KR100335963B1 - Conjugated diamine compound, epoxy compound formed therefrom and display device adopting the same as color developing substance - Google Patents
Conjugated diamine compound, epoxy compound formed therefrom and display device adopting the same as color developing substance Download PDFInfo
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- KR100335963B1 KR100335963B1 KR1019990029109A KR19990029109A KR100335963B1 KR 100335963 B1 KR100335963 B1 KR 100335963B1 KR 1019990029109 A KR1019990029109 A KR 1019990029109A KR 19990029109 A KR19990029109 A KR 19990029109A KR 100335963 B1 KR100335963 B1 KR 100335963B1
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- epoxy
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 115
- -1 diamine compound Chemical class 0.000 title claims abstract description 44
- 239000004593 Epoxy Substances 0.000 title claims abstract description 35
- 239000000126 substance Substances 0.000 title abstract description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 125000000217 alkyl group Chemical group 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 9
- 125000005843 halogen group Chemical group 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 7
- 125000003837 (C1-C20) alkyl group Chemical group 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 125000003860 C1-C20 alkoxy group Chemical group 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 5
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012954 diazonium Substances 0.000 claims description 3
- 150000001989 diazonium salts Chemical class 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 238000006276 transfer reaction Methods 0.000 claims description 3
- 229940007718 zinc hydroxide Drugs 0.000 claims description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 3
- 239000003377 acid catalyst Substances 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 3
- 238000000576 coating method Methods 0.000 abstract description 3
- 125000003700 epoxy group Chemical group 0.000 abstract description 2
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 230000000704 physical effect Effects 0.000 abstract description 2
- 239000011541 reaction mixture Substances 0.000 description 34
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000015572 biosynthetic process Effects 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- 230000005525 hole transport Effects 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 4
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 4
- UKJLNMAFNRKWGR-UHFFFAOYSA-N cyclohexatrienamine Chemical group NC1=CC=C=C[CH]1 UKJLNMAFNRKWGR-UHFFFAOYSA-N 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- 239000000706 filtrate Substances 0.000 description 4
- 239000011259 mixed solution Substances 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
- 239000000843 powder Substances 0.000 description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- XJCVRTZCHMZPBD-UHFFFAOYSA-N 3-nitroaniline Chemical compound NC1=CC=CC([N+]([O-])=O)=C1 XJCVRTZCHMZPBD-UHFFFAOYSA-N 0.000 description 3
- TYMLOMAKGOJONV-UHFFFAOYSA-N 4-nitroaniline Chemical compound NC1=CC=C([N+]([O-])=O)C=C1 TYMLOMAKGOJONV-UHFFFAOYSA-N 0.000 description 3
- 229910020808 NaBF Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229930192474 thiophene Natural products 0.000 description 3
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- OGGKVJMNFFSDEV-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(3-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound CC1=CC=CC(N(C=2C=CC=CC=2)C=2C=CC(=CC=2)C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C=C(C)C=CC=2)=C1 OGGKVJMNFFSDEV-UHFFFAOYSA-N 0.000 description 2
- HYLYJYMULGVWMX-UHFFFAOYSA-N 4-[4-amino-2-(furan-2-yl)phenyl]-3-(furan-2-yl)aniline Chemical compound C=1C(N)=CC=C(C=2C(=CC(N)=CC=2)C=2OC=CC=2)C=1C1=CC=CO1 HYLYJYMULGVWMX-UHFFFAOYSA-N 0.000 description 2
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000006193 diazotization reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 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 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- DPJCXCZTLWNFOH-UHFFFAOYSA-N 2-nitroaniline Chemical compound NC1=CC=CC=C1[N+]([O-])=O DPJCXCZTLWNFOH-UHFFFAOYSA-N 0.000 description 1
- LLQHSBBZNDXTIV-UHFFFAOYSA-N 6-[5-[[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]methyl]-4,5-dihydro-1,2-oxazol-3-yl]-3H-1,3-benzoxazol-2-one Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC1CC(=NO1)C1=CC2=C(NC(O2)=O)C=C1 LLQHSBBZNDXTIV-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910000733 Li alloy Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229910019015 Mg-Ag Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- SJCKRGFTWFGHGZ-UHFFFAOYSA-N magnesium silver Chemical compound [Mg].[Ag] SJCKRGFTWFGHGZ-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/52—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/32—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/33—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms with substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C07D207/335—Radicals substituted by nitrogen atoms not forming part of a nitro radical
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
- C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
- C07D333/14—Radicals substituted by singly bound hetero atoms other than halogen
- C07D333/20—Radicals substituted by singly bound hetero atoms other than halogen by nitrogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
- C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
- C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
- C07D407/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
- C07D407/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing three or more hetero rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
- C07D409/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
- C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 2개의 오각형 헤테로고리와 2개의 아미노페닐기를 가지고 있으면서 소정의 공액 길이를 갖는 공역화 디아민 화합물과, 이로부터 형성되어 4개의 에폭시기가 도입된 에폭시 화합물을 제공한다. 본 발명의 공역화 디아민 화합물과 이로부터 형성된 사관능성 에폭시 화합물은 모두 청색 발광 재료로서 매우 유용하다. 특히, 상기 에폭시 화합물은 경화반응을 통하여 가교되어 네트워크 구조를 형성할 수 있고, 이러한 구조로 말미암아 내열성, 기계적 성질 및 계면 접착 특성이 매우 우수하다. 그리고 이러한 에폭시 화합물은 가용성이라서 용액 상태로 코팅하여 필름 형태로 만들기가 용이하다는 잇점을 가지고 있다. 이와 같이 이 화합물들은 각종 발광 및 발색 표시소자에서 요구되어지는 화학적, 물리적 및 광학적 특성을 가지고 있어서, 그 적용범위는 매우 광범위하다.The present invention provides a conjugated diamine compound having two pentagonal heterocycles and two aminophenyl groups and having a predetermined conjugated length, and an epoxy compound formed therefrom into which four epoxy groups are introduced. The conjugated diamine compound of the present invention and the tetrafunctional epoxy compound formed therefrom are both very useful as blue light emitting materials. In particular, the epoxy compound can be cross-linked through a curing reaction to form a network structure, it is excellent in heat resistance, mechanical properties and interfacial adhesion properties by this structure. And such an epoxy compound has the advantage that it is easy to make a film form by coating in solution state because it is soluble. As such, these compounds have chemical, physical, and optical properties required in various light emitting and color display devices, and therefore their application range is very broad.
Description
본 발명은 공역화 디아민 화합물, 이로부터 형성된 에폭시 화합물과 이 화합물들을 발색재료서 채용하고 있는 표시소자에 관한 것이다.The present invention relates to a conjugated diamine compound, an epoxy compound formed therefrom, and a display device employing the compounds as a coloring material.
전자발광소자(electroluminescence device: EL device)는 자발 발광형 표시 소자로서 시야각이 넓고 콘트라스트가 우수할 뿐만 아니라 응답시간이 빠르다는 장점을 가지고 있다.An electroluminescence device (EL device) is a self-luminous display device having advantages of wide viewing angle, excellent contrast, and fast response time.
EL 소자는 발광층(emitter layer) 형성용 재료에 따라 무기 EL 소자와 유기 EL 소자로 구분된다. 여기에서 유기 EL 소자는 무기 EL 소자에 비하여 휘도, 구동전압 및 응답속도 특성이 우수하고 다색화가 가능하다는 장점을 가지고 있다.EL elements are classified into inorganic EL elements and organic EL elements according to materials for forming an emitter layer. Herein, the organic EL device has an advantage of excellent luminance, driving voltage, and response speed, and multicoloring, compared to the inorganic EL device.
일반적인 유기 EL 소자는, 기판 상부에 애노드(anode)가 형성되어 있고, 이 애노드 상부에 홀 수송층, 발광층, 전자 수송층 및 캐소드가 순차적으로 형성되어 있는 구조를 가지고 있다. 여기에서 홀 수송층, 발광층 및 전자수송층은 유기 화합물로 이루어진 유기박막들이다.A typical organic EL device has a structure in which an anode is formed on a substrate, and a hole transport layer, a light emitting layer, an electron transport layer, and a cathode are sequentially formed on the anode. Here, the hole transport layer, the light emitting layer and the electron transport layer are organic thin films made of an organic compound.
상술한 바와 같은 구조를 갖는 유기 EL 소자의 구동원리는 다음과 같다.The driving principle of the organic EL element having the above structure is as follows.
상기 애노드 및 캐소드간에 전압을 인가하면 애노드로부터 주입된 홀은 홀 수송층을 경유하여 발광층에 이동된다. 한편, 전자는 캐소드로부터 전자 수송층을 경유하여 발광층에 주입되고, 발광층 영역에서 캐리어들이 재결합하여 엑시톤(exciton)을 생성한다. 이 엑시톤이 여기상태에서 기저상태로 변화되고, 이로 인하여 발광층의 형광성 분자가 발광함으로써 화상이 형성된다.When a voltage is applied between the anode and the cathode, holes injected from the anode are moved to the light emitting layer via the hole transport layer. On the other hand, electrons are injected from the cathode into the light emitting layer via the electron transport layer, and carriers recombine in the light emitting layer region to generate excitons. This exciton is changed from an excited state to a ground state, whereby an image is formed by the fluorescent molecules of the light emitting layer emitting light.
한편, 1987년 이스트만 코닥(Eastman Kodak)사에서는 발광층 형성용 재료로서 저분자인 방향족 디아민과 알루미늄 착체를 이용하고 있는 유기 전자발광소자를 개발하였다(Appl. Phys. Lett. 51 , 913, 1987)In 1987, Eastman Kodak Corp. developed an organic electroluminescent device using a low molecular weight aromatic diamine and an aluminum complex as a material for forming a light emitting layer (Appl. Phys. Lett. 51 , 913, 1987).
이밖에도, 발광층 형성용 재료로서 폴리(p-페닐렌비닐렌)(PPV), 폴리(2-메톡시-5-(2'-에틸헥실옥시)-1,4-페닐렌비닐렌) 등과 같은 고분자를 사용하고 있는 유기 전자발광소자가 발표되었다(Nature, 347 , 539, 1990 Appl. Phys. Lett. 58 , 1982, 1991).In addition, as a light emitting layer forming material, poly (p-phenylenevinylene) (PPV), poly (2-methoxy-5- (2'-ethylhexyloxy) -1,4-phenylenevinylene) and the like Organic electroluminescent devices using polymers have been published (Nature, 347 , 539, 1990 Appl. Phys. Lett. 58 , 1982, 1991).
그런데, 상기 고분자중 PPV는 유기용매에 대한 용해도 특성이 불량하여 스핀코팅법에 의한 막형성시 많은 어려움이 있다. 이러한 문제점을 해결시키기 위하여PPV에 유기용매에 대한 용해도 특성을 개선시킬 수 있는 작용기를 도입시킨 가용성 PPV이 개발되었다. PPV 또는 그 유도체들을 발광층 재료로 채용하고 있는 유기 전자발광소자는 녹색에서 오렌지색까지의 색깔을 구현한다.However, PPV in the polymer has a great difficulty in forming a film by spin coating because of poor solubility in organic solvents. In order to solve this problem, a soluble PPV has been developed incorporating functional groups capable of improving the solubility characteristics of organic solvents in PPV. Organic electroluminescent devices employing PPV or derivatives thereof as light emitting layer materials realize colors ranging from green to orange.
한편, 현재까지 알려진 청색 발광 화합물은 다른 색상의 발광 화합물에 비하여 발광효율이 저하되는 문제점이 있으며, 이로 인하여 새로운 청색 발광 화합물 개발이 시급한 해결 과제이다.On the other hand, the blue light emitting compound known to date has a problem that the luminous efficiency is lowered compared to the light emitting compound of other colors, and therefore, a new blue light emitting compound development is an urgent problem.
본 발명이 이루고자 하는 기술적 과제는 발광 효율 등의 특성이 우수한 새로운 발광 화합물과 그 제조방법을 제공하는 것이다.SUMMARY OF THE INVENTION The present invention has been made in an effort to provide a novel light emitting compound having excellent properties such as luminous efficiency and a method of manufacturing the same.
본 발명이 이루고자 하는 다른 기술적 과제는 상기 발광 화합물들을 발색 재료로서 채용하고 있는 표시소자를 제공하는 것이다.Another object of the present invention is to provide a display device employing the light emitting compounds as a color developing material.
도 1은 본 발명에 따른 화학식 1의 공역화 디아민 화합물의 합성과정을 나타낸 도면이고, 도 2a-b는 본 발명에 따른 공역화 디아민 화합물로부터 에폭시 화합물을 합성하는 과정을 나타낸 도면이다.1 is a view showing the synthesis process of the conjugated diamine compound of formula 1 according to the present invention, Figure 2a-b is a view showing a process for synthesizing the epoxy compound from the conjugated diamine compound according to the present invention.
상기 첫번째 기술적 과제를 이루기 위하여 본 발명에서는 화학식 1로 표시되는 디아민 화합물을 제공한다.
상기식중, A는 단순히 단일 결합(single bond)을 나타내거나 또는Wherein A simply represents a single bond or
이고, ego,
R1, R2, R3, R4, R5, R6, R7, R8,R9, R10,R11, R12는 서로 독립적으로 -H, C1-C20의 알킬기, C1-C20의 할로겐화된 알킬기, C1-C20의 알콕시기, C1-C20의 할로겐화된 알콕시기, 옥시아릴기, 옥시할로아릴기, 할로겐 원자 또는R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently an alkyl group of -H, C 1 -C 20 , C 1 -C 20 halogenated alkyl group, C 1 -C 20 alkoxy group, C 1 -C 20 halogenated alkoxy group, oxyaryl group, oxyhaloaryl group, halogen atom or
로 이루어진 군으로부터 선택되고,Selected from the group consisting of
R13,R14, R15는 서로 독립적으로 -H, C1-C20의 알킬기, C1-C20의 할로겐화된 알킬기, C1-C20의 알콕시기, C1-C20의 할로겐화된 알콕시기, 옥시아릴기, 옥시할로아릴기, 할로겐 원자로 이루어진 군으로부터 선택되고,R 13 , R 14 , R 15 independently of one another are -H, C 1 -C 20 alkyl group, C 1 -C 20 halogenated alkyl group, C 1 -C 20 alkoxy group, C 1 -C 20 halogenated An alkoxy group, an oxyaryl group, an oxyhaloaryl group, a halogen atom,
X는 -O-, -S-, -NH, -NCOOR' 및 -NR'로 이루어진 군으로부터 선택되고, R'은 C1-C25지방족 알킬기이고,X is selected from the group consisting of -O-, -S-, -NH, -NCOOR 'and -NR', R 'is a C 1 -C 25 aliphatic alkyl group,
단, A가 단일결합을 나타내고, R1, R2, R3, R4, R5, R6, R7및 R8가 서로 독립적으로 수소, C1-C20의 알킬기 및 할로겐 원자로 이루어진 군으로부터 선택된 경우는 제외한다.Provided that A represents a single bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, a group consisting of C 1 -C 20 alkyl groups and halogen atoms Except when selected from.
상기 화학식 1에서 X는 -NH, -NCH3, -NCH2CH3, -NCH2(CH2)nCH3, -NCOOCH3, 및 -NCOO(CH2)nCH3로 이루어진 군으로부터 선택되며, n은 1 내지 20의 정수인 것이 바람직하다. 특히, 상기 화학식 1의 공역화 디아민 화합물은 하기 구조식의 화합물 (F) 및 (G-1)인 것이 바람직하다.In Formula 1, X is selected from the group consisting of -NH, -NCH 3 , -NCH 2 CH 3 , -NCH 2 (CH 2 ) n CH 3 , -NCOOCH 3 , and -NCOO (CH 2 ) n CH 3 . It is preferable that n is an integer of 1-20. In particular, it is preferable that the conjugated diamine compound of Formula 1 is a compound (F) and (G-1) of the following structural formula.
상기식중, X는 상술한 바와 같다.In said formula, X is as above-mentioned.
상기 화학식 1의 공역화 디아민 화합물의 유도체로는 화학식 2로 표시되는 에폭시 화합물을 들 수 있다.Examples of the derivative of the conjugated diamine compound of Formula 1 include an epoxy compound represented by Formula 2.
<화학식 2><Formula 2>
상기식중, A, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10,R11, R12, R13, R14,R15, X및 R'은 상술한 바와 같다.Wherein A, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , X and R 'are as described above.
특히, 이러한 에폭시 화합물은 하기 구조식의 화합물 (I) 및 (K-1)인 것이바람직하다.In particular, it is preferable that such epoxy compounds are compounds (I) and (K-1) of the following structural formulas.
본 발명의 두번째 기술적 과제는 (a) 아민 화합물 (A)을 디아조화(diazotization)하여 대응하는 다아조늄염(diazonium salt) 화합물 (B)을 얻는 단계;The second technical problem of the present invention is the step of (a) diazotizing the amine compound (A) to obtain a corresponding diazonium salt compound (B);
(b) 상기 디아조늄 화합물 (B)의 탈질소 반응을 실시한 다음, 오각형 헤테로 고리 화합물을 도입하여 화합물 (C)를 얻는 단계;(b) conducting denitrogenation of the diazonium compound (B), and then introducing a pentagonal heterocyclic compound to obtain a compound (C);
(c) 상기 화합물 (C)를 아연/수산화나트륨과 반응하여 아조 벤젠 화합물 (D)을 얻는 단계;(e) 산촉매하의 벤지딘 전이반응을 이용하여 상기 히드라조 화합물(E)로부터 화합물 (F) 또는 화합물 (G)을 얻는 단계: 및(f) 상기 화합물 (F)와 화합물 (G)중에서 선택된 하나와 에피클로로히드린을 반응하여 사관능성 에폭시 화합물 (I) 또는 화합물 (K)을 제조하는 단계;를 포함하는 것을 특징으로 하는 상술한 화학식 1의 공역화 디아민 화합물 및 그 유도체의 제조방법에 의하여 이루어진다.(c) reacting compound (C) with zinc / sodium hydroxide to obtain an azo benzene compound (D); (e) using a benzidine transfer reaction under an acid catalyst from compound (F) or Obtaining compound (G): and (f) reacting epichlorohydrin with one selected from compound (F) and compound (G) to prepare tetrafunctional epoxy compound (I) or compound (K); It is made by the method for producing a conjugated diamine compound of Formula 1 and its derivatives, characterized in that it comprises a.
상기식중, X는 -O-, -S-, -NH, -NCOOR' 및 -NR'로 이루어진 군으로부터 선택되고, R'은 C1-C25지방족 알킬기이고, Q는 BF4, BCl4및 BBr4로 이루어진 군으로부터 선택된다.Wherein X is selected from the group consisting of -O-, -S-, -NH, -NCOOR 'and -NR', R 'is a C 1 -C 25 aliphatic alkyl group, Q is BF 4 , BCl 4 And BBr 4 .
본 발명의 세번째 과제는 상기 화학식 1의 공역화 디아민 화합물 및 그 유도체를 발색 재료로서 채용하고 있는 표시소자에 의하여 이루어진다. 본 발명의 바람직한 일면으로 상기 공역화 디아민 화합물 및 그 유도체를 채용하고 있는 유기 전자발광소자를 들 수 있다.A third object of the present invention is achieved by a display device employing the conjugated diamine compound of Formula 1 and derivatives thereof as a color developing material. As a preferable aspect of this invention, the organic electroluminescent element which employ | adopts the said conjugated diamine compound and its derivative (s) is mentioned.
즉, 본 발명의 세번째 과제는 한 쌍의 전극사이에 구비되어 있는 유기막을 포함하고 있는 유기 전자발광소자에 있어서,That is, the third object of the present invention is to provide an organic electroluminescent device comprising an organic film provided between a pair of electrodes,
상기 유기막이 화학식 1의 공역화 디아민 화합물 및 그 유도체를 포함하고 있는 것을 특징으로 하는 유기 전자발광소자에 의하여 이루어진다.<화학식 1>상기식중, R은 수소 또는 하기 구조식으로 나타나고,The organic film is made of an organic electroluminescent device, characterized in that it comprises a conjugated diamine compound of Formula 1 and its derivatives. Wherein R is represented by hydrogen or the following structural formula,
A는 단순히 단일 결합(single bond)을 나타내거나 또는A simply represents a single bond or
이고, ego,
R1, R2, R3, R4, R5, R6, R7, R8,R9, R10,R11, R12는 서로 독립적으로 -H, C1-C20의 알킬기, C1-C20의 할로겐화된 알킬기, C1-C20의 알콕시기, C1-C20의 할로겐화된 알콕시기, 옥시아릴기, 옥시할로아릴기, 할로겐 원자 또는R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 are each independently an alkyl group of -H, C 1 -C 20 , C 1 -C 20 halogenated alkyl group, C 1 -C 20 alkoxy group, C 1 -C 20 halogenated alkoxy group, oxyaryl group, oxyhaloaryl group, halogen atom or
로 이루어진 군으로부터 선택되고,Selected from the group consisting of
R13,R14, R15는 서로 독립적으로 -H, C1-C20의 알킬기, C1-C20의 할로겐화된 알킬기, C1-C20의 알콕시기, C1-C20의 할로겐화된 알콕시기, 옥시아릴기, 옥시할로아릴기, 할로겐 원자로 이루어진 군으로부터 선택되고,R 13 , R 14 , R 15 independently of one another are -H, C 1 -C 20 alkyl group, C 1 -C 20 halogenated alkyl group, C 1 -C 20 alkoxy group, C 1 -C 20 halogenated An alkoxy group, an oxyaryl group, an oxyhaloaryl group, a halogen atom,
X는 -O-, -S-, -NH, -NCOOR' 및 -NR'로 이루어진 군으로부터 선택되고, R'은C1-C25지방족 알킬기이고,X is selected from the group consisting of -O-, -S-, -NH, -NCOOR 'and -NR', R 'is a C 1 -C 25 aliphatic alkyl group,
단, A가 단일결합을 나타내고, R1, R2, R3, R4, R5, R6, R7및 R8가 서로 독립적으로 수소, C1-C20의 알킬기 및 할로겐 원자로 이루어진 군으로부터 선택된 경우는 제외한다.Provided that A represents a single bond, and R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are each independently hydrogen, a group consisting of C 1 -C 20 alkyl groups and halogen atoms Except when selected from.
화학식 1의 공역화 디아민 화합물은 청색 발광 특성을 가지고 있는 물질로서, 그 적용범위가 특별히 한정되지 않는다. 이러한 공역화 디아민 화합물의 구체적인 예로서, 화합물 (F)에서 X가 O인 화학식 3의 화합물, X가 S인 화학식 4의 화합물, X가 NH인 화학식 5의 화합물, X가 N-CH3인 화학식 6의 화합물, 화합물 (G-1)에서 X가 O인 화학식 7 및 8의 화합물, X가 S인 화학식 9 및 10의 화합물, X가 NH인 화학식 11 및 12의 화합물, X가 N-CH3인 화학식 13 및 14의 화합물이 있다.The conjugated diamine compound of Chemical Formula 1 is a material having blue light emission characteristics, and its application range is not particularly limited. Specific examples of such conjugated diamine compounds include compounds of the formula (3) in which X is O, compounds of the formula (4) in which X is S, compounds of formula (5) in which X is NH, and X is N-CH 3 Compound of formula 6, compound of formulas 7 and 8 wherein X is O in compound (G-1), compound of formulas 9 and 10 where X is S, compound of formulas 11 and 12 where X is NH, X is N-CH 3 And compounds of Formula 13 and 14,
<화학식 3><Formula 3>
<화학식 4><Formula 4>
<화학식 5><Formula 5>
<화학식 6><Formula 6>
<화학식 7><Formula 7>
<화학식 8><Formula 8>
<화학식 9><Formula 9>
<화학식 10><Formula 10>
<화학식 11><Formula 11>
<화학식 12><Formula 12>
<화학식 13><Formula 13>
<화학식 14><Formula 14>
한편, 에폭시 수지는 일반적으로 열적 안정성, 기계적 특성, 절연특성 및 접착성은 우수하다는 장점을 가지고 있지만, 수분에 약하다는 단점을 가지고 있다. 이러한 단점을 해결하면서 네트워크 구조의 형성으로 열적 안정성 및 기계적 특성면에서 보다 향상시킨 물질로서, 테트라글리시딜(tetraglycidyl) 에폭시 수지가 개발되었다.On the other hand, epoxy resins generally have the advantages of excellent thermal stability, mechanical properties, insulation properties and adhesion, but have a disadvantage of being weak in moisture. While addressing these shortcomings, tetraglycidyl epoxy resins have been developed as materials having improved network stability and mechanical properties.
이에 본 발명은, 2개의 오각형 헤테로고리와 2개의 아미노페닐기를 가지고 있으면서 소정의 공액 길이를 갖는 화학식 1의 디아민 화합물에 4개의 에폭시기를 도입하여 수분에 대해 약하다는 단점을 극복하면서 기계적 특성, 열적 안정성 등의 특성이 향상된 화학식 2의 에폭시 화합물을 얻고자 한 데 그 특징이 있다.Accordingly, the present invention, mechanical properties, thermal stability while overcoming the disadvantage of being weak against moisture by introducing four epoxy groups in the diamine compound of Formula 1 having two pentagonal heterocycles and two aminophenyl groups having a predetermined conjugated length There is a feature to obtain an epoxy compound of the formula (2) with improved properties, such as.
<화학식 2><Formula 2>
상기식중, A, R1, R2, R3, R4, R5, R6, R7, R8, R9, R10,R11, R12, R13, R14,R15, X 및 R'은 상술한 바와 같다.Wherein A, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , X and R 'are as described above.
상술한 화학식 2의 에폭시 화합물은 유기용매에 용해되므로 용액 상태로 코팅하여 막을 형성하기가 용이하다. 따라서 가공성면에서 매우 유리할 뿐만 아니라, 경화제를 이용한 경화공정을 통하여 가교됨으로써 네트워크 구조를 형성할 수 있다. 이와 같은 구조적 특성으로 말미암아 내열성, 구조적 안정성, 기계적 특성 및 계면 접착 특성 등이 매우 우수하다. 이와 같은 에폭시 화합물은 화학식 1의 공역화 디아민 화합물과 마찬가지로 청색 발광 특성을 가지고 있는 물질로서, 유기전자발광소자 등의 표시소자에 매우 유용하다.Since the epoxy compound of Formula 2 is dissolved in an organic solvent, it is easy to form a film by coating in a solution state. Therefore, not only is it advantageous in terms of processability, but also can be formed by crosslinking through a curing process using a curing agent to form a network structure. Such structural properties are excellent in heat resistance, structural stability, mechanical properties and interfacial adhesion properties. Such an epoxy compound is a material having blue light emission characteristics similar to the conjugated diamine compound of Chemical Formula 1, and is very useful for display devices such as organic electroluminescent devices.
에폭시 화합물의 구체적인 예로서, 상기 화합물 (I)에서 X가 O인 화학식 15 화합물, X가 S인 화학식 16의 화합물, X가 NH인 화학식 17의 화합물, X가 N-CH3인 화학식 18의 화합물, 상기 화합물 (K)에서 O인 화학식 19 및 20의 화합물, X가 S인 화학식 21 및 22의 화합물, X가 NH인 화학식 23 및 24의 화합물 또는 X가 N-CH3인 화학식 25 및 26의 화합물이 있다.As a specific example of the epoxy compound, in the compound (I), the compound of formula 15 wherein X is O, the compound of formula 16 wherein X is S, the compound of formula 17 wherein X is NH, the compound of formula 18 wherein X is N-CH 3 , of the compound (K) a compound of formula 19 and 20 O in, X is S in formula 21 and a compound of 22, X is NH in formula 23 and 24 compound, or X is N-CH 3 of the formula 25 and 26 of Compound.
<화학식 15><Formula 15>
<화학식 16><Formula 16>
<화학식 17><Formula 17>
<화학식 18><Formula 18>
<화학식 19><Formula 19>
<화학식 20><Formula 20>
<화학식 21><Formula 21>
<화학식 22><Formula 22>
<화학식 23><Formula 23>
<화학식 24><Formula 24>
<화학식 25><Formula 25>
<화학식 26><Formula 26>
이하, 도 1을 참조하여, 화학식 1의 공역화 디아민 화합물과 이로부터 화학식 2의 에폭시 화합물을 제조하는 방법을 살펴보기로 한다.Hereinafter, referring to FIG. 1, a conjugated diamine compound of Formula 1 and a method of preparing an epoxy compound of Formula 2 will be described.
먼저, o-, m-, 또는 p-니트로아닐린 (A)을 디아조화(diazotization)하여 대응하는 다아조늄염(diazonium salt) 화합물 (B)을 얻는다. 이 때 디아조화 반응은 NaNO2/NaBF4조건을 이용한다. 이어서, 이 디아조늄 화합물 (B)의 탈질소 반응을 실시하고, 이 화합물의 페닐기와 공액 결합을 형성할 수 있는 오각형 헤테로고리 화합물을 도입하여 화합물 (C)을 형성하다. 여기에서 오각형 헤테로고리 화합물로는 퓨란, 퓨란 유도체, 티오펜, 티오펜 유도체, 피롤, 피롤 유도체 등을 들 수 있다.First, diazotization of o-, m-, or p-nitroaniline (A) yields the corresponding diazonium salt compound (B). At this time, the diazotization reaction uses NaNO 2 / NaBF 4 conditions. Subsequently, the denitrification reaction of this diazonium compound (B) is performed, and the compound (C) is formed by introducing the pentagonal heterocyclic compound which can form a conjugated bond with the phenyl group of this compound. The pentagonal heterocyclic compound may include furan, furan derivatives, thiophene, thiophene derivatives, pyrrole, pyrrole derivatives and the like.
그 후, 상기 화합물 (C)에 아연/수산화나트륨 조건을 부가한 다음, 이를 격렬하게 교반시키면서 24-36시간동안 환류하여 아조벤젠 화합물 (D)을 얻는다.Thereafter, zinc / sodium hydroxide conditions are added to the compound (C), followed by refluxing for vigorously stirring for 24-36 hours to obtain an azobenzene compound (D).
상기 아조벤젠 화합물 (D)을 아연/암모늄 클로라이드 조건하에서 반응시켜 히드라조 화합물 (E)을 얻는다. 이 히드라조 화합물 (E)을 저온(0∼5℃)에서 교반하면서 여기에 염산 용액을 적가하고 1∼2일동안 0∼5℃에서 보관하면 벤지딘 유도체인 화합물 (F) 및 (G)을 얻을 수 있다. 이와 같은 벤지딘 전이반응에서는 벤지딘 유도체 이외에 여러 가지 다른 이성질체가 얻어지므로 정제과정을 거쳐야 한다. 이 때 정제방법으로는 칼럼 크로마토그래피방법 및/또는 재결정법을 이용한다.The azobenzene compound (D) is reacted under zinc / ammonium chloride conditions to obtain a hydrazo compound (E). While stirring this hydrazo compound (E) at low temperature (0-5 degreeC), the hydrochloric acid solution is added dropwise, and it keeps at 0-5 degreeC for 1-2 days, and the compound (F) and (G) which are benzidine derivatives are obtained. Can be. In this benzidine transfer reaction, various other isomers are obtained in addition to the benzidine derivative, and thus, the purification process has to be performed. At this time, a column chromatography method and / or a recrystallization method are used as a purification method.
도 2a-b를 참조하여, 상술한 화합물 (F) 및 (G)로부터 화학식 2의 에폭시 화합물인 화합물 (I) 및 (K)을 제조하는 방법은 다음과 같다.Referring to Figures 2a-b, the method for preparing compounds (I) and (K) which are epoxy compounds of the formula (2) from the above-described compounds (F) and (G) is as follows.
화학식 1의 공역화 디아민 화합물인 화합물 (F)와 (G)에 에피클로로히드린을 부가한 다음, 25 내지 150℃에서 24시간정도 반응시켜서 대응하는 3급 아민 화합물 (H) 및 (J)을 형성한다. 이어서, 상기 결과물에 수산화나트륨을 적하하면 에폭시 고리가 형성된 에폭시 화합물 (I) 및 화합물 (K)가 얻어진다.Epichlorohydrin is added to compounds (F) and (G), which are conjugated diamine compounds of the formula (1), and then reacted at 25 to 150 ° C. for about 24 hours to react the corresponding tertiary amine compounds (H) and (J). Form. Subsequently, when sodium hydroxide is dripped at the said result, epoxy compound (I) and compound (K) in which an epoxy ring was formed are obtained.
이하, 본 발명에 따른 유기 전자발광소자의 제조방법을 살펴보기로 한다.Hereinafter, a method of manufacturing an organic electroluminescent device according to the present invention will be described.
먼저, 기판 상부에 애노드 전극용 물질을 코팅한다. 여기에서 기판으로는 통상적인 유기 EL 소자에서 사용되는 기판을 사용하는데, 투명성, 표면평활성, 취급용이성 및 방수성이 우수한 유리기판 또는 투명 플라스틱 기판이 바람직하다. 그리고 애노드 전극용 물질으로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화주석(SnO2), 산화아연(ZnO) 등을 사용한다.First, an anode electrode material is coated on the substrate. Here, a substrate used in a conventional organic EL device is used, and a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, ease of handling, and waterproofness is preferable. In addition, transparent and excellent indium tin oxide (ITO), tin oxide (SnO 2 ), and zinc oxide (ZnO) are used as the anode electrode material.
상기 애노드 전극 상부에 홀수송층 형성용 물질을 진공증착 또는 스핀코팅하여 홀수송층을 형성한다. 여기에서 홀 수송층은 형성하지 않고, 애노드 전극 상부에 발광층을 직접 형성하는 것도 가능하다.The hole transport layer is formed by vacuum deposition or spin coating a material for forming a hole transport layer on the anode electrode. Here, the hole transport layer is not formed, and it is also possible to form the light emitting layer directly on the anode electrode.
상기 홀수송층 물질은 특별히 제한되지는 않으며, N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1'-비페닐]-4,4'-디아민(TPD), N,N'-디(나프탈렌-1-일)-N,N'-디페닐-벤지딘{N,N'-di(naphthalene-1-yl)-N,N'-diphenyl-benzidine: α-NPD} 등이 사용된다.The hole transport layer material is not particularly limited, and N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine (TPD) , N, N'-di (naphthalen-1-yl) -N, N'-diphenyl-benzidine {N, N'-di (naphthalene-1-yl) -N, N'-diphenyl-benzidine: α- NPD} and the like.
이어서, 상기 애노드 전극 상부 또는 홀수송층 상부에 화학식 1의 공역화 아민 화합물과 화학식 2의 사관능성 에폭시 화합물중에서 선택된 적어도 하나의 발광 화합물을 진공증착 또는 스퍼터링하여 발광층을 형성한다.Subsequently, at least one light emitting compound selected from the conjugated amine compound of Formula 1 and the tetrafunctional epoxy compound of Formula 2 is formed on the anode electrode or on the hole transport layer to form a light emitting layer by vacuum deposition or sputtering.
그 후, 상기 발광층 상부에 캐소드 형성용 금속을 진공증착하여 캐소드를 형성함으로써 유기 EL 소자가 완성된다. 여기에서 캐소드 형성용 금속으로는 리튬(Li), 마그네슘(Mg), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 이용된다.Thereafter, an organic EL device is completed by forming a cathode by vacuum depositing a metal for forming a cathode on the light emitting layer. The metal for forming the cathode may be lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) and the like.
상기 발광층 상부에는 캐소드를 형성하기 이전에 전자수송층을 형성하기도 한다. 이 전자수송층은 통상적인 전자수송층 형성용 물질을 사용한다.The electron transport layer may be formed on the emission layer before forming the cathode. This electron transport layer uses a conventional material for forming an electron transport layer.
본 발명의 유기 전자발광소자는 애노드, 홀수송층, 발광층, 전자수송층 및 캐소드중에서 선택된 2개의 층사이에 특성 향상을 위한 중간층을 더 형성하는 것이 가능하다. 예를 들어, 애노드와 홀수송층 사이에 홀주입층(hole injection layer: HIL)을 더 형성할 수 있는데, 이와 같이 홀주입층을 형성하면 홀수송층(예: α-NPD)과 애노드(ITO)간의 접착력을 향상시키는 동시에 애노드로부터 홀수송층으로 홀이 주입되는 것을 도와주게 된다.The organic electroluminescent device of the present invention can further form an intermediate layer for improving properties between two layers selected from an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode. For example, a hole injection layer (HIL) may be further formed between the anode and the hole transport layer. If the hole injection layer is formed in this way, the hole transport layer (for example, α-NPD) and the anode (ITO) may be formed. This improves adhesion and helps to inject holes from the anode into the hole transport layer.
유기 전자발광소자는 상술한 바와 같은 순서 즉, 애노드/홀수송층/발광층/전자수송층/캐소드 순으로 제조하여도 되고, 그 반대의 순서 즉, 캐소드/전자수송층/발광층/홀수송층/애노드 순으로도 제조하여도 무방하다.The organic EL device may be manufactured in the order described above, that is, in the order of anode / hole transport layer / light emitting layer / electron transport layer / cathode, or in the reverse order, that is, cathode / electron transport layer / light emitting layer / hole transport layer / anode order. You may manufacture.
이하, 본 발명을 하기 실시예를 들어 상세히 설명하기로 하되, 본발명이 하기 실시예로만 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited to the following Examples.
합성예 1. 화학식 3의 비스(5-(4-아미노페닐))-2,2'-퓨릴Synthesis Example 1. Bis (5- (4-aminophenyl))-2,2'-furyl of Chemical Formula 3
p-니트로아닐린 (A-1) 10g(72.5mmol)을 염산과 물의 혼합용액에 용해한 다음, 얼음 수조를 이용하여 상기 반응 혼합물의 온도를 0∼5℃로 조절하였다. 이후, 이 반응 혼합물에 NaNO26g(85mmol)을 물 20㎖에 용해한 용액을 적가하였다.10 g (72.5 mmol) of p-nitroaniline (A-1) was dissolved in a mixed solution of hydrochloric acid and water, and then the temperature of the reaction mixture was adjusted to 0-5 占 폚 using an ice bath. Then, a solution of 6 g (85 mmol) of NaNO 2 dissolved in 20 ml of water was added dropwise to the reaction mixture.
상기 반응 혼합물을 30분동안 교반한 다음, NaBF416g(140mmol)을 한꺼번에 부가하였다. 이어서, 반응 혼합물을 1시간동안 교반하고, 생성된 고체를 여과하여 흰색의 분말을 얻었다. 이 분말을 물, 에탄올 및 에틸에테르를 이용하여 순차적으로 세척하여 목적하는 화합물 (B-1) 16.8g을 얻었다.The reaction mixture was stirred for 30 minutes and then 16 g (140 mmol) of NaBF 4 were added all at once. The reaction mixture was then stirred for 1 hour and the resulting solid was filtered to give a white powder. The powder was washed sequentially with water, ethanol and ethyl ether to obtain 16.8 g of the target compound (B-1).
상기 화합물 (B-1) 7.5 g(31.6mmol)을 질소 분위기하에서 정제된 퓨란 40㎖에 부가한 다음, 얼음수조를 이용하여 반응 혼합물의 온도를 0∼5℃로 조절하였다.7.5 g (31.6 mmol) of the compound (B-1) were added to 40 ml of purified furan under a nitrogen atmosphere, and the temperature of the reaction mixture was adjusted to 0-5 ° C. using an ice bath.
상기 반응 혼합물을 격렬하게 교반하면서, 여기에 퓨란 20㎖에 트리에틸아민 6.3㎖를 희석한 용액을 적가하였다. 트리에틸아민의 퓨란 용액의 적가가 끝나면 반응 혼합물에 과량의 헥산을 재빨리 투입하였다.While stirring the reaction mixture vigorously, a solution of 6.3 ml of triethylamine was added dropwise to 20 ml of furan. After the dropwise addition of the furan solution of triethylamine, excess hexane was quickly added to the reaction mixture.
상기 반응 혼합물을 칼럼 크로마토그래피를 이용하여 정제한 다음, 에탄올과 물의 혼합용액을 이용하여 재결정하여 화합물 (C-1) 4.9g을 얻었다.The reaction mixture was purified using column chromatography, and then recrystallized from a mixed solution of ethanol and water to obtain 4.9 g of Compound (C-1).
상기 화합물 (C-1) 21.0g(111mmol)을 n-프로필 알콜에 용해한 다음, 여기에 물 40㎖에 수산화나트륨 17.76g(444mmol)을 용해한 용액과 아연 가루 14.5g(222mmol)을 순차적으로 첨가하였다. 이어서, 이 반응 혼합물을 하루동안 환류하였다.21.0 g (111 mmol) of the compound (C-1) was dissolved in n-propyl alcohol, and then a solution of 17.76 g (444 mmol) of sodium hydroxide in 40 mL of water and 14.5 g (222 mmol) of zinc powder were sequentially added thereto. . This reaction mixture was then refluxed for one day.
상기 반응 혼합물을 뜨거운 상태에서 여과한 다음, 여액을 클로로포름으로 추출하고 이를 테트라클로로에탄으로 재결정하여 화합물 (D-1) 14.7g을 얻었다.The reaction mixture was filtered while hot and the filtrate was extracted with chloroform and recrystallized with tetrachloroethane to give 14.7 g of Compound (D-1).
상기 화합물 (D-1) 0.6g(1.9mol)을 질소 분위기하에서 아세톤 30㎖에 용해하였다. 이 반응 혼합물에 NH4Cl 포화수용액 2㎖와 아연가루 1.2g을 부가하고 나서 붉은 색이 없어질 때까지 격렬하게 흔들었다. 이어서, 이 반응 용액을 여과하고 나서, 얻어진 여액을 10% 암모니아 용액과 혼합하면 미색의 고체인 화합물 (E-1)를 얻을 수 있었다.0.6 g (1.9 mol) of the compound (D-1) was dissolved in 30 ml of acetone under a nitrogen atmosphere. 2 ml of saturated aqueous NH 4 Cl solution and 1.2 g of zinc powder were added to the reaction mixture, followed by vigorous shaking until the red color disappeared. Subsequently, after filtering this reaction solution, the obtained filtrate was mixed with the 10% ammonia solution, and the off-white solid compound (E-1) was obtained.
상기 화합물 (E-1) 1.0g(3.16mmol)을 질소 분위기하에서 에탄올 50㎖에 용해한 다음, 얼음 수조를 이용하여 반응 혼합물의 온도를 0∼5℃로 조절하였다. 이어서, 이 반응 혼합물에 에탄올과 염산의 혼합액(1:1 부피비) 20㎖를 1시간에 걸쳐 투입하였다.1.0 g (3.16 mmol) of the compound (E-1) was dissolved in 50 mL of ethanol under a nitrogen atmosphere, and then the temperature of the reaction mixture was adjusted to 0-5 ° C. using an ice bath. Subsequently, 20 ml of a mixture (1: 1 volume ratio) of ethanol and hydrochloric acid was added to the reaction mixture over 1 hour.
상기 반응 혼합물을 하루동안 냉소에 보관한 다음, 수산화나트륨을 이용하여 중화하고 에틸 아세테이트로 추출하였다. 이 결과물을 칼럼 크로마토그래피를 이용하여 정제하여 목적 화합물을 분리해내고 이를 에탄올로 재결정하여 청색의 형광을 띠는 화학식 3의 비스(5-(4-아미노페닐))-2,2'-퓨릴 0.2g을 얻었다.The reaction mixture was stored in a cold place for one day, then neutralized with sodium hydroxide and extracted with ethyl acetate. The resultant was purified using column chromatography to isolate the target compound, which was then recrystallized from ethanol to give a blue fluorescence of bis (5- (4-aminophenyl))-2,2'-puryl 0.2 g was obtained.
m.p. 203∼205℃;m.p. 203 to 205 ° C;
m/e 316(M+);m / e 316 (M + );
1H-NMR(δ, acetone-d6): 7.5(d, 4H, Ph-H), 6.72(d, 4H, Ph-H), 6.68(D, 2H, furyl-H), 6.62(m, 2H, furyl-H), 4.88(s, 4H, NH2);1 H-NMR (δ, acetone-d 6 ): 7.5 (d, 4H, Ph-H), 6.72 (d, 4H, Ph-H), 6.68 (D, 2H, furyl-H), 6.62 (m, 2H , furyl-H), 4.88 (s, 4H, NH 2 );
원소분석, 계산치(Calcd. for C20H16N2): C 75.93; H 5.09; N 8.85Elemental Analysis, Calcd. For C 20 H 16 N 2 : C 75.93; H 5.09; N 8.85
실험치: C 74.45; H 5.01; N 9.53Found: C 74.45; H 5.01; N 9.53
합성예 2. 화학식 15의 사관능성 에폭시 화합물Synthesis Example 2 Tetrafunctional Epoxy Compound of Formula 15
합성예 1에 따라 제조된 화학식 3의 비스(5-(4-아미노페닐))-2,2'-퓨릴 0.1g(0.316mmol)을 에피클로로히드린 4.6g에 용해한 다음, 여기에 물 0.8g과 메틸이소부틸케톤 1㎖를 첨가하여 80℃에서 하루동안 환류시켰다.0.1 g (0.316 mmol) of Bis (5- (4-aminophenyl))-2,2'-furyl of Formula 3 prepared according to Synthesis Example 1 was dissolved in 4.6 g of epichlorohydrin, followed by 0.8 g of water. And 1 ml of methyl isobutyl ketone were added and refluxed at 80 DEG C for one day.
그 후, 상기 반응 혼합물의 온도를 50℃로 유지한 다음, 여기에 반응혼합물의 중량을 기준으로 하여 240배 과량의 50% 수산화나트륨 수용액을 30분에 걸쳐 적가하여 8시간동안 유지하였다.Thereafter, the temperature of the reaction mixture was maintained at 50 ° C., followed by dropwise addition of a 240-fold excess of 50% aqueous sodium hydroxide solution over 30 minutes based on the weight of the reaction mixture for 8 hours.
상기 반응 혼합물을 클로로포름으로 추출하고 이를 칼럼 크로마토그래피를 이용하여 정제하여 청색 형광을 띠는 화학식 15의 4관능성 에폭시 화합물 0.1g을 얻었다.The reaction mixture was extracted with chloroform and purified by column chromatography to obtain 0.1 g of a tetrafunctional epoxy compound of Chemical Formula 15 having a blue fluorescence.
m.p. 152.2℃;m.p. 152.2 ° C .;
Mass(EI, m/e) 540.2(M+);Mass (EI, m / e) 540.2 (M + );
IR(KBr pellet) cm-1: 지방족 C-H 신축이동: 2991, 2922; 방향족 =C-H 신축이동: 3048, N-(CH2)2신축진동: 3440, 퓨란: 1612, 1512, C-O 신축진동: 1234, 1194, 에폭시(옥시란 링): 819, 779;IR (KBr pellet) cm −1 : aliphatic CH stretch: 2991, 2922; Aromatic = CH stretch: 3048, N- (CH 2 ) 2 stretch: 3440, furan: 1612, 1512, CO stretch: 1234, 1194, epoxy (oxirane ring): 819, 779;
1H-NMR(δ, CDCl3) ppm : 7.58-7.61(d, 4H, Ar-H), 6.81-6.84(d, 4H, Ar-H), 6.62(d, 2H, furyl-H), 6.52(d, 2H, furyl-H), 3.55-3.82(m, 4H, -N-CH 2-), 3.44-3.55(m, 4H, -N-CH 2-), 3.19(d, 4H, epoxy-CH-O-), 2.80-2.83(m, 4H, epoxy-O-CH 2),2.58-2.60(m, 4H, epoxy-O-CH 2); 1 H-NMR (δ, CDCl 3 ) ppm: 7.58-7.61 (d, 4H, Ar-H), 6.81-6.84 (d, 4H, Ar-H), 6.62 (d, 2H, furyl-H), 6.52 (d, 2H, furyl-H), 3.55-3.82 (m, 4H, -NC H 2- ), 3.44-3.55 (m, 4H, -NC H 2- ), 3.19 (d, 4H, epoxy-C H -O-), 2.80-2.83 (m, 4H, epoxy-OC H 2 ), 2.58-2.60 (m, 4H, epoxy-OC H 2 );
1C-NMR(δ, CDCl3) ppm: 153.8(furyl-O-C=), 147.9(furyl-O-C=), 145.6(Ar-C), 125.6(Ar-C), 120.6(Ar-C), 112.7(Ar-C), 107.1(furyl-O-C=C-), 104.7(furyl-O-C=C-), 53.3(-N-CH2-), 50.9(epoxy-CH-O), 45.8(epoxy-O-CH2); 1 C-NMR (δ, CDCl 3 ) ppm: 153.8 (furyl-O- C =), 147.9 (furyl-O- C =), 145.6 (Ar-C), 125.6 (Ar-C), 120.6 (Ar- C), 112.7 (Ar-C), 107.1 (furyl-OC = C- ), 104.7 (furyl-OC = C- ), 53.3 (-N- C H 2- ), 50.9 (epoxy- C HO), 45.8 (epoxy-O- C H2);
원소분석, 계산치(Calcd. for C32H32N2O6): C 71.09; H 5.97; N 5.18Elemental Analysis, Calcd. For C 32 H 32 N 2 O 6 : C 71.09; H 5.97; N 5.18
실험치: C 71.01; H 5.99; N 5.12Found: C 71.01; H 5.99; N 5.12
합성예 3. 화학식 7의 2,2'-비스(퓨릴)벤지딘Synthesis Example 3 2,2'-bis (furyl) benzidine of formula (7)
m-니트로아닐린 (A-2) 10g(72.5mmol)을 염산과 물의 혼합용액에 용해한 다음, 이 반응 혼합물의 온도를 얼음 수조를 이용하여 0∼5℃로 조절하였다. 이후, 이 반응 혼합물에 NaNO26g(85mmol)을 물 20㎖에 용해한 용액을 적가하였다.10 g (72.5 mmol) of m-nitroaniline (A-2) was dissolved in a mixed solution of hydrochloric acid and water, and then the temperature of the reaction mixture was adjusted to 0-5 占 폚 using an ice bath. Then, a solution of 6 g (85 mmol) of NaNO 2 dissolved in 20 ml of water was added dropwise to the reaction mixture.
상기 반응 혼합물을 30분동안 교반한 다음, NaBF416g(140mmol)을 한꺼번에 부가하였다. 이어서, 반응 혼합물을 1시간동안 교반하고, 생성된 고체를 여과하여 흰색의 분말을 얻었다. 이 분말을 물, 에탄올 및 에틸에테르를 이용하여 순차적으로 세척하여 목적하는 화합물 (B-2) 16.7g을 얻었다.The reaction mixture was stirred for 30 minutes and then 16 g (140 mmol) of NaBF 4 were added all at once. The reaction mixture was then stirred for 1 hour and the resulting solid was filtered to give a white powder. This powder was washed sequentially with water, ethanol and ethyl ether to obtain 16.7 g of the target compound (B-2).
상기 화합물 (B-2) 7.5 g(31.6mmol)을 질소 분위기하에서 정제된 퓨란 30㎖에 부가한 다음, 얼음수조를 이용하여 반응 혼합물의 온도를 0∼5℃로 조절하였다.7.5 g (31.6 mmol) of the compound (B-2) were added to 30 ml of purified furan under a nitrogen atmosphere, and the temperature of the reaction mixture was adjusted to 0-5 ° C. using an ice bath.
상기 반응 혼합물을 격렬하게 교반하면서, 여기에 퓨란 20㎖에 트리에틸아민 6.3㎖를 희석한 용액을 적가하였다. 트리에틸아민의 퓨란 용액의 적가가 끝나면 반응 혼합물에 과량의 헥산을 재빨리 투입하였다.While stirring the reaction mixture vigorously, a solution of 6.3 ml of triethylamine was added dropwise to 20 ml of furan. After the dropwise addition of the furan solution of triethylamine, excess hexane was quickly added to the reaction mixture.
상기 반응 혼합물을 칼럼 크로마토그래피를 이용하여 정제한 다음, 에탄올과 물의 혼합용액을 이용하여 재결정하여 화합물 (C-2) 3.8g을 얻었다.The reaction mixture was purified by column chromatography, and then recrystallized using a mixed solution of ethanol and water to obtain 3.8 g of compound (C-2).
상기 화합물 (C-2) 3.4g(18mmol)을 n-프로필 알콜에 용해한 다음, 여기에 물 20㎖에 수산화나트륨 2.9g(72mmol)을 용해한 용액과 아연 가루 2.3g(36mmol)을 순차적으로 첨가하였다. 이어서, 이 반응 혼합물을 하루동안 환류하였다.3.4 g (18 mmol) of the compound (C-2) was dissolved in n-propyl alcohol, followed by sequentially adding a solution of 2.9 g (72 mmol) of sodium hydroxide in 20 ml of water and 2.3 g (36 mmol) of zinc powder. . This reaction mixture was then refluxed for one day.
상기 반응 혼합물을 뜨거운 상태에서 여과한 다음, 여액을 클로로포름으로 추출하고 이를 테트라클로로에탄으로 재결정하여 화합물 (D-2) 2.7g을 얻었다.The reaction mixture was filtered while hot and the filtrate was extracted with chloroform and recrystallized with tetrachloroethane to give 2.7 g of compound (D-2).
상기 화합물 (D-2) 6.0g(19.0mol)을 질소 분위기하에서 아세톤 200㎖에 용해하였다. 이 반응 혼합물에 NH4Cl 포화수용액 20㎖와 아연가루 12.0g을 부가하고 나서 붉은 색이 없어질 때까지 격렬하게 흔들었다. 이어서, 상기 혼합물을 여과하고 나서 얻어진 여액을 10% 암모니아 용액과 혼합하면 고동색의 고체인 화합물 (E-2)을 얻을 수 있었다.6.0 g (19.0 mol) of the compound (D-2) was dissolved in 200 ml of acetone under a nitrogen atmosphere. 20 ml of saturated aqueous NH 4 Cl solution and 12.0 g of zinc powder were added to the reaction mixture, followed by vigorous shaking until the red color disappeared. Subsequently, the filtrate obtained after filtration of the mixture was mixed with a 10% ammonia solution to obtain compound (E-2) as a maroon solid.
상기 화합물 (E-2) 0.6g(1.8mmol)을 질소 분위기하에서 에탄올 30㎖에 용해한 다음, 얼음 수조를 이용하여 반응 혼합물의 온도를 0∼5℃로 조절하였다. 이어서, 반응 혼합물에 에탄올과 염산의 혼합액(1:1 부피비) 15㎖를 1시간에 걸쳐 투입하였다.0.6 g (1.8 mmol) of the compound (E-2) was dissolved in 30 ml of ethanol under a nitrogen atmosphere, and then the temperature of the reaction mixture was adjusted to 0 to 5 ° C using an ice bath. Subsequently, 15 ml of a mixture (1: 1 volume ratio) of ethanol and hydrochloric acid was added to the reaction mixture over 1 hour.
상기 반응 혼합물을 하루동안 냉소에 보관한 다음, 수산화나트륨을 이용하여 중화하고 에틸 아세테이트로 추출하였다. 이 결과물을 칼럼 크로마토그래피를 이용하여 정제하여 목적 화합물을 분리해내고 이를 에탄올로 재결정하여 청색의 형광을 띠는 화학식 7의 디아민 화합물 0.12g을 얻었다.The reaction mixture was stored in a cold place for one day, then neutralized with sodium hydroxide and extracted with ethyl acetate. The resultant was purified using column chromatography to separate the target compound, which was then recrystallized from ethanol to obtain 0.12 g of a diamine compound represented by Chemical Formula 7 having a blue fluorescence.
m.p. 156∼157℃;m.p. 156 to 157 ° C;
1H-NMR(δ, acetone-d6) ppm: 7.5(d, 2H, furyl-H), 7.25(d, 2H, Ph-H), 6.84(d, 2H, Ph-H), 6.67(dd, 2H, Ph-H), 6.17(dd, 2H, furyl-H), 5.42(d, 2H, furyl-H), 4.78(s, 4H, NH2); 1 H-NMR (δ, acetone-d 6 ) ppm: 7.5 (d, 2H, furyl-H), 7.25 (d, 2H, Ph-H), 6.84 (d, 2H, Ph-H), 6.67 (dd , 2H, Ph-H), 6.17 (dd, 2H, furyl-H), 5.42 (d, 2H, furyl-H), 4.78 (s, 4H, NH 2 );
원소분석, 계산치(Calcd. for C20H16N2): C 75.93; H 5.09; N 8.85Elemental Analysis, Calcd. For C 20 H 16 N 2 : C 75.93; H 5.09; N 8.85
실험치: C 75.71; H 4.87; N 9.50Found: C 75.71; H 4.87; N 9.50
합성예 4. 화학식 19의 사관능성 에폭시 화합물Synthesis Example 4 Tetrafunctional Epoxy Compound of Formula 19
상기 합성예 4에 따라 얻어진 화학식 7의 디아민 화합물 0.1g(0.316mmol)을에피클로로히드린 4.6g에 용해한 다음, 여기에 물 0.8g과 메틸이소부틸케톤 2㎖를 첨가하여 80℃에서 하루동안 환류시켰다.0.1 g (0.316 mmol) of the diamine compound of Chemical Formula 7 obtained according to Synthesis Example 4 was dissolved in 4.6 g of epichlorohydrin, and then 0.8 g of water and 2 ml of methyl isobutyl ketone were added thereto and refluxed at 80 ° C. for one day. I was.
그 후, 상기 반응 혼합물의 온도를 50℃로 유지한 다음, 여기에 반응혼합물의 중량을 기준으로 하여 240배 과량의 50% 수산화나트륨 수용액을 30분에 걸쳐 적가하여 8시간동안 유지하였다.Thereafter, the temperature of the reaction mixture was maintained at 50 ° C., followed by dropwise addition of a 240-fold excess of 50% aqueous sodium hydroxide solution over 30 minutes based on the weight of the reaction mixture for 8 hours.
상기 반응 혼합물을 클로로포름으로 추출하고 이를 칼럼 크로마토그래피를 이용하여 정제하여 청색 형광을 띠는 화학식 19의 4관능성 에폭시 화합물 0.12g을 얻었다.The reaction mixture was extracted with chloroform and purified by column chromatography to obtain 0.12 g of a tetrafunctional epoxy compound represented by Chemical Formula 19 having a blue fluorescence.
m.p. 167.6℃;m.p. 167.6 ° C .;
Mass(EI, m/e) 540.27(M+);Mass (EI, m / e) 540.27 (M + );
IR(KBr pellet) cm-1: 지방족 C-H 신축이동: 2992, 2919; 방향족 =C-H 신축이동: 3050, N-(CH2)2신축진동: 3435, 퓨란: 1605, 1493, C-O 신축진동: 1210, 에폭시(옥시란 링): 812, 737;IR (KBr pellet) cm −1 : aliphatic CH stretch: 2992, 2919; Aromatic = CH stretch: 3050, N- (CH 2 ) 2 stretch: 3435, furan: 1605, 1493, CO stretch: 1210, epoxy (oxirane ring): 812, 737;
1H-NMR(δ, Acetone-d6) ppm : 7.41(d, 4H, Ar-H furyl-H), 6.96-6.99(d, 2H, Ar-H), 6.89-6.93(dd, 2H, Ar-H), 6.19(dd, 2H, furyl-H), 5.49(d, 2H, furyl-H), 3.80-3.89(m, 4H, -N-CH 2-), 3.53-3.61(m, 4H, -N-CH 2-), 3.22(d, 4H, epoxy-CH-O-), 2.76-2.82(m, 4H, epoxy-O-CH 2), 2.63-2.65(m, 4H, epoxy-O-CH 2); 1 H-NMR (δ, Acetone-d 6 ) ppm: 7.41 (d, 4H, Ar-H furyl-H), 6.96-6.99 (d, 2H, Ar-H), 6.89-6.93 (dd, 2H, Ar -H), 6.19 (dd, 2H, furyl-H), 5.49 (d, 2H, furyl-H), 3.80-3.89 (m, 4H, -NC H 2- ), 3.53-3.61 (m, 4H,- NC H 2- ), 3.22 (d, 4H, epoxy-C H -O-), 2.76-2.82 (m, 4H, epoxy-OC H 2 ), 2.63-2.65 (m, 4H, epoxy-OC H 2 ) ;
1C-NMR(δ, Acetone-d6) ppm: 153.4(furyl-O-C=), 148.6(Ar-C), 141.6(furyl-O-C=), 132.4(Ar-C), 130.9(Ar-C), 127.8(Ar-C), 112.3(Ar-C), 111.7(Ar-C), 109.6(furyl-O-C=C-), 108.6(furyl-O-C=C-), 53.4(-N-CH2-), 50.5(epoxy-CH-O), 45.1(epoxy-O-CH2); 1 C-NMR (δ, Acetone-d 6 ) ppm: 153.4 (furyl-O- C =), 148.6 (Ar-C), 141.6 (furyl-O- C =), 132.4 (Ar-C), 130.9 ( Ar-C), 127.8 (Ar-C), 112.3 (Ar-C), 111.7 (Ar-C), 109.6 (furyl-OC = C- ), 108.6 (furyl-OC = C- ), 53.4 (-N C H 2- ), 50.5 (epoxy- C H-O), 45.1 (epoxy-O- C H 2 );
원소분석, 계산치(Calcd. for C32H32N2O6): C 71.09; H 5.97; N 5.18Elemental Analysis, Calcd. For C 32 H 32 N 2 O 6 : C 71.09; H 5.97; N 5.18
실험치: C 71.28; H 6.12; N 5.06Found: C 71.28; H 6.12; N 5.06
합성예 5-6Synthesis Example 5-6
퓨란 대신 티오펜을 이용한 것을 제외하고는, 합성예 1-2와 동일한 방법에 따라 실시하여 화학식 4의 디아민 화합물과 및 화학식 16의 에폭시 화합물을 합성하였다.Except for using thiophene instead of furan, the diamine compound of Formula 4 and the epoxy compound of Formula 16 were synthesized in the same manner as in Synthesis Example 1-2.
합성예 7-8Synthesis Example 7-8
퓨란 대신 N-메틸피롤을 이용한 것을 제외하고는, 합성예 1-2와 동일한 방법에 따라 실시하여 화학식 6의 디아민 화합물과 및 화학식 18의 에폭시 화합물을 합성하였다.A diamine compound of Formula 6 and an epoxy compound of Formula 18 were synthesized in the same manner as in Synthesis Example 1-2, except that N-methylpyrrole was used instead of furan.
합성예 9-10Synthesis Example 9-10
퓨란 대신 티오펜을 이용한 것을 제외하고는, 합성예 3-4와 동일한 방법에 따라 실시하여 화학식 9의 디아민 화합물과 및 화학식 21의 에폭시 화합물을 합성하였다.Except for using thiophene instead of furan, the diamine compound of Formula 9 and the epoxy compound of Formula 21 were synthesized in the same manner as in Synthesis Example 3-4.
합성예 11-12Synthesis Example 11-12
퓨란 대신 N-메틸피롤을 이용한 것을 제외하고는, 합성예 1-2와 동일한 방법에 따라 실시하여 화학식 13의 디아민 화합물과 및 화학식 25의 에폭시 화합물을 합성하였다.Except that N-methylpyrrole was used instead of furan, the diamine compound of Formula 13 and the epoxy compound of Formula 25 were synthesized in the same manner as in Synthesis Example 1-2.
실시예 1-2Example 1-2
상기 합성예 1에 따라 제조된 화학식 3의 비스(5-(4-아미노페닐))-2,2'-퓨릴과 합성예 2에 따라 제조된 화학식 15의 사관능성 에폭시 화합물을 1,4-디옥산에 각각 용해하고, 이 물질들의 가시광선 흡수 스펙트럼과 발광 스펙트럼을 측정하여 하기 표 1에 나타내었다.Bis (5- (4-aminophenyl))-2,2'-furyl of Chemical Formula 3 prepared according to Synthesis Example 1 and a tetrafunctional epoxy compound of Chemical Formula 15 prepared according to Synthesis Example 2 were prepared in 1,4-di Dissolved in oxane, the visible light absorption spectrum and emission spectrum of these materials were measured and shown in Table 1 below.
실시예 3-4Example 3-4
상기 합성예 3에 따라 제조된 화학식 7의 2,2'-비스(퓨릴)벤지딘과 합성예 4에 따라 제조된 화학식 19의 사관능성 에폭시 화합물을 1,4-디옥산에 각각 용해하고, 이 물질들의 가시광선 흡수 스펙트럼과 발광 스펙트럼을 측정하여 하기 표 1에 나타내었다.2,2'-bis (furyl) benzidine of Formula 7 prepared according to Synthesis Example 3 and a tetrafunctional epoxy compound of Formula 19 prepared according to Synthesis Example 4 were dissolved in 1,4-dioxane, respectively, The visible light absorption spectrum and the emission spectrum of the light are measured and shown in Table 1 below.
상기 표 1로부터, 실시예 1-4의 화합물들은 모두 청색 발광 재료라는 것을 확인할 수 있었다.From Table 1, it was confirmed that the compounds of Examples 1-4 were all blue light emitting materials.
실시예 5Example 5
유리 기판상에 ITO 전극을 형성한 다음, 이 상부에 N,N'-비스(3-메틸페닐)-N,N'-디페닐-[1,1'-비페닐]-4,4'-디아민(TPD)를 진공증착하여 홀수송층을 500Å 두께로 형성하였다.An ITO electrode was formed on the glass substrate, and then N, N'-bis (3-methylphenyl) -N, N'-diphenyl- [1,1'-biphenyl] -4,4'-diamine on top of this. (TPD) was vacuum deposited to form a hole transport layer with a thickness of 500 mm3.
이어서, 상기 홀수송층 상부에 화학식 3의 화합물을 진공증착하여 280Å 두께의 발광층을 형성하였다.Subsequently, the compound of Formula 3 was vacuum deposited on the hole transport layer to form a light emitting layer having a thickness of 280 Å.
그 후, 상기 발광층 상부에 하기 구조식의 화합물을 진공증착하여 350Å 두께의 전자수송층을 형성하였다.Thereafter, a compound of the following structural formula was vacuum deposited on the light emitting layer to form an electron transport layer having a thickness of 350 kHz.
이 전자수송층 상부에 Al:Li 합금을 진공증착하여 1500Å 두께의 알루미늄·리튬 전극을 형성함으로써 유기 전자발광소자를 제조하였다.An organic electroluminescent device was manufactured by vacuum depositing an Al: Li alloy on the electron transport layer to form an aluminum lithium electrode having a thickness of 1500 mW.
실시예 6-16Example 6-16
화학식 3의 화합물 대신 화학식 4-26의 화합물을 사용하는 것을 제외하고는, 실시예 5와 동일하게 실시하여 유기 전자발광소자를 제조하였다.An organic electroluminescent device was manufactured in the same manner as in Example 5, except that the compound of Formula 4-26 was used instead of the compound of Formula 3.
상기 실시예 5-16에 따라 제조된 유기 전자발광소자는 청색을 구현할 수 있었으며, 발광 효율, 구동개시전압 및 휘도 특성이 양호함을 확인할 수 있었다.The organic electroluminescent device manufactured according to Example 5-16 could realize blue color, and it was confirmed that the luminous efficiency, driving start voltage and luminance characteristics were good.
본 발명의 화학식 1의 공역화 디아민 화합물과 이로부터 형성된 화학식 2의사관능성 에폭시 화합물은 모두 청색 발광 재료로서 매우 유용하다. 특히, 상기 에폭시 화합물은 경화반응을 통하여 가교되어 네트워크 구조를 형성할 수 있고, 이러한 구조로 말미암아 내열성, 기계적 성질 및 계면 접착 특성이 매우 우수하다. 그리고 이러한 에폭시 화합물은 가용성이라서 용액 상태로 코팅하여 필름 형태로 만들기가 용이하다는 잇점을 가지고 있다. 이와 같이 이 화합물들은 각종 발광 및 발색 표시소자에서 요구되어지는 화학적, 물리적 및 광학적 특성을 가지고 있어서, 그 적용범위는 매우 광범위하다.The conjugated diamine compound of formula 1 of the present invention and the tetrafunctional epoxy compound of formula 2 formed therefrom are both very useful as blue light emitting materials. In particular, the epoxy compound can be cross-linked through a curing reaction to form a network structure, it is excellent in heat resistance, mechanical properties and interfacial adhesion properties by this structure. And such an epoxy compound has the advantage that it is easy to make a film form by coating in solution state because it is soluble. As such, these compounds have chemical, physical, and optical properties required in various light emitting and color display devices, and therefore their application range is very broad.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JPH061974A (en) * | 1992-06-19 | 1994-01-11 | Fuji Electric Co Ltd | Organic thin-film luminescent element |
| JPH0641396A (en) * | 1992-07-24 | 1994-02-15 | Toray Ind Inc | Epoxy resin composition |
| JPH07216351A (en) * | 1994-01-28 | 1995-08-15 | Fuji Electric Co Ltd | Dispersion-type el element |
| JPH10219242A (en) * | 1997-02-06 | 1998-08-18 | Yasuhiko Shirota | Compound for organic el element and organic el element |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH061974A (en) * | 1992-06-19 | 1994-01-11 | Fuji Electric Co Ltd | Organic thin-film luminescent element |
| JPH0641396A (en) * | 1992-07-24 | 1994-02-15 | Toray Ind Inc | Epoxy resin composition |
| JPH07216351A (en) * | 1994-01-28 | 1995-08-15 | Fuji Electric Co Ltd | Dispersion-type el element |
| JPH10219242A (en) * | 1997-02-06 | 1998-08-18 | Yasuhiko Shirota | Compound for organic el element and organic el element |
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