトナトＥｕＩＩＩ錯体にさらに配位するアニオンであり、下記一般式（１）〜（３）： The organic acid anion according to the present invention is an anion further coordinated to the tris β-diketonato Eu III complex, and the following general formulas (1) to (3):
［式（１）中、Ｒ１、Ｒ２は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (1), R 1 and R 2 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（２）中、Ｒ３、Ｒ４は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (2), R 3 and R 4 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（３）中、Ｒ５は、水素原子又は炭素数１〜４の炭化水素基を示す。］
で表わされる有機酸アニオンのうちの少なくとも１種である。
[In formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
It is at least 1 sort (s) of the organic acid anions represented by these.
本発明において、一般式（１）〜（３）で表わされる有機酸アニオンはそれぞれ前記トリスβ−ジケトナトＥｕＩＩＩ錯体に対して１モル当量で配位し、前記トリスβ−ジケトナトＥｕＩＩＩ錯体と前記有機酸アニオンとからなるＥｕＩＩＩ錯イオンを形成する。このときの配位原子は、前記一般式（１）〜（２）で表わされる有機酸アニオンにおいては酸素原子であり、前記一般式（３）で表わされる有機酸アニオンにおいては窒素原子である。本発明にかかる有機酸アニオンが前記トリスβ−ジケトナトＥｕＩＩＩ錯体にさらに配位することにより、本発明の発光性ＥｕＩＩＩ錯塩は高い発光強度を有する。 In the present invention, the general formula (1) coordinated with one molar equivalent for each organic acid anion is the tris β- diketonate Eu III complex represented by - (3), wherein said tris β- diketonate Eu III complex An Eu III complex ion composed of an organic acid anion is formed. The coordination atom at this time is an oxygen atom in the organic acid anion represented by the general formulas (1) to (2), and a nitrogen atom in the organic acid anion represented by the general formula (3). When the organic acid anion according to the present invention is further coordinated to the tris β-diketonato Eu III complex, the luminescent Eu III complex salt of the present invention has high emission intensity.
前記一般式（１）〜（２）中のＲ1、Ｒ2、Ｒ3、Ｒ4は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基である。このような脂肪族炭化水素基の炭素数が前記下限未満では、発光性ＥｕＩＩＩ錯塩の発光強度が低下し、また、有機酸アニオンと第４級アンモニウムカチオンとが有機酸塩となった際の結晶性が高くなるために樹脂との相溶性が低くなる。他方、炭素数が前記上限を超えると、発光性ＥｕＩＩＩ錯塩の発光強度が低下し、また、有機酸アニオンの分子量が大きくなるために系内のＥｕＩＩＩの含有率が低下する。また、このような脂肪族炭化水素基の炭素数としては、同様の観点で、より高い効果が得られる傾向にあることから８であることがより好ましい。 R 1 , R 2 , R 3 and R 4 in the general formulas (1) to (2) may be the same or different and each is an aliphatic hydrocarbon group having 4 to 10 carbon atoms. When the number of carbon atoms of such an aliphatic hydrocarbon group is less than the lower limit, the emission intensity of the luminescent Eu III complex salt decreases, and when the organic acid anion and the quaternary ammonium cation become an organic acid salt. Since the crystallinity increases, the compatibility with the resin decreases. On the other hand, when the number of carbons exceeds the upper limit, the emission intensity of the luminescent Eu III complex salt decreases, and the molecular weight of the organic acid anion increases, so that the Eu III content in the system decreases. Further, the number of carbon atoms of such an aliphatic hydrocarbon group is more preferably 8 from the same viewpoint because a higher effect tends to be obtained.
また、前記一般式（１）〜（２）中の前記脂肪族炭化水素基としては、脂肪族飽和炭化水素基であっても脂肪族不飽和炭化水素基であってもよく、直鎖状であっても分岐鎖状であってもよく、例えば、ブチル基、ブテニル基、ペンチル基、ペンテニル基、ヘキシル基、ヘキセニル基、ヘプチル基、ヘプテニル基、オクチル基、２−エチルヘキシル基、オクテニル基、ノニル基、ノネニル基、デシル基、デセニル基等が挙げられる。これらの脂肪族炭化水素基の中でも、２−エチルヘキシル基、オクチル基、３−オクテニル基が好ましく、２−エチルヘキシル基が特に好ましい。 Further, the aliphatic hydrocarbon group in the general formulas (1) to (2) may be an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group, For example, butyl, butenyl, pentyl, pentenyl, hexyl, hexenyl, heptyl, heptenyl, octyl, 2-ethylhexyl, octenyl, nonyl Group, nonenyl group, decyl group, decenyl group and the like. Among these aliphatic hydrocarbon groups, a 2-ethylhexyl group, an octyl group, and a 3-octenyl group are preferable, and a 2-ethylhexyl group is particularly preferable.
前記一般式（３）中のＲ５は、水素原子又は炭素数１〜４の炭化水素基である。このような炭化水素基の炭素数が前記上限を超えると、発光性ＥｕＩＩＩ錯塩の発光強度が低下する。また、前記一般式（３）中の前記炭化水素基としては、飽和炭化水素基であっても不飽和炭化水素基であってもよく、直鎖状であっても分岐鎖状であっても環状であってもよく、例えば、メチル基、エチル基、エチレン基、プロピル基、イソプロピル基、１−プロペニル基、２−プロペニル基、イソプロペニル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、１−ブテニル基、２−ブテニル基、３−ブテニル基、１，３−ブタジエニル基等が挙げられる。このようなＲ５としては、水素原子、メチル基、エチル基が好ましい。 R 5 in the general formula (3) is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. When the carbon number of such a hydrocarbon group exceeds the upper limit, the emission intensity of the luminescent Eu III complex salt decreases. Further, the hydrocarbon group in the general formula (3) may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and may be linear or branched. It may be cyclic, for example, methyl, ethyl, ethylene, propyl, isopropyl, 1-propenyl, 2-propenyl, isopropenyl, butyl, isobutyl, sec-butyl, tert -Butyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group and the like can be mentioned. Such R 5 is preferably a hydrogen atom, a methyl group, or an ethyl group.
このような有機酸アニオンの中でも、発光性ＥｕＩＩＩ錯塩の発光強度がより向上するという観点から、前記一般式（２）及び前記一般式（３）で表わされる有機酸アニオンが好ましく、前記一般式（２）で表わされる有機酸アニオンとしては、ジ（２−エチルヘキシル）リン酸及びジオクチルリン酸がより好ましく、前記一般式（３）で表わされる有機酸アニオンとしては、１Ｈ−ベンゾトリアゾール、５−メチルべンゾトリアゾール、５−エチルベンゾトリアゾールがより好ましい。また、発光性ＥｕＩＩＩ錯塩の空気中での安定性及び水に対する安定性がより向上し、発光がより長時間持続するという観点からは、１Ｈ−ベンゾトリアゾールが特に好ましい。これらの有機酸アニオンとしては、１種を単独で用いても２種以上を併用してもよく、下記の第４級アンモニウムカチオンとの有機酸塩として用いてもよい。 Among these organic acid anions, the organic acid anions represented by the general formula (2) and the general formula (3) are preferable from the viewpoint that the emission intensity of the luminescent Eu III complex salt is further improved. As the organic acid anion represented by (2), di (2-ethylhexyl) phosphate and dioctyl phosphate are more preferable, and as the organic acid anion represented by the general formula (3), 1H-benzotriazole, 5- Methylbenzotriazole and 5-ethylbenzotriazole are more preferable. In addition, 1H-benzotriazole is particularly preferable from the viewpoint that the stability of the luminescent Eu III complex salt in air and water is further improved and the luminescence lasts for a longer time. These organic acid anions may be used singly or in combination of two or more, and may be used as an organic acid salt with the following quaternary ammonium cation.
本発明にかかる第４級アンモニウムカチオンは、前記ＥｕＩＩＩ錯イオンの対カチオンである。本発明の発光性ＥｕＩＩＩ錯塩は、前記ＥｕＩＩＩ錯イオンの対カチオンとして前記第４級アンモニウムカチオンを備えることにより有機溶媒や樹脂等の有機媒体への優れた相溶性を有する。このような第４級アンモニウムカチオンとしては、発光性ＥｕＩＩＩ錯塩の有機媒体への相溶性がより優れる傾向にあるという観点から、下記一般式（４）〜（５）： The quaternary ammonium cation according to the present invention is a counter cation of the Eu III complex ion. The luminescent Eu III complex salt of the present invention has excellent compatibility with an organic medium such as an organic solvent or a resin by including the quaternary ammonium cation as a counter cation of the Eu III complex ion. As such a quaternary ammonium cation, from the viewpoint that the compatibility of the luminescent Eu III complex salt with an organic medium tends to be more excellent, the following general formulas (4) to (5):
［式（４）中、Ｒ６は炭素数１〜１０の脂肪族炭化水素基を示し、Ｒ７、Ｒ８、Ｒ９は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In the formula (4), R 6 represents an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and R 7 , R 8 and R 9 may be the same or different, and each represents an aliphatic group having 4 to 10 carbon atoms. Represents a hydrocarbon group. ]
［式（５）中、Ｒ１０、Ｒ１１は、同一でも異なっていてもよく、それぞれ炭素数１〜４の脂肪族炭化水素基を示し、Ｒ１２は炭素数１０〜１６の脂肪族炭化水素基を示す。］
で表わされる第４級アンモニウムカチオンのうち少なくとも１種を用いることが好ましい。
[In Formula (5), R 10 and R 11 may be the same or different and each represents an aliphatic hydrocarbon group having 1 to 4 carbon atoms; R 12 is an aliphatic hydrocarbon having 10 to 16 carbon atoms; Indicates a group. ]
It is preferable to use at least one of quaternary ammonium cations represented by the formula:
前記一般式（４）中のＲ６は炭素数１〜１０の脂肪族炭化水素基である。このような炭化水素基の炭素数が前記上限を超えると、発光性ＥｕＩＩＩ錯塩の発光強度が低下する。また、前記一般式（４）中のＲ６として選択され得る脂肪族炭化水素基としては、脂肪族飽和炭化水素基であっても脂肪族不飽和炭化水素基であってもよく、直鎖状であっても分岐鎖状であってもよく、例えば、メチル基、エチル基、エチレン基、プロピル基、イソプロピル基、１−プロペニル基、２−プロペニル基、イソプロペニル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ブテニル基、１−ブテニル基、２−ブテニル基、３−ブテニル基、１，３−ブタジエニル基、ペンチル基、ペンテニル基、ヘキシル基、ヘキセニル基、ヘプチル基、ヘプテニル基、オクチル基、２−エチルヘキシル基、オクテニル基、ノニル基、ノネニル基、デシル基、デセニル基等が挙げられる。 R 6 in the general formula (4) is an aliphatic hydrocarbon group having 1 to 10 carbon atoms. When the carbon number of such a hydrocarbon group exceeds the upper limit, the emission intensity of the luminescent Eu III complex salt decreases. In addition, the aliphatic hydrocarbon group that can be selected as R 6 in the general formula (4) may be an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group. Or a branched chain, for example, methyl group, ethyl group, ethylene group, propyl group, isopropyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, butenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1,3-butadienyl group, pentyl group, pentenyl group, hexyl group, hexenyl group, heptyl group, Examples include heptenyl group, octyl group, 2-ethylhexyl group, octenyl group, nonyl group, nonenyl group, decyl group, decenyl group and the like.
前記一般式（４）中のＲ７、Ｒ８、Ｒ９は、同一でも異なっていてもよく、それぞれ炭素数４〜１０（より好ましくは４〜８）の脂肪族炭化水素基である。このような脂肪族炭化水素基の炭素数が前記下限未満では、発光性ＥｕＩＩＩ錯塩の樹脂や有機溶媒等の有機媒体に対する相溶性が低下し、他方、前記上限を超えると、発光性ＥｕＩＩＩ錯塩の発光強度が低下する。また、前記一般式（４）中のＲ７、Ｒ８及びＲ９として選択され得る脂肪族炭化水素基としては、脂肪族飽和炭化水素基であっても脂肪族不飽和炭化水素基であってもよく、直鎖状であっても分岐鎖状であってもよく、例えば、前記一般式（４）中のＲ６として選択され得る脂肪族炭化水素基として挙げたものの中で炭素数が４〜１０のものが挙げられる。 R 7 , R 8 and R 9 in the general formula (4) may be the same or different, and each is an aliphatic hydrocarbon group having 4 to 10 (more preferably 4 to 8) carbon atoms. Such a number of carbon atoms in the aliphatic hydrocarbon group is less than the lower limit, the compatibility is lowered with respect to the organic medium such as a resin and an organic solvent luminescent Eu III complex, whereas if it exceeds the upper limit, luminescent Eu III The emission intensity of the complex salt decreases. In addition, the aliphatic hydrocarbon group that can be selected as R 7 , R 8 and R 9 in the general formula (4) is an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group. It may be linear or branched. For example, among the above-mentioned aliphatic hydrocarbon groups that can be selected as R 6 in the general formula (4), the number of carbon atoms is 4 -10.
前記一般式（５）中のＲ１０、Ｒ１１は、同一でも異なっていてもよく、それぞれ炭素数１〜４の脂肪族炭化水素基である。このような脂肪族炭化水素基の炭素数が前記上限を超えると、発光性ＥｕＩＩＩ錯塩の発光強度が低下する。また、前記一般式（５）中のＲ１０又はＲ１１として選択され得る脂肪族炭化水素基としては、脂肪族飽和炭化水素基であっても脂肪族不飽和炭化水素基であってもよく、直鎖状であっても分岐鎖状であってもよく、例えば、メチル基、エチル基、エチレン基、プロピル基、イソプロピル基、１−プロペニル基、２−プロペニル基、イソプロペニル基、ブチル基、イソブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、１−ブテニル基、２−ブテニル基、３−ブテニル基、１，３−ブタジエニル基が挙げられる。これらの脂肪族炭化水素基の中でも、メチル基が好ましい。 R 10 and R 11 in the general formula (5) may be the same or different and are each an aliphatic hydrocarbon group having 1 to 4 carbon atoms. When the carbon number of such an aliphatic hydrocarbon group exceeds the upper limit, the emission intensity of the luminescent Eu III complex salt decreases. In addition, the aliphatic hydrocarbon group that can be selected as R 10 or R 11 in the general formula (5) may be an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group, It may be linear or branched, for example, methyl group, ethyl group, ethylene group, propyl group, isopropyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, butyl group, Examples include isobutyl group, sec-butyl group, tert-butyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group and 1,3-butadienyl group. Among these aliphatic hydrocarbon groups, a methyl group is preferable.
前記一般式（５）中のＲ１２は、炭素数１０〜１６の脂肪族炭化水素基である。このような脂肪族炭化水素基の炭素数が前記下限未満では、発光性ＥｕＩＩＩ錯塩の樹脂や有機溶媒等の有機媒体に対する相溶性が低下し、他方、前記上限を超えると、発光性ＥｕＩＩＩ錯塩の発光強度が低下する。また、前記一般式（５）中のＲ１２として選択され得る脂肪族炭化水素基としては、脂肪族飽和炭化水素基であっても脂肪族不飽和炭化水素基であってもよく、直鎖状であっても分岐鎖状であってもよく、例えば、デシル基、デセニル基、ドデシル基、ドデセニル基、テトラデシル基、テトラデセニル基、ヘキサデシル基、ヘキサデセニル基等が挙げられる。これらの脂肪族炭化水素基の中でも、ドデシル基、テトラデシル基が好ましい。 R 12 in the general formula (5) is an aliphatic hydrocarbon group having 10 to 16 carbon atoms. Such a number of carbon atoms in the aliphatic hydrocarbon group is less than the lower limit, the compatibility is lowered with respect to the organic medium such as a resin and an organic solvent luminescent Eu III complex, whereas if it exceeds the upper limit, luminescent Eu III The emission intensity of the complex salt decreases. The aliphatic hydrocarbon group that can be selected as R 12 in the general formula (5) may be either an aliphatic saturated hydrocarbon group or an aliphatic unsaturated hydrocarbon group, Or a branched chain, and examples thereof include a decyl group, a decenyl group, a dodecyl group, a dodecenyl group, a tetradecyl group, a tetradecenyl group, a hexadecyl group, and a hexadecenyl group. Among these aliphatic hydrocarbon groups, a dodecyl group and a tetradecyl group are preferable.
このような第４級アンモニウムカチオンとしては、発光性ＥｕＩＩＩ錯塩の樹脂や有機溶媒等の有機媒体に対する相溶性がより向上するという観点から、テトラオクチルアンモニウム、トリオクチルメチルアンモニウム、ベンジルジメチルドデシルアンモニウム、ベンジルジメチルテトラデシルアンモニウムが好ましい。さらに、これらの中でも、発光性ＥｕＩＩＩ錯塩の空気中での安定性及び水に対する安定性がより向上し、発光がより長時間持続するという観点から、ベンジルジメチルドデシルアンモニウムが特に好ましい。また、このような第４級アンモニウムカチオンとしては、１種を単独で用いても２種以上を併用してもよく、前記有機酸アニオンとの有機酸塩として用いてもよい。 As such a quaternary ammonium cation, tetraoctylammonium, trioctylmethylammonium, benzyldimethyldodecylammonium, from the viewpoint of further improving the compatibility of the luminescent Eu III complex salt with an organic medium such as a resin or an organic solvent, Benzyldimethyltetradecylammonium is preferred. Further, among these, benzyldimethyldodecylammonium is particularly preferable from the viewpoint that the stability of the luminescent Eu III complex salt in air and water is further improved and the luminescence lasts for a longer time. Moreover, as such a quaternary ammonium cation, 1 type may be used independently or 2 or more types may be used together, and you may use as an organic acid salt with the said organic acid anion.
本発明の発光性ＥｕＩＩＩ錯塩の合成方法は特に制限されず、例えば、先ず前記有機酸アニオンと前記第４級アンモニウムカチオンとからなる有機酸塩及びトリスβ−ジケトナトＥｕＩＩＩ錯体をそれぞれ合成し、得られた有機酸塩とトリスβ−ジケトナトＥｕＩＩＩ錯体とを溶媒中で混合する方法が挙げられる。 The method for synthesizing the luminescent Eu III complex salt of the present invention is not particularly limited. For example, first, an organic acid salt composed of the organic acid anion and the quaternary ammonium cation and a tris β-diketonato Eu III complex are respectively synthesized. Examples include a method of mixing the obtained organic acid salt and the tris β-diketonato Eu III complex in a solvent.
前記有機酸塩を合成する方法としては、例えば、前記有機酸アニオンと、前記有機酸アニオンに対して０．５〜１．５モル当量の前記第４級アンモニウムカチオンとを水溶液中に溶解して得られた溶液を、２０〜８０℃程度で１時間〜１０日間程度放置して水相と油相に分相せしめた後、回収した油相を常圧又は減圧下、９０〜１１０℃で１〜４時間乾燥せしめることで有機酸塩を得る方法が挙げられる。 As a method for synthesizing the organic acid salt, for example, the organic acid anion and 0.5 to 1.5 molar equivalent of the quaternary ammonium cation with respect to the organic acid anion are dissolved in an aqueous solution. The obtained solution is allowed to stand at about 20 to 80 ° C. for about 1 hour to 10 days to separate into an aqueous phase and an oil phase. A method of obtaining an organic acid salt by drying for 4 hours is mentioned.
また、前記トリスβ−ジケトナトＥｕＩＩＩ錯体を合成する方法としては、例えば、先ず溶媒中に３価のユーロピウムからなる化合物を溶解せしめ、次いで前記ユーロピウムに対して３モル当量のβ−ジケトンを滴下して得られた溶液を室温（２５℃程度）にて２４時間攪拌することにより、トリスβ−ジケトナトＥｕＩＩＩ錯体の白色結晶を前記溶液中に得る方法が挙げられる。前記３価のユーロピウムからなる化合物としては、特に制限されず、酢酸ユーロピウム（Ｅｕ（ＣＨ３ＣＯＯ)３）、塩化ユーロピウム（ＥｕＣｌ３）、硝酸ユーロピウム（Ｅｕ（ＮＯ３）３）、炭酸ユーロピウム（Ｅｕ２（ＣＯ３）３）、シュウ酸ユーロピウム（Ｅｕ２（Ｃ２Ｏ４）３）、硫酸ユーロピウム（Ｅｕ２（ＳＯ４）３）等が挙げられる。また、前記溶媒としては、水、アルコール、酢酸エチル、アセトン等が挙げられる。 As a method for synthesizing the tris β-diketonato Eu III complex, for example, a compound composed of trivalent europium is first dissolved in a solvent, and then 3 molar equivalents of β-diketone is added dropwise to the europium. The solution obtained in this way is stirred at room temperature (about 25 ° C.) for 24 hours to obtain white crystals of the tris β-diketonato Eu III complex in the solution. The compound composed of the trivalent europium is not particularly limited, and europium acetate (Eu (CH 3 COO) 3 ), europium chloride (EuCl 3 ), europium nitrate (Eu (NO 3 ) 3 ), europium carbonate (Eu 2 (CO 3 ) 3 ), europium oxalate (Eu 2 (C 2 O 4 ) 3 ), europium sulfate (Eu 2 (SO 4 ) 3 ), and the like. Examples of the solvent include water, alcohol, ethyl acetate, acetone and the like.
有機酸塩とトリスβ−ジケトナトＥｕＩＩＩ錯体とを溶媒中で混合する方法としては、特に制限されず、本発明においては、溶媒中で混合するだけで容易に本発明の発光性ＥｕＩＩＩ錯塩を得ることができる。前記溶媒としては、水及び有機溶媒が挙げられ、前記有機溶媒としては、メタノール、アセトン、酢酸エチル、アセトニトリル、テトラヒドロフラン、ジクロロメタン、ヘキサン等が挙げられる。これらの中でも、前記有機酸塩がより溶解し易い傾向にあるという観点から、有機溶媒を用いることが好ましい。このような溶媒としては、１種を単独で用いても２種以上を併用してもよく、樹脂を含有する樹脂溶液であってもよく、また、酸化防止剤や可塑剤等の添加剤をさらに含有していてもよい。 The method for mixing the organic acid salt and the tris β-diketonato Eu III complex in a solvent is not particularly limited. In the present invention, the luminescent Eu III complex salt of the present invention can be easily mixed by simply mixing in a solvent. Obtainable. Examples of the solvent include water and organic solvents, and examples of the organic solvent include methanol, acetone, ethyl acetate, acetonitrile, tetrahydrofuran, dichloromethane, hexane, and the like. Among these, it is preferable to use an organic solvent from the viewpoint that the organic acid salt tends to dissolve more easily. As such a solvent, one kind may be used alone or two or more kinds may be used in combination, a resin solution containing a resin may be used, and additives such as an antioxidant and a plasticizer may be used. Furthermore, you may contain.
本発明の発光性ＥｕＩＩＩ錯塩において、トリスβ−ジケトナトＥｕＩＩＩ錯体に対して配位する有機酸アニオンは１モル当量であるが、本発明においては、トリスβ−ジケトナトＥｕＩＩＩ錯体に対して有機酸アニオンを過剰に添加することも可能である。このような有機酸アニオンのトリスβ−ジケトナトＥｕＩＩＩ錯体に対する添加量としては、０．９〜４．０モル当量であることが好ましい。有機酸アニオンの添加量が前記下限未満では、発光性ＥｕＩＩＩ錯塩の発光強度が低下する傾向にあり、他方、前記上限を超えると、例えば、有機酸塩とトリスβ−ジケトナトＥｕＩＩＩ錯体とを樹脂溶液中で混合して本発明の発光性ＥｕＩＩＩ錯塩を得る場合、錯塩を形成しない有機酸塩の濃度が高くなって樹脂の透明性や樹脂強度等に悪影響を及ぼす傾向にある。 In the luminescent Eu III complex salt of the present invention, the organic acid anion coordinated with respect to the tris β-diketonato Eu III complex is 1 molar equivalent, but in the present invention, the organic acid anion is organic with respect to the tris β-diketonato Eu III complex. It is also possible to add an acid anion in excess. The amount of such organic acid anions added to the tris β-diketonato Eu III complex is preferably 0.9 to 4.0 molar equivalents. When the addition amount of the organic acid anion is less than the lower limit, the emission intensity of the luminescent Eu III complex salt tends to decrease. On the other hand, when the upper limit is exceeded, for example, an organic acid salt and a tris β-diketonato Eu III complex are added. When mixed in a resin solution to obtain the light-emitting Eu III complex salt of the present invention, the concentration of the organic acid salt that does not form a complex salt tends to increase, and the transparency and resin strength of the resin tend to be adversely affected.
本発明の発光性ＥｕＩＩＩ錯塩において、前記第４級アンモニウムカチオンの添加量としては、発光性ＥｕＩＩＩ錯塩の樹脂や有機溶媒等の有機媒体に対する相溶性がより向上するという観点から、第４級アンモニウムカチオンがモノカチオンである場合には前記有機酸アニオンに対して０．５〜１．５モル当量であることが好ましい。 In the luminescent Eu III complex salt of the present invention, the addition amount of the quaternary ammonium cation is quaternary from the viewpoint that the compatibility of the luminescent Eu III complex salt with an organic medium such as a resin or an organic solvent is further improved. When the ammonium cation is a monocation, it is preferably 0.5 to 1.5 molar equivalents relative to the organic acid anion.
次に、本発明の発光増強剤について説明する。本発明の発光増強剤は、有機酸アニオンと第４級アンモニウムカチオンとを含有し、且つ、前記有機酸アニオンが下記一般式（１）〜（３）： Next, the light emission enhancer of the present invention will be described. The light emission enhancer of the present invention contains an organic acid anion and a quaternary ammonium cation, and the organic acid anion is represented by the following general formulas (1) to (3):
［式（１）中、Ｒ１、Ｒ２は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (1), R 1 and R 2 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（２）中、Ｒ３、Ｒ４は、同一でも異なっていてもよく、それぞれ炭素数４〜１０の脂肪族炭化水素基を示す。］ [In Formula (2), R 3 and R 4 may be the same or different and each represents an aliphatic hydrocarbon group having 4 to 10 carbon atoms. ]
［式（３）中、Ｒ５は、水素原子又は炭素数１〜４の炭化水素基を示す。］
で表わされる有機酸アニオンのうちの少なくとも１種であることを特徴とするものである。本発明の発光増強剤は前記トリスβ−ジケトナトＥｕＩＩＩ錯体と前記本発明のＥｕＩＩＩ錯塩を形成することにより、トリスβ−ジケトナトＥｕＩＩＩ錯体の発光強度を高める。
[In formula (3), R 5 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. ]
It is at least 1 sort (s) among the organic acid anions represented by these. The luminescence enhancer of the present invention enhances the luminescence intensity of the tris β-diketonato Eu III complex by forming the Tris β-diketonato Eu III complex and the Eu III complex salt of the present invention.
本発明にかかる有機酸アニオン及び第４級アンモニウムカチオンとしては、前記本発明の発光性ＥｕＩＩＩ錯塩において有機酸アニオン及び第４級アンモニウムカチオンとして挙げたものと同様のものをそれぞれ用いることができる。 As the organic acid anion and quaternary ammonium cation according to the present invention, those similar to those exemplified as the organic acid anion and quaternary ammonium cation in the luminescent Eu III complex of the present invention can be used.
本発明の発光増強剤としては、前記有機酸アニオンと前記第４級アンモニウムカチオンとを含有していればよく、特に制限されないが、前記有機酸アニオンと前記第４級アンモニウムカチオンとからなる有機酸塩を含有していることが好ましい。発光増強剤がこのような有機酸塩を含有している場合には、各種有機溶媒や樹脂に対する相溶性がより優れる傾向にあり、また、有機酸塩は難揮発性の塩であるため加熱による昇華が起こりにくくなる傾向にある。そのため、例えばトリスβ−ジケトナトＥｕＩＩＩ錯体及び本発明の発光増強剤を含有する発光素子を製造する場合、発光性ＥｕＩＩＩ錯塩の単離等の工程を要することなく、トリスβ−ジケトナトＥｕＩＩＩ錯体及び本発明の発光増強剤を樹脂溶液中で混合することで容易に発光強度が高い発光性ＥｕＩＩＩ錯塩を得ることができ、また、前記有機酸塩はブリードアウトしにくく、トリスβ−ジケトナトＥｕＩＩＩ錯体に対して過剰に添加することもできるため厳密な添加量の制御が不要となる。よって、発光素子の製造工程を簡略化することができる。 The light emission enhancer of the present invention is not particularly limited as long as it contains the organic acid anion and the quaternary ammonium cation, but is an organic acid composed of the organic acid anion and the quaternary ammonium cation. It preferably contains a salt. When the luminescence enhancer contains such an organic acid salt, it tends to be more compatible with various organic solvents and resins, and since the organic acid salt is a hardly volatile salt, There is a tendency that sublimation hardly occurs. Therefore, for example, when producing a light-emitting device containing the tris β-diketonato Eu III complex and the light emission enhancer of the present invention, the tris β-diketonato Eu III complex is not required, without requiring steps such as isolation of the luminescent Eu III complex salt. And a luminescent Eu III complex salt having a high luminescence intensity can be easily obtained by mixing the luminescence enhancer of the present invention in a resin solution, and the organic acid salt hardly bleeds out, and tris β-diketonato Eu. Since it can be added excessively with respect to the III complex, it is not necessary to strictly control the addition amount. Therefore, the manufacturing process of the light emitting element can be simplified.
このような有機酸塩としては、固体状であっても液体状であってもよく、有機溶媒に溶解していてもよい。前記有機溶媒としては、メタノール、アセトン、酢酸エチル、アセトニトリル、テトラヒドロフラン、ジクロロメタン、ヘキサン等が挙げられる。 Such an organic acid salt may be solid or liquid, and may be dissolved in an organic solvent. Examples of the organic solvent include methanol, acetone, ethyl acetate, acetonitrile, tetrahydrofuran, dichloromethane, hexane and the like.
本発明の発光増強剤の製造方法としては、特に制限されず、例えば、前記本発明の発光性ＥｕＩＩＩ錯塩において有機酸塩を合成する方法として挙げた方法と同様の方法を用いることができる。本発明の発光増強剤において、有機酸アニオンに対する第４級アンモニウムカチオンの添加量としては、前記本発明の発光性ＥｕＩＩＩ錯塩において述べたとおりである。 The method for producing the light emission enhancer of the present invention is not particularly limited, and for example, the same method as the method exemplified for synthesizing the organic acid salt in the light emitting Eu III complex salt of the present invention can be used. In the light emission enhancer of the present invention, the addition amount of the quaternary ammonium cation with respect to the organic acid anion is as described in the light emitting Eu III complex salt of the present invention.
次に、本発明の発光素子について説明する。本発明の発光素子は、前記本発明の発光性ＥｕＩＩＩ錯塩を含有する発光層を備えることを特徴とするものである。このような高い発光強度と優れた有機媒体への相溶性とを有する本発明の発光性ＥｕＩＩＩ錯塩を含有することにより、本発明の発光素子は高い発光強度を有すると共に透明性の高い優れた外観を有する。 Next, the light emitting device of the present invention will be described. The light emitting device of the present invention comprises a light emitting layer containing the light emitting Eu III complex salt of the present invention. By containing the luminescent Eu III complex salt of the present invention having such a high light emission intensity and excellent compatibility with an organic medium, the light emitting device of the present invention has high light emission intensity and excellent transparency. Appearance.
前記発光層は、前記本発明の発光性ＥｕＩＩＩ錯塩と基材としての透明な樹脂とを含有する。このような樹脂としては、例えば、ポリオレフィン樹脂、塩素含有ビニル樹脂、（メタ）アクリル樹脂、スチレン樹脂、ポリアミド樹脂、ポリイミド樹脂、ポリエステル樹脂、ポリウレタン樹脂、ポリアセタール樹脂、エポキシ樹脂、ポリビニルブチラール樹脂が挙げられる。前記ポリオレフィン樹脂としては、ポリエチレン、エチレン−α−オレフィン共重合体、酢酸ビニル樹脂、エチレン−酢酸ビニル共重合体、ポリプロピレン、プロピレン−α−オレフィン共重合体等が挙げられる。前記塩素含有ビニル樹脂としては、ポリ塩化ビニル、ポリ塩化ビニリデン等が挙げられる。前記（メタ）アクリル樹脂としては、（メタ）アクリル酸、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸２−エチルヘキシル及びこれらの重合体又は共重合体等が挙げられる。前記スチレン樹脂としては、ポリスチレン、ＡＳ樹脂、ＡＢＳ樹脂等が挙げられる。前記ポリアミド樹脂としては、ナイロン６、ナイロン６６等が挙げられる。前記ポリエステル樹脂としては、ＰＥＴ樹脂、ＰＥＮ樹脂、ポリカーボネート樹脂等が挙げられる。これらの樹脂の中でも、より透明性が優れる傾向にあるという観点並びに工業的な量産性、耐久性、コスト及び加工適性の観点から、ポリオレフィン樹脂、ポリ塩化ビニル、(メタ)アクリル樹脂、ポリスチレン、エポキシ樹脂、ボリビニルブチラール樹脂を用いることが好ましい。 The light emitting layer contains the light emitting Eu III complex salt of the present invention and a transparent resin as a substrate. Examples of such resins include polyolefin resins, chlorine-containing vinyl resins, (meth) acrylic resins, styrene resins, polyamide resins, polyimide resins, polyester resins, polyurethane resins, polyacetal resins, epoxy resins, and polyvinyl butyral resins. . Examples of the polyolefin resin include polyethylene, ethylene-α-olefin copolymer, vinyl acetate resin, ethylene-vinyl acetate copolymer, polypropylene, propylene-α-olefin copolymer, and the like. Examples of the chlorine-containing vinyl resin include polyvinyl chloride and polyvinylidene chloride. Examples of the (meth) acrylic resin include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and polymers or copolymers thereof. . Examples of the styrene resin include polystyrene, AS resin, ABS resin, and the like. Examples of the polyamide resin include nylon 6, nylon 66, and the like. Examples of the polyester resin include PET resin, PEN resin, and polycarbonate resin. Among these resins, polyolefin resin, polyvinyl chloride, (meth) acrylic resin, polystyrene, epoxy, from the viewpoint that transparency tends to be superior and industrial mass productivity, durability, cost, and processability. It is preferable to use a resin or a poly vinyl butyral resin.
本発明にかかる発光層において、前記発光性ＥｕＩＩＩ錯塩の含有量は特に制限されないが、前記樹脂に対して０．１〜１０質量％であることが好ましい。発光性ＥｕＩＩＩ錯塩の割合が前記下限未満では、発光素子の発光強度が十分に得られない傾向にあり、他方、前記上限を超えると、発光性ＥｕＩＩＩ錯塩がブリードアウトする傾向にある。 In the light emitting layer according to the present invention, the content of the light emitting Eu III complex salt is not particularly limited, but is preferably 0.1 to 10% by mass with respect to the resin. When the ratio of the luminescent Eu III complex salt is less than the lower limit, the luminescence intensity of the light emitting element tends not to be sufficiently obtained. On the other hand, when the ratio exceeds the upper limit, the luminescent Eu III complex salt tends to bleed out.
本発明にかかる発光層としては、前記樹脂及び前記発光性ＥｕＩＩＩ錯塩の他にさらに酸化防止剤、可塑剤等の添加剤を含有していてもよい。また、本発明の発光素子の構造としては、特に制限されず、本発明にかかる発光層を備えていればよく、公知の発光素子の構造を適宜採用することができる。 The light emitting layer according to the present invention may further contain additives such as an antioxidant and a plasticizer in addition to the resin and the light emitting Eu III complex salt. Further, the structure of the light-emitting element of the present invention is not particularly limited, and the light-emitting layer according to the present invention may be provided, and a known light-emitting element structure can be appropriately employed.
本発明の発光素子の製造方法としては、特に制限されず、例えば、前記トリスβ−ジケトナトＥｕＩＩＩ錯体と、前記有機酸アニオン及び前記第４級アンモニウムカチオンからなる有機酸塩と、前記樹脂とを溶媒中で混合して溶解せしめ、得られた組成物を成形して発光層を形成し、本発明の発光素子を得る方法が挙げられる。 The method for producing the light emitting device of the present invention is not particularly limited, and for example, the tris β-diketonato Eu III complex, the organic acid anion comprising the organic acid anion and the quaternary ammonium cation, and the resin. A method of obtaining the light emitting device of the present invention by mixing and dissolving in a solvent, molding the obtained composition to form a light emitting layer, and the like can be mentioned.
前記溶媒としては、前記本発明の発光性ＥｕＩＩＩ錯塩の製造方法において有機酸塩とトリスβ−ジケトナトＥｕＩＩＩ錯体とを混合する際に用いる有機溶媒として挙げたものと同様のものを用いることができ、混合方法としては、前述のとおりである。また、前記成形方法としては、特に制限されず、公知の方法を適宜採用することができる。 As the solvent, the same solvents as those mentioned as the organic solvent used when mixing the organic acid salt and the tris β-diketonato Eu III complex in the method for producing a luminescent Eu III complex of the present invention may be used. The mixing method is as described above. In addition, the molding method is not particularly limited, and a known method can be appropriately employed.
以下、実施例及び比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。 EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example.
＜ベンジルジメチルドデシルアンモニウムジ（２−エチルヘキシル）スルホコハク酸（ＢｚＢＥＨＳ）の合成＞
塩化ベンジルジメチルドデシルアンモニウム０．０２ｍｏｌ（６．８ｇ）とジ（２−エチルヘキシル）スルホコハク酸ナトリウム０．０２ｍｏｌ（８．８９ｇ）とを容量２００ｍｌのビーカーの中でアセトン２５ｍｌと純水２５ｍｌとの混合溶媒に溶解せしめて混合溶液（反応液）を得た。得られた反応液を大気中にて室温（２５℃）で７日間放置して水相と油相とに分相せしめ、次いで、６０℃の熱風乾燥炉中で４時間放置してアセトンを完全に揮発せしめた後、分液ロートで水相を除去して油相を得た。得られた油相を純水１００ｍｌで３回洗浄した後に減圧下（約４０ｍｍＨｇ）、９０℃で４時間減圧乾燥を施し液状化合物としてＢｚＢＥＨＳを得た。収率は９５質量％であった。
<Synthesis of benzyldimethyldodecylammonium di (2-ethylhexyl) sulfosuccinate (BzBEHS)>
A mixed solvent of 25 ml of acetone and 25 ml of pure water in a beaker having a capacity of 200 ml containing 0.02 mol (6.8 g) of benzyldimethyldodecylammonium chloride and 0.02 mol (8.89 g) of sodium di (2-ethylhexyl) sulfosuccinate To obtain a mixed solution (reaction solution). The obtained reaction solution was allowed to stand in the atmosphere at room temperature (25 ° C.) for 7 days to separate into an aqueous phase and an oil phase, and then left in a hot air drying oven at 60 ° C. for 4 hours to completely remove acetone. Then, the water phase was removed with a separatory funnel to obtain an oil phase. The obtained oil phase was washed with 100 ml of pure water three times and then dried under reduced pressure (about 40 mmHg) at 90 ° C. for 4 hours to obtain BzBEHS as a liquid compound. The yield was 95% by mass.
＜べンジルジメチルドデシルアンモニウムベンゾトリアゾール（ＢｚＢＴＡ）の
合成＞
塩化べンジルジメチルドデシルアンモニウム０．２ｍｏｌ（６０．８ｇ）、１Ｈ−べンゾトリアゾール０．２ｍｏｌ（２３．６ｇ）及び水酸化ナトリウム０．２ｍｏｌ（８ｇ）を純水５００ｍｌに加えた混合溶液（反応液）を固形分が認められなくなるまで７０℃で加熱しながら攪拌した。攪拌を停止して反応液を油相と水相とに分相せしめ、室温に冷却して固体状の油相を得た。この固体状の油相を取り出し、８０℃で２４時間乾燥した後に１００ｍｌのヘキサンに溶解してから室温に冷却しＢｚＢＴＡの結晶を得た。収率は９６質量％であった。
<Synthesis of benzyldimethyldodecylammonium benzotriazole (BzBTA)>
Benzyldimethyldodecylammonium chloride 0.2 mol (60.8 g), 1H-benzotriazole 0.2 mol (23.6 g) and sodium hydroxide 0.2 mol (8 g) added to 500 ml of pure water ( The reaction solution was stirred while heating at 70 ° C. until no solid content was observed. Stirring was stopped, the reaction solution was separated into an oil phase and an aqueous phase, and cooled to room temperature to obtain a solid oil phase. The solid oil phase was taken out, dried at 80 ° C. for 24 hours, dissolved in 100 ml of hexane, and then cooled to room temperature to obtain BzBTA crystals. The yield was 96% by mass.
＜ベンジルジメチルドデシルアンモニウムジ（２−エチルヘキシル）リン酸（ＢｚＢＥＨＰ）の合成＞
臭化ベンジルジメチルドデシルアンモニウム０．２ｍｏｌ（７６．９ｇ）とジ（２−エチルヘキシル）リン酸０．２ｍｏｌ（６４．４ｇ）とを容量５００ｍｌのビーカーの中で混合・攪拌した後、１ｍｏｌ／ｌの炭酸ナトリウム水溶液２００ｍｌを攪拌しながら少量ずつ添加した。得られた混合溶液（反応液）を大気中にて温度２５℃で１日間放置して水相と油相とに分相せしめ、分液ロートで水相を除去して油相を得た。得られた油相を１ｍｏｌ／ｌの炭酸ナトリウム水溶液２００ｍｌで洗い、次いで、純水２００ｍｌで３回洗浄した後に減圧下（約４０ｍｍＨｇ）、９０℃で４時間減圧乾燥を施し液状化合物としてＢｚＢＥＨＰを得た。収率は９３質量％であった。
<Synthesis of benzyldimethyldodecylammonium di (2-ethylhexyl) phosphate (BzBEHP)>
After mixing and stirring 0.2 mol (76.9 g) of benzyldimethyldodecylammonium bromide and 0.2 mol (64.4 g) of di (2-ethylhexyl) phosphoric acid in a 500 ml beaker, 1 mol /
＜テトラオクチルアンモニウムべンゾトリアゾール（ＴＯＡＢＴＡ）の合成＞
臭化テトラオクチルアンモニウム０．２ｍｏｌ（１０９．２ｇ）、１Ｈ−べンゾトリアゾール０．２ｍｏｌ（２３．６ｇ）及び水酸化ナトリウム０．２ｍｏｌ（８ｇ）を純水５００ｍｌに加えた混合溶液（反応液）を固形分が認められなくなるまで７０℃で加熱しながら攪拌した。攪拌を停止して反応液を油相と水相とに分相せしめ、分液ロートで水相を除去して油相を得た。得られた油相を１ｍｏｌ／ｌの炭酸ナトリウム水溶液５００ｍｌで洗い、次いで、純水５００ｍｌで３回洗浄した後に減圧下（約４０ｍｍＨｇ）、９０℃で４時間減圧乾燥を施し高粘度液状化合物としてＴＯＡＢＴＡを得た。収率は９５質量％であった。
<Synthesis of Tetraoctylammonium Benzotriazole (TOABTA)>
Tetraoctylammonium bromide 0.2 mol (109.2 g), 1H-benzotriazole 0.2 mol (23.6 g) and sodium hydroxide 0.2 mol (8 g) added to 500 ml of pure water (reaction solution) ) Was stirred while heating at 70 ° C. until no solid content was observed. Stirring was stopped, the reaction solution was separated into an oil phase and an aqueous phase, and the aqueous phase was removed with a separatory funnel to obtain an oil phase. The obtained oil phase was washed with 500 ml of a 1 mol / l aqueous sodium carbonate solution, then washed with 500 ml of pure water three times, and then dried under reduced pressure (about 40 mmHg) at 90 ° C. for 4 hours to form TOABTA as a highly viscous liquid compound. Got. The yield was 95% by mass.
＜テトラオクチルアンモニウムジ（２−エチルヘキシル）リン酸（ＴＯＡＢＥＨＰ）の合成＞
１Ｈ−べンゾトリアゾールの代わりにジ（２−エチルヘキシル）リン酸０．２ｍｏｌ（６４．４ｇ）を用い、水酸化ナトリウムを用いなかったこと以外はＴＯＡＢＴＡの合成と同様にして高粘度液状化合物としてＴＯＡＢＥＨＰを得た。収率は９２質量％であった。
<Synthesis of tetraoctylammonium di (2-ethylhexyl) phosphate (TOABEHP)>
A high-viscosity liquid compound was prepared in the same manner as TOABTA except that 0.2 mol (64.4 g) of di (2-ethylhexyl) phosphoric acid was used instead of 1H-benzotriazole and sodium hydroxide was not used. TOABEHP was obtained. The yield was 92% by mass.
＜トリオクチルメチルアンモニウムベンゾトリアゾール（ＴＯＭＡＢＴＡ）の合成＞
臭化テトラオクチルアンモニウムの代わりに臭化トリオクチルメチルアンモニウム０．２ｍｏｌ（８９．６ｇ）を用いたこと以外はＴＯＡＢＴＡの合成と同様にして高粘度液状化合物としてＴＯＭＡＢＴＡを得た。収率は９６質量％であった。
<Synthesis of trioctylmethylammonium benzotriazole (TOMABTA)>
TOMABTA was obtained as a high-viscosity liquid compound in the same manner as in the synthesis of TOABTA except that 0.2 mol (89.6 g) of trioctylmethylammonium bromide was used instead of tetraoctylammonium bromide. The yield was 96% by mass.
＜ナトリウムべンゾトリアゾール（ＮａＢＴＡ）の合成＞
１Ｈ−べンゾトリアゾール０．０５ｍｏｌ（６ｇ）と水酸化ナトリウム０．０５ｍｏｌ（２ｇ）を純水１０ｍｌに加え、約１８ｍｌの混合溶液（反応液）を得た。得られた反応液を固形分が認められなくなるまで７０℃で加熱しながら攪拌し、反応液の体積が約１０ｍｌになるまで加熱・攪拌を続けた。その後、反応液を室温で冷却し、１０ｍｌのアセトンを加えて得られた白色沈殿をろ過して室温で放置、乾燥せしめ、ＮａＢＴＡ３．６ｇを得た。
<Synthesis of sodium benzotriazole (NaBTA)>
0.05 mol (6 g) of 1H-benzotriazole and 0.05 mol (2 g) of sodium hydroxide were added to 10 ml of pure water to obtain about 18 ml of a mixed solution (reaction solution). The resulting reaction solution was stirred while being heated at 70 ° C. until no solid content was observed, and heating and stirring were continued until the volume of the reaction solution reached about 10 ml. Thereafter, the reaction solution was cooled at room temperature, 10 ml of acetone was added, and the resulting white precipitate was filtered, allowed to stand at room temperature and dried to obtain 3.6 g of NaBTA.
＜スペクトルの測定方法＞
励起スペクトル及び発光スペクトルは、日立Ｆ−４５００型分光発光光度計を用いて測定した。１ｃｍ角の石英製分光セルを用い、励起側のスリット幅を２．５ｍｍ、発光側のスリット幅を１．０ｍｍとした。各実施例及び比較例における励起スペクトルは検出波長を６１２ｎｍとし、励起光波長を２５０〜４５０ｎｍの範囲で変化させて記録した。発光スペクトルは励起波長を３３０ｎｍとし、発光波長が４５０〜７００ｎｍの範囲で記録し、発光スペクトルのピーク強度を測定した。なお、各測定毎にローダミン１０１のエタノール溶液（塩酸０．１％）を用いて発光スペクトルを測定し、スペクトル強度の変化がないことを確認しているため、各実施例及び比較例において励起スペクトル及び発光スペクトルの量子化率の補正は行っていない。
<Spectrum measurement method>
The excitation spectrum and emission spectrum were measured using a Hitachi F-4500 type spectrophotometer. A 1 cm square quartz spectroscopic cell was used, the slit width on the excitation side was 2.5 mm, and the slit width on the light emission side was 1.0 mm. The excitation spectra in each example and comparative example were recorded with a detection wavelength of 612 nm and the excitation light wavelength varied in the range of 250 to 450 nm. The emission spectrum was recorded with an excitation wavelength of 330 nm and an emission wavelength in the range of 450 to 700 nm, and the peak intensity of the emission spectrum was measured. In addition, since the emission spectrum was measured using an ethanol solution of rhodamine 101 (hydrochloric acid 0.1%) for each measurement and it was confirmed that there was no change in the spectrum intensity, the excitation spectrum in each example and comparative example. In addition, the quantization rate of the emission spectrum is not corrected.
（実施例１）
ユーロピウム（ＩＩＩ）１，１，１，２，２，３，３−ヘプタフルオロ−７，７−ジメチル−４，６−オクタンジオネート（［Ｅｕ（ＦＯＤ）３］）（アヅマックス（株）製）の酢酸エチル溶液にＢｚＢＥＨＳを添加し、［Ｅｕ（ＦＯＤ）３］濃度が０．２ｍｍｏｌ／ｌ、ＢｚＢＥＨＳ濃度が０．２ｍｍｏｌ／ｌの発光性ＥｕＩＩＩ錯塩の酢酸エチル溶液を得た。また、前記酢酸エチル溶液に代えてそれぞれアセトニトリル、テトラヒドロフラン、ジクロロメタン、ヘキサンを用いたこと以外は前記発光性ＥｕＩＩＩ錯塩の酢酸エチル溶液と同様にして発光性ＥｕＩＩＩ錯塩の各溶液をそれぞれ得た。
Example 1
Europium (III) 1,1,1,2,2,3,3-heptafluoro-7,7-dimethyl-4,6-octanedionate ([Eu (FOD) 3 ]) (manufactured by Amax Co., Ltd.) BzBEHS was added to an ethyl acetate solution to obtain an ethyl acetate solution of a luminescent Eu III complex salt having a [Eu (FOD) 3 ] concentration of 0.2 mmol / l and a BzBEHS concentration of 0.2 mmol / l. Moreover, each solution of the luminescent Eu III complex salt was obtained in the same manner as the ethyl acetate solution of the luminescent Eu III complex except that acetonitrile, tetrahydrofuran, dichloromethane and hexane were used in place of the ethyl acetate solution, respectively.
（実施例２）
ＢｚＢＥＨＳに代えてＢｚＢＴＡを用いたこと以外は実施例１と同様にして発光性ＥｕＩＩＩ錯塩の各溶液をそれぞれ得た。
(Example 2)
Each solution of the luminescent Eu III complex salt was obtained in the same manner as in Example 1 except that BzBTA was used instead of BzBEHS.
（実施例３）
ＢｚＢＥＨＳに代えてＢｚＢＥＨＰを用いたこと以外は実施例１と同様にして発光性ＥｕＩＩＩ錯塩の各溶液をそれぞれ得た。
(Example 3)
Each solution of the luminescent Eu III complex salt was obtained in the same manner as in Example 1 except that BzBEHP was used instead of BzBEHS.
（実施例４）
ＢｚＢＥＨＳに代えてＴＯＡＢＴＡを用いたこと以外は実施例１と同様にして発光性ＥｕＩＩＩ錯塩の各溶液をそれぞれ得た。
Example 4
Each solution of luminescent Eu III complex salt was obtained in the same manner as in Example 1 except that TOABTA was used instead of BzBEHS.
（実施例５）
ＢｚＢＥＨＳに代えてＴＯＡＢＥＨＰを用いたこと以外は実施例１と同様にして発光性ＥｕＩＩＩ錯塩の酢酸エチル溶液を得た。
(Example 5)
A luminescent Eu III complex ethyl acetate solution was obtained in the same manner as in Example 1 except that TOABEHP was used instead of BzBEHS.
（実施例６）
ＢｚＢＥＨＳに代えてＴＯＭＡＢＴＡを用いたこと以外は実施例１と同様にして発光性ＥｕＩＩＩ錯塩の酢酸エチル溶液を得た。
(Example 6)
A luminescent Eu III complex ethyl acetate solution was obtained in the same manner as in Example 1 except that TOMABTA was used instead of BzBEHS.
（比較例１）
ＢｚＢＥＨＳを加えなかったこと以外は実施例１と同様にしてＥｕＩＩＩ錯体の各溶液をそれぞれ得た。
(Comparative Example 1)
Each solution of Eu III complex was obtained in the same manner as in Example 1 except that BzBEHS was not added.
（比較例２）
ＢｚＢＥＨＳに代えてジメチルスルホキシド（ＤＭＳＯ）を用いたこと以外は実施例１と同様にしてＤＭＳＯの濃度が０．４ｍｍｏｌ／ｌのＥｕＩＩＩ錯体の各溶液をそれぞれ得た。
(Comparative Example 2)
Each solution of Eu III complex having a DMSO concentration of 0.4 mmol / l was obtained in the same manner as in Example 1 except that dimethyl sulfoxide (DMSO) was used instead of BzBEHS.
（比較例３）
ＢｚＢＥＨＳに代えてトリオクチルホスフィンオキシド（ＴＯＰＯ）を用いたこと以外は実施例１と同様にしてＴＯＰＯの濃度が０．４ｍｍｏｌ／ｌのＥｕＩＩＩ錯体の各溶液をそれぞれ得た。
(Comparative Example 3)
Each solution of Eu III complex having a TOPO concentration of 0.4 mmol / l was obtained in the same manner as in Example 1 except that trioctylphosphine oxide (TOPO) was used instead of BzBEHS.
（比較例４）
ＢｚＢＥＨＳに代えてＮａＢＴＡを用いたこと以外は実施例１と同様にしてＥｕＩＩＩ錯塩の酢酸エチル溶液を得ようとしたが、ＮａＢＴＡが酢酸エチルに溶けなかったため、得ることができなかった。
(Comparative Example 4)
An attempt was made to obtain an ethyl acetate solution of Eu III complex salt in the same manner as in Example 1 except that NaBTA was used in place of BzBEHS, but this could not be obtained because NaBTA did not dissolve in ethyl acetate.
＜発光スペクトル特性の評価＞
実施例１〜６及び比較例１〜４で得られた溶液について、励起スペクトル及び発光スペクトルを測定した。得られた発光スペクトルのピーク強度を表１に示す。また、図１に実施例１〜３で得られたＥｕＩＩＩ錯塩、図２に比較例１で得られたＥｕＩＩＩ錯体、図３に比較例２で得られたＥｕＩＩＩ錯体の各酢酸エチル溶液の励起スペクトル及び発光スペクトルをそれぞれ示す。図１〜３において、左図は励起スペクトルを示し、右図は発光スペクトルを示す。
<Evaluation of emission spectrum characteristics>
Excitation spectra and emission spectra were measured for the solutions obtained in Examples 1 to 6 and Comparative Examples 1 to 4. The peak intensity of the obtained emission spectrum is shown in Table 1. Further, FIG. 1 shows an Eu III complex salt obtained in Examples 1 to 3, FIG. 2 shows an Eu III complex obtained in Comparative Example 1, and FIG. 3 shows an ethyl acetate solution of Eu III complex obtained in Comparative Example 2. Excitation spectrum and emission spectrum of are respectively shown. 1-3, the left figure shows an excitation spectrum, and the right figure shows an emission spectrum.
励起スペクトル及び発光スペクトルの測定では、全ての溶媒において、ＢｚＢＥＨＳ（図１、実施例１）、ＢｚＢＴＡ（図１、実施例２）、ＢｚＢＥＨＰ（図１、実施例３）、ＴＯＡＢＴＡ（実施例４）、ＴＯＡＢＥＨＰ（実施例５）、ＴＯＭＡＢＴＡ（実施例６）、ＤＭＳＯ（図３、比較例２）及びＴＯＰＯ（比較例３）をそれぞれ［Ｅｕ（ＦＯＤ）３］に添加しても励起スペクトル及び発光スペクトルのピーク波長はこれらを添加する前の［Ｅｕ（ＦＯＤ）３］溶液の波長（図２、比較例１）と比べて変化しないことが確認された。また、表１に示した結果から明らかなように、本発明の発光性ＥｕＩＩＩ錯塩（実施例１〜６）は、酢酸エチル、アセトニトリル、テトラヒドロフラン、ジクロロメタン、ヘキサンに溶け、トリスβ−ジケトナトＥｕＩＩＩ錯体である［Ｅｕ（ＦＯＤ）３］（比較例１）よりも高い発光強度を有することが確認された。一方、対カチオンがナトリウムであるＥｕＩＩＩ錯塩（比較例４）は酢酸エチルには溶けず、有機媒体への相溶性が劣ることが確認された。また、ＢＴＡ−、ＢＥＨＰ−を含む有機酸塩をトリスβ−ジケトナトＥｕＩＩＩ錯体に添加して得られた発光性ＥｕＩＩＩ錯塩（実施例２〜６）はほとんどの溶媒中で高い発光強度を示した。一方、従来の中性配位子であるＤＭＳＯや、同じく中性配位子であるＴＯＰＯを配位子として有するＥｕＩＩＩ錯体（比較例２〜３）は発光強度が劣るものがほとんどであった。 In the measurement of excitation spectrum and emission spectrum, BzBEHS (FIG. 1, Example 1), BzBTA (FIG. 1, Example 2), BzBEHP (FIG. 1, Example 3), TOABTA (Example 4) were used in all solvents. , TOABEHP (Example 5), TOMABTA (Example 6), DMSO (FIG. 3, Comparative Example 2) and TOPO (Comparative Example 3) are added to [Eu (FOD) 3 ], respectively, and the excitation spectrum and emission spectrum It was confirmed that the peak wavelength of γ was not changed compared to the wavelength of the [Eu (FOD) 3 ] solution before adding these (FIG. 2, Comparative Example 1). As is clear from the results shown in Table 1, the luminescent Eu III complex salts (Examples 1 to 6) of the present invention were dissolved in ethyl acetate, acetonitrile, tetrahydrofuran, dichloromethane and hexane, and tris β-diketonato Eu III. It was confirmed that the light emission intensity was higher than that of the complex [Eu (FOD) 3 ] (Comparative Example 1). On the other hand, Eu III complex salt (Comparative Example 4) whose counter cation is sodium was not soluble in ethyl acetate, and it was confirmed that the compatibility with an organic medium was inferior. Further, the luminescent Eu III complex salts (Examples 2 to 6) obtained by adding organic acid salts containing BTA − and BEHP − to the tris β-diketonato Eu III complex show high emission intensity in most solvents. It was. On the other hand, most of Eu III complexes (Comparative Examples 2 to 3) having DMSO, which is a conventional neutral ligand, and TOPO, which is also a neutral ligand, as ligands have low emission intensity. .
＜トリスβ−ジケトナトＥｕＩＩＩ錯体に対する有機酸アニオンの添加量の評価＞
（実施例７）
［Ｅｕ（ＦＯＤ）３］のヘキサン溶液にＢｚＢＥＨＳを添加し、［Ｅｕ（ＦＯＤ）３］濃度が０．２ｍｍｏｌ／ｌ、ＢｚＢＥＨＳ濃度が４０、８０、１２０、１６０、２００、２４０、２８０、３２０、３６０μｍｏｌ／ｌの発光性ＥｕＩＩＩ錯塩のヘキサン溶液を得た。
<Evaluation of Addition Amount of Organic Acid Anion to Tris β-Diketonato Eu III Complex>
(Example 7)
[Eu (FOD) 3] was added BzBEHS in hexane, [Eu (FOD) 3] concentration 0.2mmol / l, BzBEHS concentration 40,80,120,160,200,240,280,320, A hexane solution of 360 μmol / l luminescent Eu III complex salt was obtained.
（実施例８）
ヘキサンに代えて酢酸エチル、ＢｚＢＥＨＳに代えてＢｚＢＥＨＰを用いたこと以外は実施例７と同様にして発光性ＥｕＩＩＩ錯塩の溶液を得た。
(Example 8)
A luminescent Eu III complex salt solution was obtained in the same manner as in Example 7 except that ethyl acetate was used instead of hexane and BzBEHP was used instead of BzBEHS.
（実施例９）
ヘキサンに代えて酢酸エチル、ＢｚＢＥＨＳに代えてＢｚＢＴＡを用いたこと以外は実施例７と同様にして発光性ＥｕＩＩＩ錯塩の溶液を得た。
Example 9
A luminescent Eu III complex salt solution was obtained in the same manner as in Example 7 except that ethyl acetate was used instead of hexane and BzBTA was used instead of BzBEHS.
実施例７〜９で得られた溶液について、各有機酸塩濃度における発光スペクトルを測定した。得られた結果を図４Ａ〜図４Ｃに示す。図４Ａ〜図４Ｃにおいて、発光スペクトルのピーク強度の値（Ｉｅｍ／Ｉｅｍ、０）は、発光スペクトルのピーク強度（Ｉｅｍ）と、［Ｅｕ（ＦＯＤ）３］濃度が０．２ｍｍｏｌ／ｌの有機酸を含まないヘキサン溶液の発光スペクトルのピーク強度（Ｉｅｍ、０）との比として示す。 About the solution obtained in Examples 7-9, the emission spectrum in each organic acid salt density | concentration was measured. The obtained results are shown in FIGS. 4A to 4C. In FIG. 4A to FIG. 4C, the peak intensity values (Iem / Iem, 0 ) of the emission spectrum are the peak intensity (Iem) of the emission spectrum and the organic acid having a [Eu (FOD) 3 ] concentration of 0.2 mmol / l. It is shown as a ratio with the peak intensity (Iem, 0 ) of the emission spectrum of a hexane solution containing no.
図４Ａ〜図４Ｃに示す結果から明らかなように、発光性ＥｕＩＩＩ錯塩の溶液において有機酸塩濃度が２００μｍｏｌ／ｌ付近でグラフが屈曲点示していることから、有機酸塩（Ｃ＋ＸＡ−）由来の本発明にかかる有機酸アニオン（ＸＡ−）とトリスβ−ジケトナトＥｕＩＩＩ錯体（［Ｅｕ（ＦＯＤ）３］）とが以下の反応式で示されるように１：１のモル比で反応していることが確認された。
反応式：［Ｅｕ（ＦＯＤ）３］＋Ｃ＋ＸＡ− → Ｃ＋＋［Ｅｕ（ＦＯＤ）３ＸＡ］−
また、これらの有機酸塩が［Ｅｕ（ＦＯＤ）３］に対して１モル当量を超えて過剰に添加されていても発光スペクトルのピーク強度がほとんど減少しないことから、有機酸塩を過剰に添加しても発光強度に悪影響を及ぼしにくいことが確認された。
As is clear from the results shown in FIGS. 4A to 4C, the organic acid salt (C + XA − is obtained by the graph showing the inflection point when the organic acid salt concentration is around 200 μmol / l in the luminescent Eu III complex salt solution. ) -Derived organic acid anion (XA − ) and tris β-diketonato Eu III complex ([Eu (FOD) 3 ]) are reacted at a molar ratio of 1: 1 as shown in the following reaction formula. It was confirmed that
Reaction formula: [Eu (FOD) 3 ] + C + XA − → C + + [Eu (FOD) 3 XA] −
Moreover, even if these organic acid salts are added excessively in excess of 1 molar equivalent with respect to [Eu (FOD) 3 ], the peak intensity of the emission spectrum is hardly reduced, so that organic acid salts are added excessively. Even in this case, it was confirmed that the light emission intensity was hardly adversely affected.
＜発光性ＥｕＩＩＩ錯塩の安定性評価＞
（実施例１０）
水とアセトニトリルとの混合比（質量比）が１：９である溶媒中に［Ｅｕ（ＦＯＤ）３］及びＢｚＢＴＡを添加し、［Ｅｕ（ＦＯＤ）３］濃度が０．２ｍｍｏｌ／ｌ、ＢｚＢＴＡ濃度が０．２ｍｍｏｌ／ｌである発光性ＥｕＩＩＩ錯塩の溶液を得た。
<Stability Evaluation of Luminescent Eu III Complex>
(Example 10)
[Eu (FOD) 3 ] and BzBTA are added to a solvent having a mixing ratio (mass ratio) of water and acetonitrile of 1: 9, the [Eu (FOD) 3 ] concentration is 0.2 mmol / l, and the BzBTA concentration is A solution of the luminescent Eu III complex salt having a valence of 0.2 mmol / l was obtained.
（比較例５）
ＢｚＢＴＡを加えなかったこと以外は実施例１０と同様にしてＥｕＩＩＩ錯体の溶液を得た。
(Comparative Example 5)
A solution of Eu III complex was obtained in the same manner as in Example 10 except that BzBTA was not added.
（比較例６）
ＢｚＢＴＡに代えてＴＯＰＯを用いたこと以外は実施例１０と同様にしてＥｕＩＩＩ錯体の溶液を得た。
(Comparative Example 6)
A solution of Eu III complex was obtained in the same manner as in Example 10 except that TOPO was used instead of BzBTA.
実施例１〜３で得られた溶液について、発光スペクトルを測定した後に空気中において室温で１カ月間放置し、再び発光スペクトルを測定して発光性ＥｕＩＩＩ錯塩の空気中における安定性を評価した。また、実施例１０及び比較例５〜６で得られた溶液について、発光スペクトルを測定した後に空気中において室温で１週間放置し、再び発光スペクトルを測定して水分を含む溶媒中での安定性を評価した。各評価は、先ず、それぞれの溶液について以下の式により発光スペクトルの維持率を算出した。
維持率＝１カ月間（又は１週間）放置後の発光スペクトルのピーク強度／放置前の発光スペクトルのピーク強度×１００
次いで、得られた各維持率を以下の評価基準に基づいて評価した。得られた結果をそれぞれ表２及び表３に示す。
（安定性の評価基準）
９５％以上：Ａ
５１〜９５％未満：Ｂ
５０％以下：Ｃ
The solutions obtained in Examples 1 to 3 were measured for emission spectra and then allowed to stand at room temperature for 1 month in the air. The emission spectra were measured again to evaluate the stability of the luminescent Eu III complex salt in the air. . Moreover, about the solution obtained in Example 10 and Comparative Examples 5-6, after measuring an emission spectrum, it was left to stand at room temperature in the air for 1 week, and the emission spectrum was measured again, and the stability in the solvent containing a water | moisture content was measured. Evaluated. In each evaluation, first, the retention rate of the emission spectrum was calculated for each solution by the following formula.
Maintenance rate = peak intensity of emission spectrum after standing for 1 month (or 1 week) / peak intensity of emission spectrum before standing × 100
Subsequently, each obtained maintenance rate was evaluated based on the following evaluation criteria. The obtained results are shown in Table 2 and Table 3, respectively.
(Stability evaluation criteria)
95% or more: A
51 to less than 95%: B
50% or less: C
表２に示す結果から明らかなように、本発明の発光性ＥｕＩＩＩ錯塩（実施例１〜３）は空気中で１ヶ月間放置しても安定性を維持できることが確認された。さらに、表３に示す結果から明らかなように、トリスβ−ジケトナトＥｕＩＩＩ錯体にＢｚＢＴＡを添加して得られた本発明の発光性ＥｕＩＩＩ錯塩（実施例１０）は水が混入した溶媒中でも安定性を維持できることが確認された。一方、トリスβ−ジケトナトＥｕＩＩＩ錯体のみ（比較例５）及び中性配位子であるＴＯＰＯを配位子として有するＥｕＩＩＩ錯体（比較例６）は水が混入した溶媒中で安定性を維持できないことが確認された。 As is clear from the results shown in Table 2, it was confirmed that the luminescent Eu III complex salts (Examples 1 to 3) of the present invention can maintain stability even when left in the air for one month. Further, as apparent from the results shown in Table 3, the luminescent Eu III complex salt of the present invention obtained by adding BzBTA to the tris β-diketonato Eu III complex (Example 10) is stable even in a solvent mixed with water. It was confirmed that the sex could be maintained. On the other hand, only the tris β-diketonato Eu III complex (Comparative Example 5) and the Eu III complex (Comparative Example 6) having the neutral ligand TOPO as a ligand maintain stability in a solvent mixed with water. It was confirmed that it was not possible.
＜樹脂中における発光特性及び相溶性の評価＞
（実施例１１）
ポリビニルブチラール（ＰＶＢ）０．４ｇと［Ｅｕ（ＦＯＤ）３］４ｍｇとをテトラヒドロフラン４０ｍｌに溶解せしめ、次いで、ＢｚＢＥＨＳ８ｍｇを添加して溶解せしめた。この溶液を内径７６ｍｍのシャーレに注ぎ、室温にて４時間乾燥後、さらに１２０℃にて３０分間乾燥せしめ、発光性ＥｕＩＩＩ錯塩を含むＰＶＢフィルムを得た。
<Evaluation of luminous characteristics and compatibility in resin>
(Example 11)
0.4 g of polyvinyl butyral (PVB) and 4 mg of [Eu (FOD) 3 ] were dissolved in 40 ml of tetrahydrofuran, and then 8 mg of BzBEHS was added and dissolved. This solution was poured into a petri dish having an inner diameter of 76 mm, dried at room temperature for 4 hours, and further dried at 120 ° C. for 30 minutes to obtain a PVB film containing a luminescent Eu III complex salt.
（実施例１２）
ＢｚＢＥＨＳに代えてＢｚＢＴＡを用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Example 12)
A PVB film was obtained in the same manner as in Example 11 except that BzBTA was used instead of BzBEHS.
（実施例１３）
ＢｚＢＥＨＳに代えてＢｚＢＥＨＰを用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Example 13)
A PVB film was obtained in the same manner as in Example 11 except that BzBEHP was used instead of BzBEHS.
（実施例１４）
ＢｚＢＥＨＳに代えてＴＯＡＢＴＡを用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Example 14)
A PVB film was obtained in the same manner as in Example 11 except that TOABTA was used instead of BzBEHS.
（比較例７）
ＢｚＢＥＨＳを加えなかったこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Comparative Example 7)
A PVB film was obtained in the same manner as in Example 11 except that BzBEHS was not added.
（比較例８）
ＢｚＢＥＨＳに代えてＴＯＰＯを用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Comparative Example 8)
A PVB film was obtained in the same manner as in Example 11 except that TOPO was used instead of BzBEHS.
（比較例９）
ＢｚＢＥＨＳに代えて１Ｈ−ベンゾトリアゾール（ＨＢＴＡ）を用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Comparative Example 9)
A PVB film was obtained in the same manner as in Example 11 except that 1H-benzotriazole (HBTA) was used instead of BzBEHS.
（比較例１０）
ＢｚＢＥＨＳに代えてジ（２−エチルヘキシル）リン酸（ＨＢＥＨＰ）を用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得た。
(Comparative Example 10)
A PVB film was obtained in the same manner as in Example 11 except that di (2-ethylhexyl) phosphoric acid (HBEHP) was used instead of BzBEHS.
（比較例１１）
ＢｚＢＥＨＳに代えてＮａＢＴＡを用いたこと以外は実施例１１と同様にしてＰＶＢフィルムを得ようとしたが、ＮａＢＴＡがテトラヒドロフランに溶けなかったため、得ることができなかった。
(Comparative Example 11)
An attempt was made to obtain a PVB film in the same manner as in Example 11 except that NaBTA was used instead of BzBEHS, but this could not be obtained because NaBTA did not dissolve in tetrahydrofuran.
実施例１１〜１４及び比較例７〜１１で得られたＰＶＢフィルムに対して、紫外線ランプで３６５ｎｍの光を照射して発光強度を観察した。発光強度は比較例７で得られたＰＶＢフィルムの発光強度を基準として以下の評価基準により評価した。得られた結果を表４に示す。 The PVB films obtained in Examples 11 to 14 and Comparative Examples 7 to 11 were irradiated with 365 nm light with an ultraviolet lamp, and the emission intensity was observed. The emission intensity was evaluated according to the following evaluation criteria based on the emission intensity of the PVB film obtained in Comparative Example 7. Table 4 shows the obtained results.
（発光強度の評価基準）
Ａ：比較例７で得られたＰＶＢフィルムよりも発光強度が高い
Ｂ：比較例７で得られたＰＶＢフィルムと同程度の発光強度
Ｃ：比較例７で得られたＰＶＢフィルムよりも発光強度が低い
また、実施例１１〜１４及び比較例７〜１１で得られたＰＶＢフィルムについて、フィルムの外観を以下の評価基準により評価した。得られた結果を前記発光強度の評価結果と併せて表４に示す。
(Evaluation criteria for emission intensity)
A: Luminous intensity higher than that of the PVB film obtained in Comparative Example 7 B: Luminous intensity equivalent to that of the PVB film obtained in Comparative Example 7 C: Luminous intensity as compared with the PVB film obtained in Comparative Example 7 Moreover, about the PVB film obtained by Examples 11-14 and Comparative Examples 7-11, the external appearance of the film was evaluated by the following evaluation criteria. The obtained results are shown in Table 4 together with the evaluation results of the emission intensity.
（フィルム外観の評価基準）
Ａ：フィルムが透明である
Ｂ：フィルム表面の一部にまだらに吹き出しが観察される
Ｃ：フィルム表面の全体にわたって白濁が観察される。
(Evaluation criteria for film appearance)
A: The film is transparent. B: Splashes are observed on a part of the film surface. C: White turbidity is observed over the entire film surface.
表４に示す結果から明らかなように、実施例１１〜１４のＰＶＢフィルムにおいて、ＢｚＢＥＨＳ（実施例１１）、ＢｚＢＴＡ（実施例１２）、ＢｚＢＥＨＰ（実施例１３）、ＴＯＡＢＴＡ（実施例１４）の添加量が［Ｅｕ（ＦＯＤ）３］に対して１モル当量以上であったにも拘わらず、フィルムの外観は透明でブリードアウトは認められなかった。さらに、実施例１１〜１４のＰＶＢフィルムにおいては比較例７のＰＶＢフィルムよりも明瞭な赤の発光が観察され、発光強度が十分に高いことが確認された。一方、比較例８〜１１のＰＶＢフィルムは、発光強度及び／又は樹脂への相溶性が劣るものであった。 As is clear from the results shown in Table 4, in the PVB films of Examples 11 to 14, addition of BzBEHS (Example 11), BzBTA (Example 12), BzBEHP (Example 13), TOABTA (Example 14) Although the amount was 1 molar equivalent or more with respect to [Eu (FOD) 3 ], the appearance of the film was transparent and no bleed out was observed. Furthermore, in the PVB films of Examples 11 to 14, clear red light emission was observed as compared with the PVB film of Comparative Example 7, and it was confirmed that the light emission intensity was sufficiently high. On the other hand, the PVB films of Comparative Examples 8 to 11 were inferior in light emission intensity and / or compatibility with the resin.
以上説明したように、本発明によれば、高い発光強度と優れた有機媒体への相溶性とを有する発光性ＥｕＩＩＩ錯塩及びそれを用いた発光素子、並びにトリスβ−ジケトナトＥｕＩＩＩ錯体に対する発光増強剤を提供することが可能となる。 As described above, according to the present invention, a luminescent Eu III complex salt having high emission intensity and excellent compatibility with an organic medium, a light emitting device using the same, and luminescence with respect to a tris β-diketonato Eu III complex An enhancer can be provided.
また、本発明の発光性ＥｕＩＩＩ錯塩及びトリスβ−ジケトナトＥｕＩＩＩ錯体の発光増強剤は優れた有機媒体への相溶性を有すると共に、加熱による昇華がおこりにくく、また、水や空気に対する安定性に優れるため、容易に透明性及び発光強度が高く且つ高い発光強度が持続する発光素子を製造することができ、非常に有用である。 The light emitting enhancer luminescent Eu III complex and tris β- diketonate Eu III complexes of the present invention which has a compatibility with the good organic medium, hardly occurs sublimation by heating and stability to water and air Therefore, it is possible to easily manufacture a light emitting device having high transparency and high emission intensity and maintaining high emission intensity, which is very useful.
Claims (6)
で表わされる有機酸アニオンのうちの少なくとも１種であることを特徴とする発光性ＥｕＩＩＩ錯塩。 A tris β-diketonato Eu III complex and an Eu III complex ion composed of an organic acid anion coordinated with the complex and a quaternary ammonium cation, and the organic acid anion is represented by the following general formula (1) to (3):
A luminescent Eu III complex salt, which is at least one of organic acid anions represented by the formula:
で表わされる第４級アンモニウムカチオンのうち少なくとも１種であることを特徴とする請求項１に記載の発光性ＥｕＩＩＩ錯塩。 The quaternary ammonium cation is represented by the following general formulas (4) to (5):
The luminescent Eu III complex salt according to claim 1, which is at least one of quaternary ammonium cations represented by the formula:
で表わされるβ−ジケトンであることを特徴とする請求項１又は２に記載の発光性ＥｕＩＩＩ錯塩。 The β-diketone in the tris β-diketonato Eu III complex is represented by the following general formula (6):
The luminescent Eu III complex salt according to claim 1, which is a β-diketone represented by the formula:
で表わされる有機酸アニオンのうちの少なくとも１種であることを特徴とする発光増強剤。 An organic acid anion and a quaternary ammonium cation are contained, and the organic acid anion is represented by the following general formulas (1) to (3):
A luminescence enhancer characterized by being at least one of organic acid anions represented by the formula:
で表わされる第４級アンモニウムカチオンのうち少なくとも１種であることを特徴とする請求項４に記載の発光増強剤。 The quaternary ammonium cation is represented by the following general formulas (4) to (5):
The luminescence enhancer according to claim 4, which is at least one of quaternary ammonium cations represented by the formula:
A light emitting device comprising a light emitting layer containing the light emitting Eu III complex salt according to any one of claims 1 to 3.
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