KR102346098B1 - Compound for organic electronic element having benzocyclobutene functional group for cross-linked bond, organic electronic element using the same, and an electronic device thereof - Google Patents
Compound for organic electronic element having benzocyclobutene functional group for cross-linked bond, organic electronic element using the same, and an electronic device thereof Download PDFInfo
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- KR102346098B1 KR102346098B1 KR1020200025291A KR20200025291A KR102346098B1 KR 102346098 B1 KR102346098 B1 KR 102346098B1 KR 1020200025291 A KR1020200025291 A KR 1020200025291A KR 20200025291 A KR20200025291 A KR 20200025291A KR 102346098 B1 KR102346098 B1 KR 102346098B1
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- Prior art keywords
- organic
- organic compound
- electrode
- thin film
- electric device
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- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical group C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 title description 12
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 126
- 239000010409 thin film Substances 0.000 claims abstract description 65
- 239000000463 material Substances 0.000 claims description 60
- 238000002347 injection Methods 0.000 claims description 41
- 239000007924 injection Substances 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 41
- 239000000203 mixture Substances 0.000 claims description 38
- 239000000126 substance Substances 0.000 claims description 35
- 239000000243 solution Substances 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 24
- 230000000903 blocking effect Effects 0.000 claims description 23
- 230000005525 hole transport Effects 0.000 claims description 19
- 239000002019 doping agent Substances 0.000 claims description 12
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 4
- 239000000049 pigment Substances 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 126
- 238000006243 chemical reaction Methods 0.000 description 75
- 239000000543 intermediate Substances 0.000 description 65
- 239000012044 organic layer Substances 0.000 description 34
- 238000004440 column chromatography Methods 0.000 description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 18
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 18
- 239000012299 nitrogen atmosphere Substances 0.000 description 16
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 238000010992 reflux Methods 0.000 description 15
- 230000015572 biosynthetic process Effects 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- MHYCRLGKOZWVEF-UHFFFAOYSA-N ethyl acetate;hydrate Chemical compound O.CCOC(C)=O MHYCRLGKOZWVEF-UHFFFAOYSA-N 0.000 description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 11
- 125000000217 alkyl group Chemical group 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 10
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 10
- SSJXIUAHEKJCMH-PHDIDXHHSA-N (1r,2r)-cyclohexane-1,2-diamine Chemical compound N[C@@H]1CCCC[C@H]1N SSJXIUAHEKJCMH-PHDIDXHHSA-N 0.000 description 9
- 238000000605 extraction Methods 0.000 description 9
- 229910000160 potassium phosphate Inorganic materials 0.000 description 9
- 235000011009 potassium phosphates Nutrition 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 7
- 125000000623 heterocyclic group Chemical group 0.000 description 7
- 229910052700 potassium Inorganic materials 0.000 description 7
- 239000011591 potassium Substances 0.000 description 7
- 239000004215 Carbon black (E152) Chemical group 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 6
- 229930195733 hydrocarbon Chemical group 0.000 description 6
- 150000002430 hydrocarbons Chemical group 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- ZRXVCYGHAUGABY-UHFFFAOYSA-N 4-bromo-n,n-bis(4-bromophenyl)aniline Chemical compound C1=CC(Br)=CC=C1N(C=1C=CC(Br)=CC=1)C1=CC=C(Br)C=C1 ZRXVCYGHAUGABY-UHFFFAOYSA-N 0.000 description 5
- 125000003118 aryl group Chemical group 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- -1 nitro, hydroxyl Chemical class 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 238000001771 vacuum deposition Methods 0.000 description 5
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical compound C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 4
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 4
- GBRBMTNGQBKBQE-UHFFFAOYSA-L copper;diiodide Chemical compound I[Cu]I GBRBMTNGQBKBQE-UHFFFAOYSA-L 0.000 description 4
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 description 4
- 125000000547 substituted alkyl group Chemical group 0.000 description 4
- 125000003107 substituted aryl group Chemical group 0.000 description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 3
- 239000011368 organic material Substances 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000007142 ring opening reaction Methods 0.000 description 3
- FVAUCKIRQBBSSJ-UHFFFAOYSA-M sodium iodide Chemical compound [Na+].[I-] FVAUCKIRQBBSSJ-UHFFFAOYSA-M 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical compound C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OBIKAXXGBIXXKF-UHFFFAOYSA-N CCCCOC(CC1=C2)C1=CC=C2C(C=C1)=CC=C1NC(C=C1)=CC=C1C1=CC=C(C(C2)OCCCC)C2=C1 Chemical compound CCCCOC(CC1=C2)C1=CC=C2C(C=C1)=CC=C1NC(C=C1)=CC=C1C1=CC=C(C(C2)OCCCC)C2=C1 OBIKAXXGBIXXKF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000003545 alkoxy group Chemical class 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 125000002915 carbonyl group Chemical class [*:2]C([*:1])=O 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 125000004093 cyano group Chemical class *C#N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 238000007645 offset printing Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 2
- ICPSWZFVWAPUKF-UHFFFAOYSA-N 1,1'-spirobi[fluorene] Chemical compound C1=CC=C2C=C3C4(C=5C(C6=CC=CC=C6C=5)=CC=C4)C=CC=C3C2=C1 ICPSWZFVWAPUKF-UHFFFAOYSA-N 0.000 description 1
- LNAOKZKISWEZNY-UHFFFAOYSA-N 1,2-bis(dibromomethyl)benzene Chemical compound BrC(Br)C1=CC=CC=C1C(Br)Br LNAOKZKISWEZNY-UHFFFAOYSA-N 0.000 description 1
- JRCJYPMNBNNCFE-UHFFFAOYSA-N 1,6-dibromopyrene Chemical compound C1=C2C(Br)=CC=C(C=C3)C2=C2C3=C(Br)C=CC2=C1 JRCJYPMNBNNCFE-UHFFFAOYSA-N 0.000 description 1
- HQJQYILBCQPYBI-UHFFFAOYSA-N 1-bromo-4-(4-bromophenyl)benzene Chemical group C1=CC(Br)=CC=C1C1=CC=C(Br)C=C1 HQJQYILBCQPYBI-UHFFFAOYSA-N 0.000 description 1
- HLJCMNHMFMKNNK-UHFFFAOYSA-N 1-bromo-4-[(4-bromophenyl)-diphenylmethyl]benzene Chemical compound C1=CC(Br)=CC=C1C(C=1C=CC(Br)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 HLJCMNHMFMKNNK-UHFFFAOYSA-N 0.000 description 1
- GLEBDDAQOXQQGE-UHFFFAOYSA-N 1-bromo-4-[1-(4-bromophenyl)cyclohexyl]benzene Chemical compound C1=CC(Br)=CC=C1C1(C=2C=CC(Br)=CC=2)CCCCC1 GLEBDDAQOXQQGE-UHFFFAOYSA-N 0.000 description 1
- BLMBNEVGYRXFNA-UHFFFAOYSA-N 1-methoxy-2,3-dimethylbenzene Chemical compound COC1=CC=CC(C)=C1C BLMBNEVGYRXFNA-UHFFFAOYSA-N 0.000 description 1
- JTXMVXSTHSMVQF-UHFFFAOYSA-N 2-acetyloxyethyl acetate Chemical compound CC(=O)OCCOC(C)=O JTXMVXSTHSMVQF-UHFFFAOYSA-N 0.000 description 1
- APSMUYYLXZULMS-UHFFFAOYSA-N 2-bromonaphthalene Chemical compound C1=CC=CC2=CC(Br)=CC=C21 APSMUYYLXZULMS-UHFFFAOYSA-N 0.000 description 1
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- QNGUSFKMKLSUKS-UHFFFAOYSA-N 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-n,n-bis[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]aniline Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N(C=2C=CC(=CC=2)B2OC(C)(C)C(C)(C)O2)C=2C=CC(=CC=2)B2OC(C)(C)C(C)(C)O2)C=C1 QNGUSFKMKLSUKS-UHFFFAOYSA-N 0.000 description 1
- FDRNXKXKFNHNCA-UHFFFAOYSA-N 4-(4-anilinophenyl)-n-phenylaniline Chemical compound C=1C=C(C=2C=CC(NC=3C=CC=CC=3)=CC=2)C=CC=1NC1=CC=CC=C1 FDRNXKXKFNHNCA-UHFFFAOYSA-N 0.000 description 1
- CCIVUDMVXNBUCY-UHFFFAOYSA-N 4-bromo-n-phenylaniline Chemical compound C1=CC(Br)=CC=C1NC1=CC=CC=C1 CCIVUDMVXNBUCY-UHFFFAOYSA-N 0.000 description 1
- HSNBRDZXJMPDGH-UHFFFAOYSA-N 5-bromo-2-iodopyridine Chemical compound BrC1=CC=C(I)N=C1 HSNBRDZXJMPDGH-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 229910001148 Al-Li alloy Inorganic materials 0.000 description 1
- OIOUFXVGKAUUKJ-UHFFFAOYSA-N BrC(C=C1)=CC=C1N(C(C=C1)=CC=C1C1=CC=C(C2=CC=CC=C2)S1)C(C=C1)=CC=C1Br Chemical compound BrC(C=C1)=CC=C1N(C(C=C1)=CC=C1C1=CC=C(C2=CC=CC=C2)S1)C(C=C1)=CC=C1Br OIOUFXVGKAUUKJ-UHFFFAOYSA-N 0.000 description 1
- BNNMRJLVUHPODQ-UHFFFAOYSA-N CC1(C)OB(C2=CC=CC(N(C3=CC(B4OC(C)(C)C(C)(C)O4)=CC=C3)C3=CC(B4OC(C)(C)C(C)(C)O4)=CC=C3)=C2)OC1(C)C Chemical compound CC1(C)OB(C2=CC=CC(N(C3=CC(B4OC(C)(C)C(C)(C)O4)=CC=C3)C3=CC(B4OC(C)(C)C(C)(C)O4)=CC=C3)=C2)OC1(C)C BNNMRJLVUHPODQ-UHFFFAOYSA-N 0.000 description 1
- XJSPCMXTOYCQCY-UHFFFAOYSA-N CCCCOC1C2=CC=CC=C2C1C(C=C1C2(C)C)=CC=C1C1=C2C=C(B2OC(C)(C)C(C)(C)O2)C=C1 Chemical compound CCCCOC1C2=CC=CC=C2C1C(C=C1C2(C)C)=CC=C1C1=C2C=C(B2OC(C)(C)C(C)(C)O2)C=C1 XJSPCMXTOYCQCY-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UJOBWOGCFQCDNV-UHFFFAOYSA-N Carbazole Natural products C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- YKDBPHNXPMHPSP-UHFFFAOYSA-N FC(S(=O)(=O)OC1=C(C=C(C=C1)Br)[Si](C)(C)C)(F)F Chemical compound FC(S(=O)(=O)OC1=C(C=C(C=C1)Br)[Si](C)(C)C)(F)F YKDBPHNXPMHPSP-UHFFFAOYSA-N 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
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- CZPWVGJYEJSRLH-UHFFFAOYSA-N Pyrimidine Chemical compound C1=CN=CN=C1 CZPWVGJYEJSRLH-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Natural products C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- DHXVGJBLRPWPCS-UHFFFAOYSA-N Tetrahydropyran Chemical compound C1CCOCC1 DHXVGJBLRPWPCS-UHFFFAOYSA-N 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- JHYLKGDXMUDNEO-UHFFFAOYSA-N [Mg].[In] Chemical compound [Mg].[In] JHYLKGDXMUDNEO-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- JTXHBTQCQCFUQW-UHFFFAOYSA-N bicyclo[4.2.0]octa-1(6),2,4-trien-4-amine Chemical compound NC1=CC=C2CCC2=C1 JTXHBTQCQCFUQW-UHFFFAOYSA-N 0.000 description 1
- SKLKSDFOCXHYOO-UHFFFAOYSA-N bicyclo[4.2.0]octa-1,3,5-trien-7-ol Chemical compound C1=CC=C2C(O)CC2=C1 SKLKSDFOCXHYOO-UHFFFAOYSA-N 0.000 description 1
- UTEBJTKMYMQRIF-UHFFFAOYSA-N bis(4-bromophenyl)-diphenylsilane Chemical compound C1=CC(Br)=CC=C1[Si](C=1C=CC(Br)=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 UTEBJTKMYMQRIF-UHFFFAOYSA-N 0.000 description 1
- IPWKHHSGDUIRAH-UHFFFAOYSA-N bis(pinacolato)diboron Chemical compound O1C(C)(C)C(C)(C)OB1B1OC(C)(C)C(C)(C)O1 IPWKHHSGDUIRAH-UHFFFAOYSA-N 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001716 carbazoles Chemical group 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- CFBGXYDUODCMNS-UHFFFAOYSA-N cyclobutene Chemical compound C1CC=C1 CFBGXYDUODCMNS-UHFFFAOYSA-N 0.000 description 1
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005137 deposition process Methods 0.000 description 1
- CZYWAPBZHJZHJD-UHFFFAOYSA-N dibenzocyclooctadiene Chemical group C1CCCC2=CC=CC=C2C2=CC=CC=C21 CZYWAPBZHJZHJD-UHFFFAOYSA-N 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
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Abstract
본 발명은 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물로서, 그 말단에 적어도 하나 이상의 벤조시클로부텐기(benzocyclobutene)를 포함하는 것을 특징으로 한다.The present invention is an organic compound for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric device, and comprises at least one benzocyclobutene group at the end thereof.
Description
본 발명은 OLED 적용에서 사용하기 위한 유기화학 조성물에 관한 것으로서, 특히, 가교결합성 벤조시클로부텐기를 갖는 유기전기소자용 화합물, 이를 이용한 유기전기소자 및 그 전자 장치에 관한 것이다. The present invention relates to an organic chemical composition for use in OLED applications, and more particularly, to a compound for an organic electric device having a cross-linkable benzocyclobutene group, an organic electric device using the same, and an electronic device thereof.
일반적으로 유기 발광 현상이란 유기 물질을 이용하여 전기에너지를 빛 에너지로 전환시켜주는 현상을 말한다. 유기 발광 현상을 이용하는 유기전기소자는 통상 양극과 음극 및 이 사이에 유기물층을 포함하는 구조를 가진다. 여기서 유기물 층은 유기전기소자의 효율과 안정성을 높이기 위하여 각기 다른 물질로 구성된 다층의 구조로 이루어진 경우가 많으며, 예컨대 정공주입층, 정공수송층, 발광층, 전자수송층 및 전자주입층 등으로 이루어질 수 있다. In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic electric device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.
유기전기소자에서 유기물층으로 사용되는 재료는 기능에 따라, 발광 재료와 전하수송 재료, 예컨대 정공주입 재료, 정공수송 재료, 전자수송 재료, 전자주입 재료 등으로 분류될 수 있다. A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.
본 발명에서 사용되는 용어 '유기전기소자'는, 유기 집적 회로(OIC), 유기 전계-효과 트랜지스터(OFET), 유기 박막 트랜지스터(OTFT), 유기 발광 트랜지스터(OLET), 유기 태양 전지(OSC), 유기 광검출기, 유기 광수용체, 유기 전계-켄치 소자(OFQD), 유기 발광 전기화학 전지(OLEC), 유기 레이저 다이오드(O-laser) 및 유기 전계 발광 소자(OLED) 등을 포함하는 것으로 정의된다. The term 'organic electronic device' used in the present invention includes an organic integrated circuit (OIC), an organic field-effect transistor (OFET), an organic thin film transistor (OTFT), an organic light emitting transistor (OLET), an organic solar cell (OSC), It is defined to include organic photodetectors, organic photoreceptors, organic electro-quenching devices (OFQDs), organic light emitting electrochemical cells (OLECs), organic laser diodes (O-lasers) and organic electroluminescent devices (OLEDs), and the like.
본 발명에서는 특히, OLED로서 지칭되는 유기전기소자에 사용되는 신규한 유기화합물을 제공하는 것에 관심이 있다. OLED의 일반 구조 및 이의 기능적 원리는 당업자에게 널리 공지되어 있고, 특히 US 4539507, US 5151629, EP 0676461 및 WO 1998/27136에 기재되어 있다. The present invention is particularly interested in providing novel organic compounds for use in organic electric devices referred to as OLEDs. The general structure of OLEDs and their functional principles are well known to the person skilled in the art and are described in particular in US 4539507, US 5151629, EP 0676461 and WO 1998/27136.
차세대 디스플레이 디바이스로 주목받고 있는 OLED(organic photoelectric device)는 ITO와 같은 투명 양극재가 코팅된 기판과 음극 사이에 유기발광층을 형성하여, 전극에 소정의 전압을 가하면 양극으로부터 주입된 정공과 음극으로부터 주입된 전자가 유기발광층에서 결합하여 빛을 방출하는 원리를 이용한 소자이다. OLED는 평판 디스플레이, 조명 및 백라이팅과 같은 전자 장치에 응용되면서 점점 관심을 받고 있다. OLED 기술은 Geffroy 등의, "유기 발광 다이오드 (OLED) 기술: 재료 소자 및 디스플레이 기술", Polym, Int., 55:572-582(2006)에서 설명되며, 미국 특허 제 5,844,363 호, 제 6,303,238 호 및 제 5,707,745 호에서 설명된 여러 OLED 재료 및 구성에서 설명되고, 이들 모두는 본 명세서에 참고로 인용된다. OLED (organic photoelectric device), which is attracting attention as a next-generation display device, forms an organic light emitting layer between a substrate coated with a transparent anode material such as ITO and a cathode. It is a device using the principle that electrons combine in an organic light emitting layer to emit light. OLEDs are receiving increasing attention for their applications in electronic devices such as flat panel displays, lighting and backlighting. OLED technology is described in Geffroy et al., "Organic Light Emitting Diode (OLED) Technology: Materials Devices and Display Technologies," Polym, Int., 55:572-582 (2006), and in US Pat. Nos. 5,844,363, 6,303,238 and 5,707,745, the various OLED materials and configurations described, all of which are incorporated herein by reference.
유기 전계 발광 소자(OLED)는 산업적으로 적용 가능한 수준의 성능을 구현하기 위하여 유기발광층 이외에 정공주입층, 정공수송층, 전자수송층, 전자주입층 및 발광층의 특성에 따라 전하차단층을 더 포함하여 다층 구조로 제작된다. An organic electroluminescent device (OLED) has a multilayer structure including a charge blocking layer according to the characteristics of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, and a light emitting layer in addition to an organic light emitting layer in order to realize industrially applicable level of performance. is made with
종래기술에서 유기전기소자(특히, OLED)를 구성하는 각 층들은 일반적으로 진공증착공정에 의해 형성된다. 일본 공개특허 제 2006-156847 호(특허문헌 1)는 유기 화합물 및 이를 진공증착법으로 기판에 증착시켜 단층구조의 유기막을 포함하는 유기전기소자를 제조하는 기술을 개시하고 있다. 진공증착법은 10-4 Torr 이하의 고진공 분위기에서 시료에 열을 가하여 승화시키고, 승화된 시료는 상대적으로 낮은 온도의 기판에서 고체로 성장하는 방식으로 박막을 형성시키는 원리이다. 그러나, 진공증착법은 증착장치가 크고 설치가 용이하지 못하며, 공정시 진공을 유지해야 하고, 공정 온도가 높으며, 특히 패턴을 위해 마스크를 사용하기 때문에 재료의 소비율이 높아 생산성이 낮고 제조비용이 많이 소비되기 때문에 대면적으로 유기전기소자를 제조하기 어렵다. In the prior art, each layer constituting an organic electric device (especially, OLED) is generally formed by a vacuum deposition process. Japanese Patent Laid-Open No. 2006-156847 (Patent Document 1) discloses an organic compound and a technique for manufacturing an organic electric device including an organic film having a single-layer structure by depositing the same on a substrate by vacuum deposition. The vacuum deposition method is a principle of forming a thin film by applying heat to a sample in a high vacuum atmosphere of 10 -4 Torr or less to sublimate it, and the sublimated sample is grown as a solid on a substrate at a relatively low temperature. However, in the vacuum deposition method, the deposition apparatus is large and not easy to install, the vacuum must be maintained during the process, the process temperature is high, and in particular, because a mask is used for the pattern, the material consumption rate is high, so the productivity is low and the manufacturing cost is high Therefore, it is difficult to manufacture an organic electric device in a large area.
이러한 문제점을 해소하기 위하여 저가의 용액공정을 통해 유기박막을 형성하고자 하는 연구가 꾸준히 진행되어왔다. 용액공정은 진공증착 공정에 비해 분해능이 높지 않은 단점이 있지만, 대기압과 대기 온도에서 제조가 가능하기 때문에 별도의 진공장치가 필요하지 않으며, 재료의 소비율이 낮기 때문에, 생산성이 높고, 제조비용이 적게 들며, 대면적화가 가능한 것이 장점이다.In order to solve this problem, research to form an organic thin film through a low-cost solution process has been continuously conducted. The solution process has the disadvantage of not having a high resolution compared to the vacuum deposition process, but since it can be manufactured at atmospheric pressure and atmospheric temperature, a separate vacuum device is not required. The advantage is that it can be expanded to a large area.
이와 같은 용액공정의 종류에는 스핀 코팅, 잉크젯 코팅, 스크린 프린팅, 스프레이 코팅, 롤 투 롤 코팅, 그리고 블레이드 코팅 등이 있다. 용액공정을 기반으로 한 대면적 유기 박막 제조 방법 및 그 장치에 대한 구체적인 예들은 대한민국 공개특허공보 제 2016-0069799 호, 대한민국 등록특허공보 제 10-1618395 호, 대한민국 공개특허공보 제 2017-0066703 호, 대한민국 등록특허공보 제 10-1618395 호, 대한민국 공개특허공보 제 2016-0141127 호 및 대한민국 공개특허공보 제 2016-0138845 호에 상세되어 있다. 또한, 사용될 수 있는 열프린팅 기술 및 장치는 예를 들면 미국 특허 출원 공개 US 2008/0311307 A1, US 2008/0308037 A1, US2006/0115585 A1, US 2010/0188457 A1, US 2011/0008541 A1, US 2010/0171780 A1, 및 US 2010/0201749 A1에 설명된 것들을 포함하며, 그 전체가 본 명세서에 참고로 인용된다.Such solution processes include spin coating, inkjet coating, screen printing, spray coating, roll-to-roll coating, and blade coating. Specific examples of a method for manufacturing a large-area organic thin film based on a solution process and an apparatus thereof are disclosed in Korean Patent Application Laid-Open No. 2016-0069799, Korean Patent Publication No. 10-1618395, Korean Patent Application Laid-Open No. 2017-0066703, It is detailed in Korean Patent Publication No. 10-1618395, Korean Patent Application Laid-Open No. 2016-0141127, and Korean Patent Publication No. 2016-0138845. In addition, thermal printing techniques and devices that can be used are described, for example, in US Patent Application Publications US 2008/0311307 A1, US 2008/0308037 A1, US2006/0115585 A1, US 2010/0188457 A1, US 2011/0008541 A1, US 2010/ 0171780 A1, and those described in US 2010/0201749 A1, which are incorporated herein by reference in their entirety.
그러나, 용액공정을 이용하여 유기전기소자용 다층 유기막을 코팅할 때, 위층의 유기 화합물에 포함된 유기용매에 의해 아래층의 유기박막이 손상되는 문제가 있어 다층 박막을 형성함에 어려움이 있다. 이를 해결하기 위해서는 가교가 가능한 작용기를 가지는 유기 화합물을 사용해야 하는데, 이제까지 알려진 가교기들은 스티렌(styrene), 아크릴레이트(acrylate), 옥세탄(oxetane) 등이다. 그러나, 이들 가교기들은 가교반응을 위해 높은 가교온도를 요구하고 있어서 플라스틱 기판을 사용하는데 있어 어려움이 있다. 또한, 자외선 가교의 경우에는 광개시제를 사용하거나 부산물(byproduct)이 발생하여 유기전기소자의 수명과 효율에 문제를 발생시키는 단점이 있다. However, when coating the multilayer organic film for an organic electric device using a solution process, there is a problem in that the organic thin film of the lower layer is damaged by the organic solvent contained in the organic compound of the upper layer, so it is difficult to form the multilayer thin film. In order to solve this problem, an organic compound having a cross-linking functional group must be used, and the known cross-linking groups are styrene, acrylate, oxetane, and the like. However, since these crosslinking groups require a high crosslinking temperature for the crosslinking reaction, it is difficult to use a plastic substrate. In addition, in the case of UV crosslinking, there is a disadvantage in that a photoinitiator is used or a byproduct is generated, which causes problems in the lifespan and efficiency of the organic electric device.
한편, 벤조시클로부텐(BCB : Benzocyclobutene)기는, 전형적으로 200℃ 이상에서 열적으로 활성화된 이량체화를 경험하는 일 부분의 예이고, 이 경우에, 시클로부텐의 C-C 결합 중 하나의 절단에 의해 형성된, 디벤조시클로옥타디엔 고리를 형성하고, 그 다음 비가역적 고리화가 부가된다. 이러한 시클로부텐 고리에서, 산소-기반 공여체의 치환이 BCB의 개환 온도에 관해 극적 효과를 가짐이 공개 문헌(Dobish, JN; Hamilton, SK; Harth, EPolymer Chemistry 2012, 3, 857-860)에서 문서로 기록되어 있다. 그러나, 이 현상은 OLED 적용에 아직 이용되지 않고 있다. On the other hand, a benzocyclobutene (BCB: Benzocyclobutene) group is an example of a moiety that typically undergoes thermally activated dimerization at 200° C. or higher, in this case formed by cleavage of one of the CC bonds of cyclobutene, A dibenzocyclooctadiene ring is formed, followed by irreversible cyclization. It is documented in publications (Dobish, JN; Hamilton, SK; Harth, EPolymer Chemistry 2012, 3, 857-860) that substitution of an oxygen-based donor in these cyclobutene rings has a dramatic effect on the ring opening temperature of the BCB. It is recorded. However, this phenomenon has not yet been exploited in OLED applications.
OLED에서 벤조시클로부텐(BCB) 화학 및 그의 용도는 하기 공개 문헌들에서 기재된다: US20040004433, US20080315757, US20080309229, US20100133566, US20110095278, US20110065222, US20110198573, US20110042661, JP2010062120, US7893160, US20110089411, US20070181874, US20070096082, CN102329411, US20120003790, WO2012052704, WO2012175975, WO2013007966, 국제출원 PCT/CN14/084918(8/21/14 출원), US 가출원 62/039935(8/21/14 출원)Benzocyclobutene (BCB) chemistry and its use in OLEDs are described in the following publications: US20040004433, US20080315757, US20080309229, US20100133566, US20110095278, US20110065222, US201100198573, US20110042661, JP2010062120, US7893160, US201100189411, US2007007002120, US20110089411, US2007000089411, US200 , WO2012052704, WO2012175975, WO2013007966, international application PCT/CN14/084918 (filed on 8/21/14), US provisional application 62/039935 (filed on 8/21/14)
특히, 대한민국 공개특허공보 제 2017-0043557 호(특허문헌 2)는 OLED 적용에서 사용을 위하여 가교결합성 BCB-작용화된 물질을 포함하는 조성물을 제공한다. 특허문헌 2의 조성물은 전계발광(electroluminescent) 디바이스에서 사용을 위하여 정공 전달(hole-transporting) 물질을 형성하기 위해 사용될 수 있다. 특히, 특허문헌 2는 아래의 [구조 A]로부터 선택된 적어도 하나의 화합물을 포함하는 조성물을 제공한다. 즉, 아래 [구조 A]로부터 선택된 적어도 하나의 화합물을 포함하는 조성물은 벤조시클로부텐으로 치환된 카르바졸을 함유하는 조성물일 수 있다. In particular, Korean Patent Publication No. 2017-0043557 (Patent Document 2) provides a composition comprising a crosslinkable BCB-functionalized material for use in OLED applications. The composition of Patent Document 2 may be used to form a hole-transporting material for use in an electroluminescent device. In particular, Patent Document 2 provides a composition comprising at least one compound selected from the following [Structure A]. That is, the composition including at least one compound selected from the following [Structure A] may be a composition containing carbazole substituted with benzocyclobutene.
[구조 A][Structure A]
그러나, 가교결합성 BCB-작용화된 물질을 포함하는 OLED 적용에서 사용을 위한 새롭고도 신규한 유기전기소자용 화합물의 필요성은 여전하다. 이들 필요성은 본 발명에 의하여 충족되고 있다. However, there remains a need for new and novel organic electrophoretic compounds for use in OLED applications comprising crosslinkable BCB-functionalized materials. These needs are met by the present invention.
본 발명이 이루고자 하는 기술적 과제는 OLED 적용에 사용하기 적합한 가교결합성 BCB-작용화된 물질을 포함하는 새롭고도 신규한 유기전기소자용 화합물을 제공하는 것이다. The technical task to be achieved by the present invention is to provide novel and novel compounds for organic electronic devices comprising crosslinkable BCB-functionalized materials suitable for use in OLED applications.
또한, 본 발명은 120℃ 이하의 낮은 온도에서 가교가 가능하고, 부산물(byproduct)을 발생시키지 않아 효율과 수명 특성이 우수한 신규한 유기전기소자용 화합물 및 이 화합물을 제조하는 방법을 제공하는 것이다. In addition, the present invention is to provide a novel compound for an organic electric device, which can be cross-linked at a low temperature of 120° C. or less, and has excellent efficiency and lifespan characteristics by not generating a byproduct, and a method for preparing the compound.
특히, 본 발명은 120℃ 정도의 낮은 온도에서 가열을 통해 가교결합이 발생되고, 이로 인해 유기용매에 용해되지 않는 유기전기소자용 유기박막을 제공하는 것을 다른 일 목적으로 한다. In particular, another object of the present invention is to provide an organic thin film for an organic electric device that is cross-linked through heating at a low temperature of about 120° C. and is not soluble in an organic solvent.
또한, 본 발명은 이러한 유기박막을 다층 적층하여 형성되는 OLED를 포함하는 유기전기소자 및 이 유기전기소자를 포함하는 전자장치를 제공하는 것을 또 다른 일 목적으로 한다. In addition, another object of the present invention is to provide an organic electric device including an OLED formed by stacking such an organic thin film in multiple layers, and an electronic device including the organic electric element.
본 발명이 이루고자 하는 기술적 과제는 이상에서 언급한 기술적 과제로 제한되지 않으며, 언급되지 않은 또 다른 기술적 과제들은 아래의 기재로부터 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에게 명확하게 이해될 수 있을 것이다.The technical problems to be achieved by the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned can be clearly understood by those of ordinary skill in the art to which the present invention belongs from the description below. There will be.
상기한 기술적 과제를 달성하기 위한 본 발명의 제 1 양태는 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서,상기 유기화합물은, 아래 [구조식 A]로부터 선택된 적어도 하나의 화합물을 포함하는 것을 특징으로 한다. A first aspect of the present invention for achieving the above technical problem is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, The organic compound is, It is characterized in that it comprises at least one compound selected from
[구조식 A][Structure A]
상기 [구조식 A]에서, R1, R2, R3, R4, R5, R6, R7, R8, R9는 서로 같거나 상이하고, 각각 독립적으로 수소, 알킬기(alkyl group), 치환된 알킬기(alkyl group), 헤테로사이클로기(heterocyclic group), 치환된 헤테로사이클로기(heterocyclic group), 아릴기(aryl group), 치환된 아릴기(aryl group), 아민기(amine group)으로부터 선택되고; In the [Structural Formula A], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are the same as or different from each other, and each independently hydrogen, an alkyl group (alkyl group) , a substituted alkyl group, a heterocyclo group, a substituted heterocyclic group, an aryl group, a substituted aryl group, an amine group from selected;
상기 R1, R2, R3, R4, R5, R6, R7, R8, R9중 선택된 적어도 2곳 이상에는 아래 [구조식 B]의 벤조시클로부텐기(benzocyclobutene)가 직접 적용되거나 수소, 알킬기(alkyl group), 치환된 알킬기(alkyl group), 헤테로사이클로기(heterocyclic group), 치환된 헤테로사이클로기(heterocyclic group), 아릴기(aryl group), 치환된 아릴기(aryl group), 아민기(amine group) 등에 아래 [구조식 B]의 벤조시클로부텐기(benzocyclobutene)로 치환된 유도체가 적용되며; The R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 A benzocyclobutene group of the following [Structural Formula B] is directly applied to at least two places selected from the group consisting of: or hydrogen, an alkyl group, a substituted alkyl group, a heterocyclic group, a substituted heterocyclic group, an aryl group, a substituted aryl group , a derivative substituted with a benzocyclobutene group of the following [Structural Formula B] is applied to an amine group;
[구조식 B][Structural Formula B]
상기 [구조식 B]에서, Y는 수소 또는 탄화수소, 특히, C1~C13의 탄소 체인을 가진 알킬기 또는 치환된 알칼기, 수소, 아민 또는 할로겐을 가지고 있는 알킬기이고, X1, X2, X3, X4, X5는 서로 같거나 상이하고, 각각 독립적으로 수소, 탄화수소, 치환된 탄화수소, 할로겐, 시아노, 니트로, 하이드록실, 알콕시, 아민 또는 치환된 아민, 카보닐로부터 선택된다. In the above [Formula B], Y is hydrogen or hydrocarbon, in particular, an alkyl group having a C 1 ~ C 13 carbon chain or an alkyl group having a substituted alkali group, hydrogen, amine or halogen, X 1 , X 2 , X 3 , X 4 , X 5 are the same as or different from each other and are each independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, halogen, cyano, nitro, hydroxyl, alkoxy, amine or substituted amine, carbonyl.
상기 [구조식 A]는 아래의 [화학식 a] 내지 [화학식 k]로부터 선택될 수 있다. The [Structural Formula A] may be selected from the following [Formula a] to [Formula k].
[화학식 a][Formula a]
[화학식 b][Formula b]
[화학식 c][Formula c]
[화학식 d][Formula d]
[화학식 e][Formula e]
[화학식 f][Formula f]
[화학식 g][Formula g]
[화학식 h][Formula h]
[화학식 i][Formula i]
[화학식 j][Formula j]
[화학식 k][Formula k]
본 발명의 다른 제 2 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다. Another second aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 3 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다. Another third aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
본 발명의 다른 제 4 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another fourth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 5 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another fifth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 6 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another sixth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 7 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another seventh aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 8 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another eighth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 9 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another ninth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
본 발명의 다른 제 10 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another tenth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of the organic electric device, characterized in that it has the following chemical formula.
본 발명의 다른 제 11 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another eleventh aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
본 발명의 다른 제 12 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another twelfth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
본 발명의 다른 제 13 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another thirteenth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
본 발명의 다른 제 14 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another fourteenth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
본 발명의 다른 제 15 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 유기화합물으로서, 아래의 화학식을 갖는 것을 특징으로 한다.Another fifteenth aspect of the present invention is an organic compound for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, and has the following chemical formula.
상기 유기화합물은 유기전기소자용 유기박막 재료중 발광층 물질, 정공주입층 물질, 정공수송층 물질, 전자주입층 물질, 전자수송층 물질, 전자차단층 물질 및 정공차단층 물질로 이루어진 군으로부터 선택된 적어도 하나의 용도로 사용되는 것을 특징으로 한다. The organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material among organic thin film materials for an organic electric device It is characterized in that it is used for the purpose.
본 발명의 또 다른 제 16 양태는, 유기전기소자의 제1전극과 제2전극 사이에 배치되는 유기박막을 형성하기 위한 잉크 조성물로서, 상기 잉크 조성물은 상기 제 1 양태 내지 제 15 양태중 선택된 어느 하나의 유기화합물을 포함하는 것을 특징으로 한다. Another sixteenth aspect of the present invention is an ink composition for forming an organic thin film disposed between the first electrode and the second electrode of an organic electric device, wherein the ink composition is any one selected from the first to fifteenth aspects It is characterized in that it contains an organic compound of
상기 잉크 조성물은 용매를 더 포함하는 용액 또는 현탁액인 것을 특징으로 한다. 또한, 상기 잉크 조성물은 안료 또는 염료를 더 포함할 수 있다. The ink composition is characterized in that it is a solution or suspension further containing a solvent. In addition, the ink composition may further include a pigment or dye.
상기 잉크 조성물은 인광 도펀트 또는 형광 도펀트를 더 포함할 수도 있다. The ink composition may further include a phosphorescent dopant or a fluorescent dopant.
본 발명의 또 다른 제 17 양태는, 음극과 양극 사이에 적어도 발광층을 포함하는 일층 또는 복수층으로 이루어지는 유기 박막층이 협지되어 있는 유기전기소자에 있어서, 상기 유기 박막층을 형성하기 위한 유기화합물이 상기 제 1 양태 내지 제 15 양태중 선택된 어느 하나의 유기화합물을 포함하는 것을 특징으로 한다. Another seventeenth aspect of the present invention is an organic electric device in which an organic thin film layer comprising at least a light emitting layer or a plurality of layers is sandwiched between a cathode and an anode, wherein the organic compound for forming the organic thin film layer comprises the first It is characterized in that it contains any one organic compound selected from the first aspect to the fifteenth aspect.
상기 유기 박막층을 형성하는 유기화합물의 말단의 벤조시클로부텐기(benzocyclobutene)간에 가교결합이 형성된다. A crosslink is formed between benzocyclobutene groups at the ends of the organic compound forming the organic thin film layer.
상기 유기 박막층은 발광층, 정공주입층, 정공수송층, 전자주입층, 전자수송층, 전자차단층 및 정공차단층으로 이루어진 군으로부터 선택된 적어도 하나이고, 양극, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 및 음극이 이 순서대로 적층된 구조를 갖는다. The organic thin film layer is at least one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer and a hole blocking layer, and an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, It has a structure in which the electron injection layer and the cathode are stacked in this order.
또한, 상기 유기 박막층은 상기 유기화합물을 포함하는 잉크 조성물을 용액 공정에 의해 도포하고 건조시켜 성막하여 제조된 것을 특징으로 한다. In addition, the organic thin film layer is characterized in that it is prepared by coating the ink composition containing the organic compound by a solution process and drying it to form a film.
본 발명의 또 다른 제 18 양태는, 상기 제 17 양태에 따른 유기전기소자를 포함하는 전자기기에 관한 것이다. Another eighteenth aspect of the present invention relates to an electronic device including the organic electric device according to the seventeenth aspect.
본 발명의 일 실시예에 따르면, 유기전기소자용 화합물에 BCB-가교결합성 치환기를 구비함으로써 용해도가 낮은 저분자 유기 화합물의 용해성을 향상시킬 수 있고, 용해성이 증진됨에 따라 생산성이 높은 용액 공정에 적용할 수 있다는 제1효과, 유기화합물에 BCB-가교결합성 치환기를 적어도 2개 이상 구비하는 경우, 비교적 낮은 온도(150℃ 이하)에서 BCB-가교결합성 치환기간의 가교결합으로 안정한 유기박막을 형성할 수 있다는 제2효과, 용액공정을 통해 다층 구조의 유기박막층을 형성하여도 인접한 층이 용액에 의해 용해되는 현상 없이 안정한 다층구조의 소자제작이 가능하다는 제3효과, 유기소자의 대면적화 및 저비용화가 가능하다는 제4효과를 갖는다.According to an embodiment of the present invention, by providing a BCB-crosslinking substituent in a compound for an organic electric device, the solubility of a low molecular weight organic compound with low solubility can be improved, and as the solubility is improved, it is applied to a solution process with high productivity The first effect is that, when an organic compound has at least two BCB-crosslinking substituents, a stable organic thin film is formed by crosslinking of the BCB-crosslinking substituents at a relatively low temperature (150° C. or less). The second effect that a multi-layered organic film layer can be formed through a solution process, but the third effect that a stable multi-layered device can be manufactured without the phenomenon that adjacent layers are dissolved by the solution, the large area of the organic device and low cost It has the fourth effect that painting is possible.
본 발명에 따른 유기화합물은 가교결합이 가능한 BCB 치환기를 구비함으로써 각종 용매에 대한 용해성이 향상될 수 있다. 또한, 종래기술에서 저분자 유기화합물은 용해성이 떨어지는 문제로 인하여 주로 증착공정을 통해 유기박막을 형성하였는데, 본 발명에 따른 유기화합물은 용해성의 향상으로 각종 용액공정에 적합한 특성을 제공할 수 있다. The organic compound according to the present invention may have improved solubility in various solvents by having a BCB substituent capable of crosslinking. In addition, in the prior art, low molecular weight organic compounds have poor solubility, so organic thin films are mainly formed through a deposition process. The organic compounds according to the present invention can provide properties suitable for various solution processes by improving solubility.
또한, 종래기술에서는 용액공정을 통해 유기박막을 형성하더라도, 안정한 유기박막을 형성하기 위하여 고온 조건에서 수행하여야 하는 문제점이 있었다. 그러나 본 발명에 따른 유기화합물은 용매에 대한 용해성이 우수할 뿐만 아니라, 화합물에 구비된 BCB 치환기간의 가교결합으로 저온공정으로도 열에 안정한 박막을 형성할 수 있기 때문에 유기소자의 대량생산, 대면적화 및 저비용화를 가능케 할 수 있는 것이다. In addition, in the prior art, even if an organic thin film is formed through a solution process, there is a problem in that it must be performed under high temperature conditions in order to form a stable organic thin film. However, the organic compound according to the present invention not only has excellent solubility in solvents, but also can form a heat-stable thin film even at a low temperature process due to crosslinking of the BCB substitution period provided in the compound. and cost reduction.
본 발명의 효과는 상기한 효과로 한정되는 것은 아니며, 본 발명의 상세한 설명 또는 특허청구범위에 기재된 발명의 구성으로부터 추론 가능한 모든 효과를 포함하는 것으로 이해되어야 한다.It should be understood that the effects of the present invention are not limited to the above-described effects, and include all effects that can be inferred from the configuration of the invention described in the detailed description or claims of the present invention.
이하에서 본 발명의 구현예를 상세하게 설명하기로 한다. 그러나 본 발명은 여러 가지 상이한 형태로 구현될 수 있으며, 따라서 여기에서 설명하는 실시예로 한정되는 것은 아니다. Hereinafter, embodiments of the present invention will be described in detail. However, the present invention may be embodied in several different forms, and thus is not limited to the embodiments described herein.
명세서 전체에서, 어떤 부분이 다른 부분과 "연결(접속, 접촉, 결합)"되어 있다고 할 때, 이는 "직접적으로 연결"되어 있는 경우뿐 아니라, 그 중간에 다른 부재를 사이에 두고 "간접적으로 연결"되어 있는 경우도 포함한다. 또한, 어떤 부분이 어떤 구성요소를 "포함"한다고 할 때, 이는 특별히 반대되는 기재가 없는 한 다른 구성요소를 제외하는 것이 아니라 다른 구성요소를 더 구비할 수 있다는 것을 의미한다. Throughout the specification, when a part is said to be “connected (connected, contacted, coupled)” with another part, it is not only “directly connected” but also “indirectly connected” with another member interposed therebetween. "Including cases where In addition, when a part "includes" a certain component, this means that other components may be further provided, rather than excluding other components, unless otherwise stated.
본 명세서에서 사용한 용어는 단지 특정한 실시예를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 명세서에서, "포함하다" 또는 "가지다" 등의 용어는 명세서상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. The terminology used herein is used only to describe specific embodiments, and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It should be understood that this does not preclude the existence or addition of numbers, steps, operations, components, parts, or combinations thereof.
명세서에서 사용한 용어는 단지 특정한 구현예(태양, 態樣, aspect)(또는 실시예)를 설명하기 위해 사용된 것으로, 본 발명을 한정하려는 의도가 아니다. 단수의 표현은 문맥상 명백하게 다르게 뜻하지 않는 한, 복수의 표현을 포함한다. 본 출원에서, ~포함하다~ 또는 ~이루어진다~ 등의 용어는 명세서 상에 기재된 특징, 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것이 존재함을 지정하려는 것이지, 하나 또는 그 이상의 다른 특징들이나 숫자, 단계, 동작, 구성요소, 부분품 또는 이들을 조합한 것들의 존재 또는 부가 가능성을 미리 배제하지 않는 것으로 이해되어야 한다. 다르게 정의되지 않는 한, 기술적이거나 과학적인 용어를 포함해서 여기서 사용되는 모든 용어들은 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자에 의해 일반적으로 이해되는 것과 동일한 의미를 가지고 있다. 일반적으로 사용되는 사전에 정의되어 있는 것과 같은 용어들은 관련 기술의 문맥 상 가지는 의미와 일치하는 의미를 가지는 것으로 해석되어야 하며, 본 출원에서 명백하게 정의하지 않는 한, 이상적이거나 과도하게 형식적인 의미로 해석되지 않는다. The terminology used in the specification is used only to describe a specific embodiment (aspect, aspect, aspect) (or embodiment), and is not intended to limit the present invention. The singular expression includes the plural expression unless the context clearly dictates otherwise. In the present application, terms such as comprises or consists of are intended to designate that the features, numbers, steps, operations, components, parts, or combinations thereof described in the specification exist, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Unless defined otherwise, all terms used herein, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Terms such as those defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related art, and should not be interpreted in an ideal or excessively formal meaning unless explicitly defined in the present application. does not
이하, 구조화된 화학식 등을 참조하여 본 발명의 실시예를 구체적으로 설명하기로 한다. Hereinafter, embodiments of the present invention will be described in detail with reference to structured chemical formulas and the like.
가교결합성 BCB-작용화된 물질은 종래의 OLED 적용에서도 발견되어 왔다. 본 발명에서는 벤조시클로부텐 화합물의 고리상에 다양한 작용기(예를 들어, 산소 공여체, 수산기, 아미노기 등)를 치환시키는 것에 의해 개환 온도(temperature of ring opening)를 150℃ 이하, 특히, 120℃ 이하의 저온으로 낮출 수 있고, 이로인해, OLED 적용에서의 용액-공정 조건을 충분히 만족시킬 수 있음을 알았다. 특히, 산소 공여체의 치환은 벤조시클로부텐 화합물의 개환 온도를 100~120℃로 유의미하게 감소시킬 수 있어 유의미한 공정 잇점을 가질 수 있다. Crosslinkable BCB-functionalized materials have also been found in conventional OLED applications. In the present invention, by substituting various functional groups (for example, oxygen donor, hydroxyl group, amino group, etc.) on the ring of the benzocyclobutene compound, the temperature of ring opening is 150 ° C. or less, in particular, 120 ° C. or less. It was found that it can be lowered to a low temperature, thereby sufficiently satisfying the solution-processing conditions in OLED applications. In particular, substitution of the oxygen donor can significantly reduce the ring-opening temperature of the benzocyclobutene compound to 100-120° C., which can have significant process advantages.
구체적으로 본 발명은 OLED 적용을 위한 유기박막을 형성하는 코어 물질의 말단에 적어도 2개 이상의 벤조시클로부텐 가교결합성 유도체를 포함하는 유기화합물에 관한 것이다. 특히, 본 발명에 따른 유기화합물은 아래 [구조식 1]로부터 선택된 적어도 하나의 화합물을 포함하는 조성물을 제공한다. Specifically, the present invention relates to an organic compound comprising at least two or more benzocyclobutene crosslinking derivatives at the end of a core material forming an organic thin film for OLED application. In particular, the organic compound according to the present invention provides a composition comprising at least one compound selected from the following [Structural Formula 1].
[구조식 1][Structural Formula 1]
상기 [구조식 1]에서, R1, R2, R3, R4, R5, R6, R7, R8, R9는 서로 같거나 상이하고, 각각 독립적으로 수소, 알킬기(alkyl group), 치환된 알킬기(alkyl group), 헤테로사이클로기(heterocyclic group), 치환된 헤테로사이클로기(heterocyclic group), 아릴기(aryl group), 치환된 아릴기(aryl group), 아민기(amine group) 등으로부터 선택된다. In the [Structural Formula 1], R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 are the same as or different from each other, and each independently hydrogen, an alkyl group (alkyl group) , a substituted alkyl group, a heterocyclo group, a substituted heterocyclic group, an aryl group, a substituted aryl group, an amine group, etc. is selected from
특히, 상기 R1, R2, R3, R4, R5, R6, R7, R8, R9중 선택된 적어도 2곳 이상에는 아래 [구조식 2]의 벤조시클로부텐기(benzocyclobutene)가 직접 적용되거나 수소, 알킬기(alkyl group), 치환된 알킬기(alkyl group), 헤테로사이클로기(heterocyclic group), 치환된 헤테로사이클로기(heterocyclic group), 아릴기(aryl group), 치환된 아릴기(aryl group), 아민기(amine group) 등에 아래 [구조식 2]의 벤조시클로부텐기(benzocyclobutene)로 치환된 유도체가 적용될 수 있다. In particular, in at least two places selected from among R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , and R 9 , a benzocyclobutene group of the following [Formula 2] is Directly applied or applied to hydrogen, an alkyl group, a substituted alkyl group, a heterocyclic group, a substituted heterocyclic group, an aryl group, a substituted aryl group group), an amine group, etc. may be applied to a derivative substituted with a benzocyclobutene group of [Structural Formula 2] below.
[구조식 2][Structural Formula 2]
상기 [구조식 2]에서, Y는 수소 또는 탄화수소, 특히, C1~C13의 탄소 체인을 가진 알킬기 또는 치환된 알칼기, 수소, 아민 또는 할로겐을 가지고 있는 알킬기이고, X1, X2, X3, X4, X5는 서로 같거나 상이하고, 각각 독립적으로 수소, 탄화수소, 치환된 탄화수소, 할로겐, 시아노, 니트로, 하이드록실, 알콕시, 아민 또는 치환된 아민, 카보닐로부터 선택된다.In the [Structural Formula 2], Y is hydrogen or hydrocarbon, in particular, an alkyl group having a C 1 to C 13 carbon chain or an alkyl group having a substituted alkali group, hydrogen, amine or halogen, X 1 , X 2 , X 3 , X 4 , X 5 are the same as or different from each other and are each independently selected from hydrogen, hydrocarbon, substituted hydrocarbon, halogen, cyano, nitro, hydroxyl, alkoxy, amine or substituted amine, carbonyl.
본 발명에서 적용 가능한 상기 헤테로사이클로기(heterocyclic group)의 예로는 테트라히드로푸란(tetrahyrofuran), 싸이오펜(thiophene), 피리딘(pyridine), 피리미딘(pyrimidine), 벤조싸이오펜(benzothiophene), 벤조푸란(benzofuran), 디벤조푸란(dibenzofuran) 등을 포함한다.Examples of the heterocyclic group applicable in the present invention include tetrahydrofuran, thiophene, pyridine, pyrimidine, benzothiophene, benzofuran ( benzofuran), dibenzofuran (dibenzofuran), and the like.
또한, 본 발명에서 적용 가능한 상기 아릴기(aryl group)의 예로는 페닐(phenyl), 나프틸(naphthyl), 페난트릴(phenanthryl), 피렌일(pyrenyl), 플루오렌일(fluorenyl), 카바조일(cabazolyl), 스피로바이플루오렌(spirobifluorene), 테트라페닐실란(traphenylsilane), 테트라페닐메탄(tetraphenylmethane) 등을 포함한다. In addition, examples of the aryl group applicable in the present invention include phenyl, naphthyl, phenanthryl, pyrenyl, fluorenyl, carbazoyl ( cabazolyl), spirobifluorene, tetraphenylsilane, tetraphenylmethane, and the like.
또한, 본 발명에서 적용 가능한 아민기(amine group)의 예로는 디페닐아민(diphenylamine), 트리페닐아민(triphenylamine) 등을 포함한다.In addition, examples of the amine group applicable in the present invention include diphenylamine, triphenylamine, and the like.
본 발명에 따른 상기 [구조식 2]로 표현되는 유기화합물은 유기전기소자의 제1전극과 제2전극 사이에 배치되는 각종 유기박막을 형성하기 위한 발광층(EML)물질, 정공주입층(HIL) 물질, 정공수송층(HTL) 물질, 전자주입층(EIL) 물질, 전자수송층(ETL) 물질, 전자차단층(EBL) 물질 및 정공차단층(HBL) 물질 등에 다각적으로 사용될 수 있다. The organic compound represented by the [Structural Formula 2] according to the present invention is a light emitting layer (EML) material and a hole injection layer (HIL) material for forming various organic thin films disposed between the first electrode and the second electrode of the organic electric device. , a hole transport layer (HTL) material, an electron injection layer (EIL) material, an electron transport layer (ETL) material, an electron blocking layer (EBL) material, a hole blocking layer (HBL) material, and the like.
본 발명에 따른 유기화합물은 120℃ 정도의 낮은 온도에서 가열되는 것에 의해 상기 [구조식 2]의 벤조시클로부텐기(benzocyclobutene group)간에 열이성질체화(thermal isomerization) 반응을 통해 가교 결합을 발생시킨다. When the organic compound according to the present invention is heated at a low temperature of about 120° C., cross-linking occurs through a thermal isomerization reaction between the benzocyclobutene groups of [Structural Formula 2].
이로 인해, 본 발명에 따른 유기화합물로 이루어진 유기박막의 경우 인접한 유기박막층의 유기용매에 용해되지 않기 때문에 용액공정을 통해 다층의 박막을 적층하더라도 박막이 손상되지 않아 대면적의 다층 구조의 유기전기소자를 제작하는데 최적화된다. For this reason, since the organic thin film made of the organic compound according to the present invention does not dissolve in the organic solvent of the adjacent organic thin film layer, the thin film is not damaged even when multi-layered thin films are stacked through a solution process. optimized for making
본 발명의 일 구현예에서, 상기 [구조식 1]로 표현되는 본 발명의 유기화합물의 구체적인 예를 들면, 아래의 [화학식 1] 내지 [화학식 22]로부터 선택될 수 있다. In one embodiment of the present invention, specific examples of the organic compound of the present invention represented by the [Structural Formula 1] may be selected from the following [Formula 1] to [Formula 22].
본 발명의 다른 구현예에서, 본 발명에 따른 상기 [구조식 1]에 따른 유기화합물, 특히, 상기 [화학식 1] 내지 [화학식 25]의 유기화합물을 포함하는 잉크 조성물을 제공한다.In another embodiment of the present invention, there is provided an ink composition comprising the organic compound according to the [Structural Formula 1] according to the present invention, in particular, the organic compound of the [Formula 1] to [Formula 25].
상기 잉크 조성물은 용매를 포함하는 용액 또는 현탁액일 수 있고, 상기 용매는, 예를 들어, 아니솔, 디메틸 아니솔, 크실렌, o-크실렌, m-크실렌, p-크실렌, 톨루엔, 메시틸렌, 메틸 벤조에이트, 다이옥산, 테트라하이드로 퓨란, 메틸 테트라하이드로퓨란, 테트라하이드로 피란, 테트랄린, 베라트롤, 클로로벤젠, N-메틸 피롤리돈, N,N-디메틸포름아마이드, 디메틸술폭사이드 및 이들의 조합으로 이루어진 군으로부터 선택된 하나를 포함할 수 있다. The ink composition may be a solution or suspension containing a solvent, and the solvent is, for example, anisole, dimethyl anisole, xylene, o-xylene, m-xylene, p-xylene, toluene, mesitylene, methyl. Benzoate, dioxane, tetrahydrofuran, methyl tetrahydrofuran, tetrahydropyran, tetralin, veratrol, chlorobenzene, N-methyl pyrrolidone, N,N-dimethylformamide, dimethylsulfoxide and combinations thereof It may include one selected from the group consisting of.
상기 잉크 조성물을 도포한 뒤 용매를 제거하여 성막함으로써 유기 박막층을 형성할 수 있다. 상기 잉크 조성물은 안료 또는 염료를 더 포함할 수 있다. 상기 잉크 조성물은 인광 도펀트 또는 형광 도펀트를 더 포함할 수도 있다. An organic thin film layer may be formed by coating the ink composition and then forming a film by removing the solvent. The ink composition may further include a pigment or dye. The ink composition may further include a phosphorescent dopant or a fluorescent dopant.
본 발명의 또 다른 구현예에서, 음극과 양극 사이에 적어도 발광층을 포함하는 일층 또는 복수층으로 이루어지는 유기 박막층이 다층으로 적층되어 있는 유기전기소자에 있어서, 상기 유기 박막층 중 적어도 1층이 상기 [구조식 1]에 따른 유기화합물, 특히, 상기 [화학식 1] 내지 [화학식 25]의 유기화합물을 함유하는 것을 특징으로 하는 유기전기소자를 제공한다. 특히, 상기 유기전기소자는 유기전계발광소자(OLED)인 것이 바람직하다. In another embodiment of the present invention, in the organic electric device in which an organic thin film layer comprising at least a light emitting layer or a plurality of layers is stacked between the cathode and the anode in a multi-layered manner, at least one of the organic thin film layers is the [Structural formula The organic compound according to 1], in particular, the [Formula 1] to [Formula 25] provides an organic electric device characterized in that it contains the organic compound. In particular, the organic electric device is preferably an organic electroluminescent device (OLED).
상기 유기 박막층은 본 발명에 따른 유기화합물을 포함하는 상술한 잉크 조성물을 이용하여 용액공정으로 성막하여 제조될 수 있다. 이러한 용액 공정은 스핀코팅, 그라비아 옵셋 인쇄, 리버스 옵셋 인쇄, 스크린 인쇄, 롤투롤 인쇄, 슬롯다이코팅, 침지코팅, 스프레이코팅, 닥터블레이드 코팅, 잉크젯 코팅으로 이루어지는 군으로부터 선택되는 어느 하나의 방법을 포함한다. The organic thin film layer may be prepared by forming a film through a solution process using the above-described ink composition including the organic compound according to the present invention. This solution process includes any one method selected from the group consisting of spin coating, gravure offset printing, reverse offset printing, screen printing, roll-to-roll printing, slot die coating, dip coating, spray coating, doctor blade coating, and inkjet coating. do.
상기 유기 박막층은 상기 유기화합물이 발광층 물질, 정공주입층 물질, 정공수송층 물질, 전자주입층 물질, 전자수송층 물질, 전자차단층 물질 및 정공차단층 물질로 이루어진 군으로부터 선택된 적어도 하나를 포함하여 형성된 층을 포함할 수 있다. 상기 발광층 물질은 인광 또는 형광 호스트 및 인광 도펀트 또는 형광 도펀트 물질일 수 있다. The organic thin film layer is a layer in which the organic compound includes at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material. may include The light emitting layer material may be a phosphorescent or fluorescent host and a phosphorescent dopant or fluorescent dopant material.
특히, 상기 유기전계발광소자(OLED)는 양극, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 및 음극이 이 순서대로 적층된 구조를 가질 수 있다. 상기 발광층은 본 발명에 따른 유기화합물과 함께, 적색, 녹색, 청색 또는 백색을 포함하는 인광 도펀트 또는 형광 도펀트를 포함할 수 있다. 예를 들어, 상기 인광 도펀트는 Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb 및 Tm으로 이루어진 군으로부터 선택된 하나 이상의 원소를 포함하는 유기금속화합물일 수 있다. In particular, the organic light emitting diode (OLED) may have a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are stacked in this order. The light emitting layer may include a phosphorescent dopant or a fluorescent dopant including red, green, blue, or white together with the organic compound according to the present invention. For example, the phosphorescent dopant may be an organometallic compound including at least one element selected from the group consisting of Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb and Tm.
상기 정공수송층, 정공주입층, 정공차단층, 전자주입수송층, 전자수송층, 전자주입층 및 전자차단층은 전술한 본 발명에 따른 유기화합물을 포함할 수 있다. The hole transport layer, the hole injection layer, the hole blocking layer, the electron injection transport layer, the electron transport layer, the electron injection layer and the electron blocking layer may include the organic compound according to the present invention described above.
이하에서, 본 발명에 따른 유기전기소자로서 유기전계발광소자에 대하여 예를들어 설명한다. 본 발명의 유기전계발광소자는 양극(정공주입전극), 정공주입층(HIL) 및/또는 정공수송층(HTL), 발광층(EML) 및 음극(전자주입전극)이 순차적으로 적층된 구조를 가질 수 있으며, 바람직하게는, 양극과 발광층 사이에 전자차단층(EBL)을, 그리고 음극과 발광층 사이에 전자수송층(ETL), 전자주입층(EIL) 또는 정공차단층(HBL)을 추가로 포함할 수 있다. Hereinafter, an organic electroluminescent device as an organic electric device according to the present invention will be described as an example. The organic electroluminescent device of the present invention may have a structure in which an anode (hole injection electrode), a hole injection layer (HIL) and/or a hole transport layer (HTL), a light emitting layer (EML) and a cathode (electron injection electrode) are sequentially stacked. and, preferably, an electron blocking layer (EBL) between the anode and the light emitting layer, and an electron transport layer (ETL), an electron injection layer (EIL) or a hole blocking layer (HBL) between the cathode and the light emitting layer. have.
본 발명에 따른 유기전계발광소자의 제조방법으로는, 먼저 기판 표면에 양극용 물질을 통상적인 방법으로 코팅하여 양극을 형성한다. 이때, 사용되는 기판은 투명성, 표면 평활성, 취급 용이성 및 방수성이 우수한 유리기판 또는 투명 플라스틱 기판이 바람직하다. 또한, 양극용 물질로는 투명하고 전도성이 우수한 산화인듐주석(ITO), 산화인듐아연(IZO), 산화주석(SnO2), 산화아연(ZnO) 등이 사용될 수 있다. In the method of manufacturing an organic light emitting diode according to the present invention, first, a material for an anode is coated on the surface of a substrate in a conventional manner to form an anode. In this case, the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), zinc oxide (ZnO), etc. which are transparent and have excellent conductivity may be used.
다음으로, 상기 양극 표면에 정공주입층(HIL) 물질을 스핀 코팅하여 정공주입층을 형성하고, 상기 정공주입층 표면에 정공수송층(HTL) 물질을 스핀 코팅하여 정공수송층을 형성하고, 상기 정공수송층 표면에 발광층(EML) 물질을 스핀 코팅하여 발광층을 형성하고, 상기 발광층 표면에 전자수송층(ETL) 물질을 스핀 코팅하여 전자수송층을 형성한다. Next, a hole injection layer (HIL) material is spin coated on the surface of the anode to form a hole injection layer, and a hole transport layer (HTL) material is spin coated on the surface of the hole injection layer to form a hole transport layer, and the hole transport layer An emission layer is formed by spin-coating an EML material on the surface, and an electron transport layer (ETL) material is spin-coated on the surface of the emission layer to form an electron transport layer.
이때, 선택적으로는, 발광층과 전자수송층 사이에 정공차단층(HBL)을 추가로 형성하고 발광층에 인광 도펀트를 함께 사용함으로써, 삼중항 여기자 또는 정공이 전자수송층으로 확산되는 현상을 방지할 수 있다. 정공차단층의 형성은 정공차단층 물질을 스핀 코팅하여 실시할 수 있으며, 정공차단층 물질의 경우 본 발명의 유기화합물이 사용될 수 있다. At this time, optionally, by additionally forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant together in the light emitting layer, it is possible to prevent the phenomenon of triplet excitons or holes from being diffused into the electron transport layer. The hole blocking layer may be formed by spin coating the hole blocking layer material, and in the case of the hole blocking layer material, the organic compound of the present invention may be used.
상기 전자수송층 표면에 전자주입층(EIL) 물질을 스핀 코팅하여 전자주입층을 형성한다. 마지막으로, 상기 전자주입층 표면에 음극용 물질을 통상적인 방법으로 진공 열증착하여 음극을 형성한다. 이때, 사용되는 음극용 물질로는 리튬(Li), 알루미늄(Al), 알루미늄-리튬(Al-Li), 칼슘(Ca), 마그네슘(Mg), 마그네슘-인듐(Mg-In), 마그네슘-은(Mg-Ag) 등이 사용될 수 있다. 또한, 전면발광 유기전계발광소자의 경우 산화인듐주석(ITO) 또는 산화인듐아연(IZO)를 사용하여 빛이 투과할 수 있는 투명한 음극을 형성할 수도 있다. An electron injection layer is formed by spin coating an electron injection layer (EIL) material on the surface of the electron transport layer. Finally, a cathode is formed by vacuum thermal evaporation of a material for a cathode on the surface of the electron injection layer in a conventional manner. At this time, as the material for the anode used, lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used. In addition, in the case of a top light emitting organic light emitting device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode through which light can pass.
본 발명에 따른 유기 전계발광소자는 상술한 바와 같은 순서, 즉 양극/정공주입층/정공수송층/발광층/정공차단층/전자수송층/전자주입층/음극 순으로 제조하여도 되고, 그 반대로 음극/전자주입층/전자수송층/정공차단층/발광층/정공수송층/정공주입층/양극의 순서로 제조하여도 무방하다. The organic electroluminescent device according to the present invention may be manufactured in the same order as described above, that is, anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode, and vice versa Electron injection layer / electron transport layer / hole blocking layer / light emitting layer / hole transport layer / hole injection layer / anode may be prepared in the order.
본 발명의 또 다른 구현예에서, 상기 유기전계발광소자를 포함하는 전자기기(또는 전자장치)를 제공한다. In another embodiment of the present invention, an electronic device (or electronic device) including the organic electroluminescent device is provided.
이하에서, 본 발명에 따른 유기화합물들의 합성방법을 대표적인 실시예를 통해서 아래에서 설명한다. 그러나, 본 발명의 유기화합물들의 합성방법이 하기 예시된 방법으로 한정되는 것은 아니며, 본 발명의 유기화합물들은 하기에 예시된 방법과 이 분야의 공지의 방법에 의해 제조될 수 있다.Hereinafter, a method for synthesizing organic compounds according to the present invention will be described below through representative examples. However, the method for synthesizing the organic compounds of the present invention is not limited to the methods exemplified below, and the organic compounds of the present invention may be prepared by the methods illustrated below and methods known in the art.
<중간체 합성><Synthesis of intermediates>
아래와 같은 과정을 통해서 본 발명에 따른 유기화합물을 제조하기 위한 중간체들을 합성한다.The intermediates for preparing the organic compound according to the present invention are synthesized through the following process.
(1) 중간체(a)(1) intermediate (a)
상기 반응식을 참조하면, 질소 분위기 하에서 250mL 둥근바닥 플라스크에 1,2-bis(dibromomethyl)benzene(5g, 0.012mol)를 넣고, DMF(50mL)를 넣어 교반하여, 플라스크 안의 스타팅 물질을 모두 녹인다. 0℃의 ice-bath에서 Sodium iodide (4.5g, 0.03mol)을 플라스크에 적가한다. 그리고, 60℃에서 48시간 동안 반응을 진행한다. 반응 종료 후 추출하여 유기물을 분리하고, 증류시켜 용매를 감압 제거한다. 진공오븐에서 건조시킨 후 아래의 중간체(a)(수율:48%)를 얻는다.Referring to the above reaction scheme, 1,2-bis(dibromomethyl)benzene (5 g, 0.012 mol) was put into a 250 mL round-bottom flask under a nitrogen atmosphere, DMF (50 mL) was added and stirred, and all the starting materials in the flask were dissolved. Sodium iodide (4.5 g, 0.03 mol) is added dropwise to the flask in an ice-bath at 0°C. Then, the reaction proceeds at 60 ℃ for 48 hours. After completion of the reaction, the organic material is separated by extraction, followed by distillation to remove the solvent under reduced pressure. After drying in a vacuum oven, the following intermediate (a) (yield: 48%) is obtained.
중간체(a)Intermediate (a)
(2) 중간체(b)(2) intermediate (b)
상기 반응식을 참조하면, 질소 분위기 하에서 250mL 둥근바닥 플라스크에 중간체(a)(2g, 0.0076mol), 1-butanol(0.6mL, 0.0076mol), Cuprous iodode(0.08eq), potassium phosphate(4g, 0.02mol), trans-1,2-cyclohexanediamine(1.1mL, 0.0076mol)을 넣고, 110℃에서 24시간 동안 환류시켜 반응을 진행한다. MC/증류수를 이용하여 유기층을 분리한다. 증발(Evaporation)시켜 용매를 감압 제거하고, 컬럼크로마토그래피를 통해 정제하여 아래의 중간체(b)(수율:54%)를 얻는다.Referring to the above reaction formula, intermediate (a) (2g, 0.0076mol), 1-butanol (0.6mL, 0.0076mol), Cuprous iodode (0.08eq), potassium phosphate (4g, 0.02mol) in a 250mL round-bottom flask under a nitrogen atmosphere ), trans-1,2-cyclohexanediamine (1.1mL, 0.0076mol) was added, and the reaction was carried out by refluxing at 110°C for 24 hours. The organic layer is separated using MC/distilled water. The solvent is removed under reduced pressure by evaporation, and purified through column chromatography to obtain the following intermediate (b) (yield: 54%).
중간체(b)Intermediate (b)
(3) 중간체(c)(3) intermediate (c)
상기 반응식을 참조하면, 질소 분위기 하에서 250mL 둥근바닥 플라스크에 중간체(a)(2g, 0.0076mol), pentanamide(0.8g, 0.0076mol), bippyphos10(0.09g, 0.0002mol), Pd(dba)3(0.2g, 0.0002mol), K3PO4(4.7g, 0.0225mol)을 넣은 후에 1,4-dioxane(80mL)를 넣는다. 그 후, 85℃에서 24시간 동안 반응을 진행한다. 반응 종료 후, 추출하여 유기층을 분리시키고, 증발(Evaporation)시켜 용매를 감압 제거 한다. 컬럼크로마토그래피를 통해 정제하여 아래의 중간체(c)(수율:38%)를 얻는다.Referring to the above reaction formula, intermediate (a) (2g, 0.0076mol), pentanamide (0.8g, 0.0076mol), bippyphos10 (0.09g, 0.0002mol), Pd(dba) 3 (0.2 g, 0.0002mol), K 3 PO 4 (4.7 g, 0.0225 mol) is added, and then 1,4-dioxane (80 mL) is added. Then, the reaction proceeds at 85 ℃ for 24 hours. After completion of the reaction, the organic layer is separated by extraction, and the solvent is removed under reduced pressure by evaporation. Purification through column chromatography to obtain the following intermediate (c) (yield: 38%).
중간체(c)Intermediate (c)
(4) 중간체(d)(4) intermediate (d)
상기 반응식을 참조하면, 질소 분위기 하에서 250mL 둥근바닥 플라스크에, 중간체(b)(2.56g, 0.01mol), Bis(Pinacolato)diboron(2.5g, 0.01mol), potassium acetate(0.5g, 0.015mol), Pd(pph3)4(0.34g, 0.0005mol)을 넣고 1,4-dioxane(100mL)를 넣어 교반시킨다. 110℃에서 24시간 동안 환류시켜 반응을 진행한다. 반응 종료 후 상온에서 식혀 에틸렌아세테이트로 씻어준다. 여과액을 받아 용매를 모두 날린 후, 컬럼크로마토그래피(EA : Hx =1:10)로 아래의 중간체(d)(수율:62%)를 얻는다. Referring to the above reaction formula, in a 250 mL round-bottom flask under a nitrogen atmosphere, intermediate (b) (2.56 g, 0.01 mol), Bis (Pinacolato) diboron (2.5 g, 0.01 mol), potassium acetate (0.5 g, 0.015 mol), Pd(pph 3 ) 4 (0.34 g, 0.0005 mol) was added, and 1,4-dioxane (100 mL) was added and stirred. The reaction proceeds by refluxing at 110° C. for 24 hours. After completion of the reaction, it is cooled at room temperature and washed with ethylene acetate. After receiving the filtrate and blowing off all the solvent, the following intermediate (d) (yield: 62%) is obtained by column chromatography (EA: Hx = 1:10).
중간체(d)intermediate (d)
(5) 중간체(e)(5) intermediate (e)
상기 반응식을 참조하면, 둥근플라스크에 cesium fluoride(11.4g, 75.0mmol)을 넣고 건조시킨다. 건조 후에 10mL의 acetonitrile에 butyl vinyl ether(4.9 mL, 38 mmol)와 4-bromo-2-(trimethylsilyl)phenyl trifluoromethanesulfonate(5.70g, 15.7mmol)을 분산시킨 용액을 cesium fluoride의 용액에 천천히 적가한다. 실온에서 5시간 반응 후에 물로 반응을 종결한다. DCM으로 추출한 후에 컬럼크로마토그래피로 정제하여 아래의 중간체(e)(수율:65%)를 얻는다.Referring to the above reaction scheme, cesium fluoride (11.4 g, 75.0 mmol) was put in a round flask and dried. After drying, a solution of butyl vinyl ether (4.9 mL, 38 mmol) and 4-bromo-2-(trimethylsilyl)phenyl trifluoromethanesulfonate (5.70 g, 15.7 mmol) in 10 mL of acetonitrile is slowly added dropwise to the cesium fluoride solution. After 5 hours of reaction at room temperature, the reaction is terminated with water. After extraction with DCM, it is purified by column chromatography to obtain the following intermediate (e) (yield: 65%).
중간체(e)Intermediate (e)
(6) 중간체(f)(6) intermediate (f)
상기 반응식을 참조하면, 질소 분위기하에서, 25℃에서 2-neck 플라스크에 bicyclo[4.2.0]octa-1,3,5-trien-7-ol(1.2g, 10mmol), NBS(2.53g, 14.2mmol), DMF (20mL)를 넣고 5시간 환류하며 반응시킨다. 반응 종료 후, 상온에서 식히고 MC/증류수로 추출하여 유기층을 분리한다. 유기층의 용매를 모두 제거하고 컬럼크로마토그래피(MC:Hex = 1:2)로 정제하여 아래의 중간체(f)(수율:52%)를 얻는다. Referring to the above reaction scheme, in a nitrogen atmosphere, bicyclo [4.2.0] octa-1,3,5-trien-7-ol (1.2 g, 10 mmol), NBS (2.53 g, 14.2) in a 2-neck flask at 25 ° C. mmol), DMF (20mL) was added, and the reaction was carried out under reflux for 5 hours. After completion of the reaction, the mixture is cooled at room temperature and extracted with MC/distilled water to separate the organic layer. All solvents in the organic layer are removed and purified by column chromatography (MC:Hex = 1:2) to obtain the following intermediate (f) (yield: 52%).
중간체(f)Intermediate (f)
(7) 중간체(g)(7) intermediate (g)
상기 반응식을 참조하면, 질소 분위기 하에서 500mL two-neck 플라스크에, 3-bromo-9H-carbazole(0.48g, 0.002mol), 상기 중간체(d)(1.21g, 0.004mol), Pd(pph3)4(0.2g, 0.0002mol)를 넣고, THF(100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)을 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:4)로 정제하여 아래의 중간체(g)(수율:35%)를 얻는다. Referring to the above reaction scheme, in a 500mL two-neck flask under a nitrogen atmosphere, 3-bromo-9H-carbazole (0.48g, 0.002mol), the intermediate (d) (1.21g, 0.004mol), Pd(pph 3 ) 4 (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all the solvent of the separated organic layer was blown off, it was purified by column chromatography (MC: Hx = 1:4) to obtain the following intermediate (g) (yield: 35%).
중간체(g)Intermediate (g)
<실시예<Example 1> 1>
아래의 연속적인 반응식을 통해 상기 [화학식 1]의 유기화합물을 합성하였다. The organic compound of [Formula 1] was synthesized through the following continuous reaction scheme.
(1) 중간체(1)의 합성(1) Synthesis of Intermediate (1)
질소 분위기 하에서 500mL two-neck 플라스크에, 4-bromo-N-phenylaniline (0.5g, 0.002mol), 상기 중간체(d)(1.21g, 0.004mol), Pd(pph3)4(0.2g, 0.0002mol) 를 넣고, THF(100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonate solution(2N, 100mL)를 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:4)로 정제하여 아래의 중간체(1)(수율:38%)을 얻는다.In a 500 mL two-neck flask under nitrogen atmosphere, 4-bromo-N-phenylaniline (0.5 g, 0.002 mol), the above intermediate (d) (1.21 g, 0.004 mol), Pd (pph 3 ) 4 (0.2 g, 0.0002 mol) ), and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonate solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all the solvent of the separated organic layer was blown off, it was purified by column chromatography (MC: Hx = 1:4) to obtain the following intermediate (1) (yield: 38%).
중간체(1)Intermediate (1)
(2) 유기화합물의 합성(2) Synthesis of organic compounds
다음으로, One-neck 플라스크에 상기 중간체(1)(1g, 2.88mmol), tris(4-bromophenyl)amine(0.44g, 0.92mmol), copper iodide(0.07g, 0.367mol), potassium phosphate(2g, 0.0147mol), 1,2-trans-cyclohexane diamine(0.4mL, 3.67mmol)을 넣고, 1,4-dioxane(100mL)을 넣어 교반시킨다. 110℃에서 48시간 동안 반응을 진행시킨다. 반응 종료 후, 상온에서 식히고 MC와 증류수로 워크업(work up)하여 유기층을 분리한다. 유기층의 용매를 모두 날리고 컬럼크로마토그래피(MC : Hx =1:10)로 정제하여 아래 [화학식 1](수율:70%)의 유기화합물을 얻는다. Next, the intermediate (1) (1g, 2.88mmol), tris(4-bromophenyl)amine (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147 mol), 1,2-trans-cyclohexane diamine (0.4 mL, 3.67 mmol) was added, and 1,4-dioxane (100 mL) was added and stirred. The reaction proceeds at 110° C. for 48 hours. After completion of the reaction, it is cooled at room temperature, and the organic layer is separated by working up with MC and distilled water. All the solvent of the organic layer is blown off and purified by column chromatography (MC: Hx = 1:10) to obtain an organic compound of the following [Formula 1] (yield: 70%).
[화학식 1][Formula 1]
<실시예 2><Example 2>
아래의 반응식을 통해 상기 [화학식 2]의 유기화합물을 합성하였다. The organic compound of [Formula 2] was synthesized through the following reaction scheme.
One-neck 플라스크에 상기 중간체(g)(1g, 2.8mmol), tris(4-bromophenyl)amine(0.44g, 0.92mmol), copper iodide(0.07g, 0.367mol), potassium phosphate(2g, 0.0147mol), 1,2-trans-cyclohexane diamine(0.4mL, 3.67mmol)을 넣고, 1,4-dioxane(100mL)을 넣어 교반시킨다. 110℃에서 48시간 동안 반응을 진행시킨다. 반응 종료 후, 상온에서 식히고 MC와 증류수로 워크업(work up)하여 유기층을 분리한다. 유기층의 용매를 모두 날리고 컬럼크로마토그래피(MC : Hx =1:8)로 정제하여 아래 [화학식 2]의 유기화합물(수율:58%)을 얻는다. The intermediate (g) (1g, 2.8mmol), tris(4-bromophenyl)amine (0.44g, 0.92mmol), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol) in a one-neck flask , 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol) was added, and 1,4-dioxane (100mL) was added and stirred. The reaction proceeds at 110° C. for 48 hours. After completion of the reaction, it is cooled at room temperature, and the organic layer is separated by working up with MC and distilled water. All of the solvent of the organic layer is blown off and purified by column chromatography (MC: Hx = 1:8) to obtain an organic compound of the following [Formula 2] (yield: 58%).
[화학식 2][Formula 2]
<실시예 3><Example 3>
아래의 반응식을 통해 상기 [화학식 3]의 유기화합물을 합성하였다. The organic compound of [Formula 3] was synthesized through the following reaction scheme.
One-neck 플라스크에 상기 중간체(g)(1g, 2.88mmol), tris(4-bromophenyl)amine(0.47g, 1.2mmol), copper iodide(0.07g, 0.367mol), potassium phosphate(2g, 0.0147mol), 1,2-trans-cyclohexane diamine(0.4mL, 3.67mmol)을 넣고, 1,4-dioxane(100mL)을 넣어 교반시킨다. 110℃에서 48시간 동안 반응을 진행시킨다. 반응 종료 후, 상온에서 식히고 MC와 증류수로 워크업(work up)하여 유기층을 분리한다. 유기층의 용매를 모두 날리고 컬럼크로마토그래피(MC : Hx =1:8)로 정제하여 아래 [화학식 3]의 유기화합물(수율:72%)을 얻는다. The intermediate (g) (1g, 2.88mmol), tris(4-bromophenyl)amine (0.47g, 1.2mmol), copper iodide (0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol) in a one-neck flask , 1,2-trans-cyclohexane diamine (0.4mL, 3.67mmol) was added, and 1,4-dioxane (100mL) was added and stirred. The reaction was allowed to proceed at 110° C. for 48 hours. After completion of the reaction, it is cooled at room temperature, and the organic layer is separated by working up with MC and distilled water. All of the solvent of the organic layer is blown off and purified by column chromatography (MC: Hx = 1:8) to obtain the organic compound of the following [Formula 3] (yield: 72%).
[화학식 3][Formula 3]
<실시예 4><Example 4>
아래의 반응식을 통해 상기 [화학식 4]의 유기화합물을 합성하였다. The organic compound of [Formula 4] was synthesized through the following reaction scheme.
질소 분위기 하에서 500mL 둥근바닥 플라스크에, 상기 중간체(g)(1.4g, 0.004mol), bis(4-bromophenyl)diphenylsilane(1.0g, 0.002mol), Cuprous iodide(0.09g, 0.00047mol), potassium phosphate(6.4g, 0.03mol), trans-1,2-cyclohexane diamine(0.6mL, 0.0047mol)을 넣고, 1,4-dioxane(100mL)를 넣어 교반시킨다. 110℃에서 19시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식힌 후, EA/증류수로 추출하여 유기층을 분리시킨다. 컬럼크로마토그래피로 아래 [화학식 4]의 유기화합물(수율:42%)을 얻는다. In a 500mL round-bottom flask under a nitrogen atmosphere, the intermediate (g) (1.4 g, 0.004 mol), bis(4-bromophenyl)diphenylsilane (1.0 g, 0.002 mol), Cuprous iodide (0.09 g, 0.00047 mol), potassium phosphate ( 6.4g, 0.03mol), trans-1,2-cyclohexane diamine (0.6mL, 0.0047mol) was added, and 1,4-dioxane (100mL) was added and stirred. The reaction proceeds by refluxing at 110° C. for 19 hours. After completion of the reaction, after cooling to room temperature, the organic layer was separated by extraction with EA/distilled water. By column chromatography, an organic compound of the following [Formula 4] (yield: 42%) is obtained.
[화학식 4][Formula 4]
<실시예 5><Example 5>
아래의 반응식을 통해 상기 [화학식 5]의 유기화합물을 합성하였다. The organic compound of [Formula 5] was synthesized through the following reaction scheme.
One-neck 플라스크에 상기 중간체(g)(1.4g, 0.004mol), (1s,3s,5r,7r)-1,3-bis(4-bromophenyl)adamantane(0.9g, 0.002mol), copper iodide(0.07g, 0.367mol), potassium phosphate(2g, 0.0147mol), 1,2-trans-cyclohexane diamine(0.4 mL, 3.67mmol)을 넣고, 1,4-dioxane(100mL)을 넣어 교반시킨다. 110℃에서 48시간 동안 반응을 진행시킨다. 반응 종료 후, 상온에서 식히고 MC와 증류수로 워크업(work up)하여 유기층을 분리한다. 유기층의 용매를 모두 날리고 컬럼크로마토그래피(MC : Hx =1:8)로 정제하여 아래 [화학식 5]의 유기화합물(수율:65%)을 얻는다. The above intermediate (g) (1.4 g, 0.004 mol), (1s,3s,5r,7r)-1,3-bis(4-bromophenyl)adamantane (0.9g, 0.002mol), copper iodide ( 0.07g, 0.367mol), potassium phosphate (2g, 0.0147mol), 1,2-trans-cyclohexane diamine (0.4 mL, 3.67mmol) were added, and 1,4-dioxane (100mL) was added and stirred. The reaction was allowed to proceed at 110° C. for 48 hours. After completion of the reaction, it is cooled at room temperature, and the organic layer is separated by working up with MC and distilled water. All of the solvent of the organic layer is blown off and purified by column chromatography (MC: Hx = 1:8) to obtain an organic compound of the following [Formula 5] (yield: 65%).
[화학식 5][Formula 5]
<실시예 6><Example 6>
아래의 연속적인 반응식을 통해 상기 [화학식 6]의 유기화합물을 합성하였다. The organic compound of [Formula 6] was synthesized through the following continuous reaction scheme.
(1) 중간체(h)의 합성(1) Synthesis of intermediate (h)
상기 반응식을 참조하면, 질소 분위기 하에서 500mL two-neck 플라스크에, 1,6-dibromopyrene(1.4g, 0.002mol), 상기 중간체(d)(0.71g, 0.002mol), Pd(pph3)4(0.2g, 0.0002mol)를 넣고, THF(100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)를 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:6)로 정제하여 아래의 중간체(h)(수율:41%)를 얻는다. Referring to the above scheme, in a 500 mL two-neck flask under a nitrogen atmosphere, 1,6-dibromopyrene (1.4 g, 0.002 mol), the intermediate (d) (0.71 g, 0.002 mol), Pd (pph 3 ) 4 (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all the solvent of the separated organic layer was blown off, it was purified by column chromatography (MC: Hx = 1:6) to obtain the following intermediate (h) (yield: 41%).
중간체(h)Intermediate (h)
(2) 유기화합물의 합성 (2) Synthesis of organic compounds
다음으로, 질소 분위기 하에서 500mL two-neck 플라스크에, tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine(0.62g, 0.001mol), 상기 중간체(h)(1.4g, 0.0033mol), Pd(pph3)4(0.2g, 0.0002mol)를 넣고, THF (100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)을 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:6)로 정제하여 아래 [화학식 6]의 유기화합물(수율:35%)을 얻는다. Next, in a 500mL two-neck flask under a nitrogen atmosphere, tris(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.62g, 0.001mol) , The intermediate (h) (1.4 g, 0.0033 mol), Pd (pph 3 ) 4 (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all the solvent of the separated organic layer is blown off, it is purified by column chromatography (MC: Hx = 1:6) to obtain the organic compound (Yield: 35%) of the following [Formula 6].
[화학식 6][Formula 6]
<실시예 7><Example 7>
아래의 연속적인 반응식을 통해 상기 [화학식 7]의 유기화합물을 합성하였다. The organic compound of [Formula 7] was synthesized through the following continuous reaction scheme.
(1) 중간체(i)의 합성(1) Synthesis of intermediate (i)
상기 반응식을 참조하면, 질소 분위기 하에서 500mL two-neck 플라스크에, 5-bromo-2-iodopyridine(1.4g, 0.002mol), 중간체(d)(0.56g, 0.002mol), Pd(pph3)4 (0.2g, 0.0002mol)를 넣고, THF(100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)을 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:6)로 정제하여 아래의 중간체(i)(수율:32%)를 얻는다. Referring to the above reaction scheme, in a 500 mL two-neck flask under a nitrogen atmosphere, 5-bromo-2-iodopyridine (1.4 g, 0.002 mol), intermediate (d) (0.56 g, 0.002 mol), Pd (pph 3 ) 4 ( 0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all of the solvent of the separated organic layer was blown off, it was purified by column chromatography (MC: Hx = 1:6) to obtain the following intermediate (i) (yield: 32%).
중간체(i)Intermediate (i)
(2) 유기화합물의 합성(2) Synthesis of organic compounds
다음으로, 질소 분위기 하에서 500mL two-neck 플라스크에, tris(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine(0.62g, 0.001mol), 상기 중간체(i)(1.1g, 0.0033mol), Pd(pph3)4(0.2g, 0.0002mol)를 넣고, THF (100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)을 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:6)로 정제하여 아래 [화학식 7]의 유기화합물(수율:32%)을 얻는다. Next, in a 500mL two-neck flask under a nitrogen atmosphere, tris(3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)amine (0.62g, 0.001mol) , The intermediate (i) (1.1 g, 0.0033 mol), Pd (pph 3 ) 4 (0.2 g, 0.0002 mol) was added, and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all the solvent of the separated organic layer is blown off, it is purified by column chromatography (MC: Hx = 1:6) to obtain the organic compound (Yield: 32%) of the following [Formula 7].
[화학식 7][Formula 7]
<실시예 8><Example 8>
아래의 연속적인 반응식을 통해 상기 [화학식 8]의 유기화합물을 합성하였다. The organic compound of [Formula 8] was synthesized through the following sequential reaction scheme.
(1) 중간체(j)의 합성(1) Synthesis of intermediate (j)
질소 분위기 하에서 500mL two-neck 플라스크에, tris(4-bromophenyl)amine(0.48g, 0.002mol), 상기 중간체(d)(1.21g, 0.004mol), Pd(pph3)4(0.2g, 0.0002mol)를 넣고, THF(100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)을 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:4)로 정제하여 아래의 중간체(j)(수율:35%)를 얻는다. In a 500 mL two-neck flask under nitrogen atmosphere, tris(4-bromophenyl)amine (0.48 g, 0.002 mol), the above intermediate (d) (1.21 g, 0.004 mol), Pd(pph 3 ) 4 (0.2 g, 0.0002 mol) ), and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all of the solvent of the separated organic layer is blown off, it is purified by column chromatography (MC: Hx = 1:4) to obtain the following intermediate (j) (yield: 35%).
중간체(j)intermediate (j)
(2) 유기화합물의 합성 (2) Synthesis of organic compounds
다음으로, 플라스크에 상기 중간체(j)(0.47g, 1.2mmol), P(t-Bu)3(0.012g, 0.061mmol), Pd2(dba)3(0.033g, 0.035mmol)를 넣고, 톨루엔에 녹인 후 충분히 질소 퍼징을 실시한다. 그 후, N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine(1g, 2.97mmol)과 NaOtBu(0.28g, 2.97mmol)을 부가한다. 그리고, 100℃에서 24시간 동안 반응시킨 후, 물과 methylene chloride을 넣어 반응을 종결한 후에 methylene chloride을 분리하고, 컬럼크로마토그래피를 이용하여 정제하여 아래 [화학식 8]의 유기화합물을 얻는다. Next, the intermediate (j) (0.47 g, 1.2 mmol), P(t-Bu) 3 (0.012 g, 0.061 mmol), Pd 2 (dba) 3 (0.033 g, 0.035 mmol) was put in a flask, and toluene After dissolving in , perform sufficient nitrogen purging. Then, N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (1 g, 2.97 mmol) and NaOtBu (0.28 g, 2.97 mmol) were added. And, after reacting at 100° C. for 24 hours, after terminating the reaction by adding water and methylene chloride, methylene chloride is separated, and purified using column chromatography to obtain the organic compound of [Formula 8] below.
[화학식 8][Formula 8]
<실시예 9><Example 9>
아래의 연속적인 반응식을 통해 상기 [화학식 9]의 유기화합물을 합성하였다. The organic compound of [Formula 9] was synthesized through the following sequential reaction scheme.
(1) 중간체(j)의 합성(1) Synthesis of intermediate (j)
질소 분위기 하에서 500mL two-neck 플라스크에, tris(4-bromophenyl)amine(0.48g, 0.002mol), 상기 중간체(d)(1.21g, 0.004mol), Pd(pph3)4(0.2g, 0.0002mol)를 넣고, THF(100mL)를 넣어 교반시킨다. 플라스크 안에 물질이 모두 녹으면 potassium carbonzte solution(2N, 100mL)을 넣는다. 80℃에서 12시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식히고 EA/증류수로 추출하여 유기층을 분리한다. 분리한 유기층의 용매를 모두 날린 후, 컬럼크로마토그래피(MC : Hx = 1:4)로 정제하여 아래의 중간체(j)(수율:35%)를 얻는다. In a 500 mL two-neck flask under nitrogen atmosphere, tris(4-bromophenyl)amine (0.48 g, 0.002 mol), the above intermediate (d) (1.21 g, 0.004 mol), Pd(pph 3 ) 4 (0.2 g, 0.0002 mol) ), and THF (100 mL) was added and stirred. When all the substances are dissolved in the flask, add potassium carbonzte solution (2N, 100mL). The reaction proceeds by refluxing at 80° C. for 12 hours. After completion of the reaction, the mixture was cooled at room temperature and extracted with EA/distilled water to separate the organic layer. After all of the solvent of the separated organic layer was blown off, it was purified by column chromatography (MC: Hx = 1:4) to obtain the following intermediate (j) (yield: 35%).
중간체(j)intermediate (j)
(2) 중간체(k)의 합성(2) Synthesis of intermediate (k)
다음으로, 플라스크에 2-bromonaphthalene(2.69g, 13.0mmol), P(t-Bu)3(0.021g, 0.11mmol), Pd2(dba)3(0.06g, 0.063mmol)를 넣고, 톨루엔에 녹인 후 충분히 질소 퍼징을 실시한다. 그 후, benzidine(1g, 5.4mmol)과 NaOtBu(0.51g, 5.4mmol)을 부가한다. 100℃에서 24시간동안 반응시킨다. 물과 methylene chloride을 넣어 반응을 종결한 후에 methylene chloride을 분리하고, 컬럼크로마토그래피를 이용하여 정제하여 아래의 중간체(k)를 얻는다. Next, 2-bromonaphthalene (2.69 g, 13.0 mmol), P(t-Bu) 3 (0.021 g, 0.11 mmol), Pd 2 (dba) 3 (0.06 g, 0.063 mmol) was added to a flask and dissolved in toluene. After that, perform a sufficient nitrogen purging. Then, benzidine (1 g, 5.4 mmol) and NaOtBu (0.51 g, 5.4 mmol) are added. The reaction was carried out at 100°C for 24 hours. After completion of the reaction by adding water and methylene chloride, methylene chloride is separated and purified using column chromatography to obtain the following intermediate (k).
중간체(k)Intermediate (k)
(3) 유기화합물의 합성(3) Synthesis of organic compounds
다음으로, 플라스크에 상기 중간체(j)(8.5g, 13.0mmol), P(t-Bu)3(0.021g, 0.11mmol), Pd2(dba)3(0.06g, 0.063mmol)를 넣고, 톨루엔에 녹인 후 충분히 질소 퍼징을 실시한다. 그 후, 상기 중간체(k)(1g, 5.4mmol)와 NaOtBu(0.51g, 5.4mmol)을 부가한다. 그리고, 100 ℃에서 24시간 동안 반응시킨 후, 물과 methylene chloride을 넣어 반응을 종결한 후에 methylene chloride을 분리하고, 컬럼크로마토그래피를 이용하여 정제하여 하기 [화학식 9]의 유기화합물을 얻는다. Next, put the intermediate (j) (8.5 g, 13.0 mmol), P(t-Bu) 3 (0.021 g, 0.11 mmol), Pd 2 (dba) 3 (0.06 g, 0.063 mmol) in a flask, and toluene After dissolving in , perform sufficient nitrogen purging. Then, the intermediate (k) (1 g, 5.4 mmol) and NaOtBu (0.51 g, 5.4 mmol) are added. And, after reacting at 100 ° C. for 24 hours, after terminating the reaction by adding water and methylene chloride, methylene chloride is separated and purified using column chromatography to obtain an organic compound of the following [Formula 9].
[화학식 9][Formula 9]
<실시예 10><Example 10>
아래의 반응식을 통해 상기 [화학식 10]의 유기화합물을 합성하였다. The organic compound of [Formula 10] was synthesized through the following reaction scheme.
질소 분위기 하에서, 500mL 둥근바닥 플라스크에, bis(4-(7-butoxybicyclo[4.2.0]octa-1,3,5-trien-3-yl)phenyl)amine(2.07g, 4mmol), bis(4-bromophenyl)diphenylmethane(0.95g, 2mmol), Cuprous iodide(0.09g, 0.00047mol), potassium phosphate(6.4g, 0.03mol), trans-1,2-cyclohexane diamine(0.6mL, 0.0047mol)을 넣고, 1,4-dioxane(100mL)를 넣어 교반시킨다. 110℃ 에서 24시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식힌 후, EA/증류수로 추출하여 유기층을 분리시킨다. 컬럼크로마토그래피로 정제하여 아래 [화학식 10]의 유기화합물을 얻는다. In a nitrogen atmosphere, in a 500 mL round-bottom flask, bis(4-(7-butoxybicyclo[4.2.0]octa-1,3,5-trien-3-yl)phenyl)amine (2.07 g, 4 mmol), bis(4 -bromophenyl)diphenylmethane (0.95g, 2mmol), Cuprous iodide (0.09g, 0.00047mol), potassium phosphate (6.4g, 0.03mol), trans-1,2-cyclohexane diamine (0.6mL, 0.0047mol) was added, and 1 ,4-dioxane (100 mL) was added and stirred. The reaction proceeds by refluxing at 110° C. for 24 hours. After completion of the reaction, after cooling to room temperature, the organic layer was separated by extraction with EA/distilled water. Purification by column chromatography to obtain an organic compound of the following [Formula 10].
[화학식 10][Formula 10]
<실시예 11><Example 11>
아래의 연속적인 반응식을 통해 상기 [화학식 11]의 유기화합물을 합성하였다. The organic compound of [Formula 11] was synthesized through the following continuous reaction scheme.
(1) 중간체(l)의 합성(1) Synthesis of intermediate (l)
상기 반응식을 참조하면, 이구 둥근바닥 플라스크에 2-(7-(8-butoxybicyclo[4.2.0]octa-1,3,5-trien-7-yl)-9,9-dimethyl-9H-fluoren-2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane(1.0g, 2.0mmol)와 4-bromo-N-(4-(8-butoxybicyclo[4.2.0]octa-1,3,5-trien-7-yl)phenyl)aniline(0.84g, 2.0mmol)를 넣고 THF(25mL)에 녹인다. 질소를 충분히 흘린 후, 4M K2CO3(7mL)와 에탄올(8mL)을 넣어 준다. 반응물에 Pd(PPh3)4(0.23g, 0.2mmol)를 넣고 80℃에서 환류시킨다. 반응 종료 후 물과 MC로 추출해준다. MgSO4로 잔여 수분을 제거 한 후에 EA:Hex을 사용하여 관크로마토그래피로 정제하여 아래의 중간체(l)을 얻는다.Referring to the above reaction scheme, 2-(7-(8-butoxybicyclo[4.2.0]octa-1,3,5-trien-7-yl)-9,9-dimethyl-9H-fluoren- 2-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.0 g, 2.0 mmol) and 4-bromo-N- (4- (8-butoxybicyclo [4.2.0] octa- Add 1,3,5-trien-7-yl)phenyl)aniline (0.84g, 2.0mmol) and dissolve in THF (25mL). After sufficient nitrogen flow, 4M K 2 CO 3 (7mL) and ethanol (8mL) are added. Pd(PPh 3 ) 4 (0.23 g, 0.2 mmol) was added to the reactant and refluxed at 80 °C. After completion of the reaction, extraction is performed with water and MC. After removing residual moisture with MgSO 4 , it is purified by column chromatography using EA:Hex to obtain the following intermediate (l).
중간체(l)Intermediate (l)
(2) 유기화합물의 합성(2) Synthesis of organic compounds
다음으로, 질소 분위기 하에서 500mL 둥근바닥 플라스크에, 상기 중간체(l)(1.4g, 2mmol), 4,4'-dibromo-1,1'-biphenyl(0.31g, 1mmol), Cuprous iodide(0.09g, 0.00047mol), potassium phosphate(6.4g, 0.03mol), trans-1,2-cyclohexane diamine(0.6mL, 0.0047mol)을 넣고, 1,4-dioxane(100mL)를 넣어 교반시킨다. 110℃ 에서 24시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식힌 후, EA/증류수로 추출하여 유기층을 분리시킨다. 컬럼크로마토그래피로 정제하여 아래 [화학식 11]의 유기화합물을 얻는다.Next, in a 500 mL round-bottom flask under a nitrogen atmosphere, the intermediate (l) (1.4 g, 2 mmol), 4,4'-dibromo-1,1'-biphenyl (0.31 g, 1 mmol), Cuprous iodide (0.09 g, 0.00047mol), potassium phosphate (6.4g, 0.03mol), trans-1,2-cyclohexane diamine (0.6mL, 0.0047mol) were added, and 1,4-dioxane (100mL) was added and stirred. The reaction proceeds by refluxing at 110° C. for 24 hours. After completion of the reaction, after cooling to room temperature, the organic layer was separated by extraction with EA/distilled water. Purification by column chromatography to obtain an organic compound of the following [Formula 11].
[화학식 11][Formula 11]
<실시예 12><Example 12>
아래의 반응식을 통해 상기 [화학식 12]의 유기화합물을 합성하였다. The organic compound of [Formula 12] was synthesized through the following reaction scheme.
둥근바닥 플라스크에 4-bromo-N-(4-bromophenyl)-N-(4-(5-phenylthiophen-2-yl)phenyl)aniline(0.56g, 1.0mmol)와 7-butoxy-N-(7-butoxybicyclo[4.2.0]octa-1,3,5-trien-3-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl)bicyclo[4.2.0]octa-1,3,5-trien-3-amine(1.13g, 2.0mmol)를 넣고, THF(25mL)에 녹인다. 질소를 충분히 흘린후 4M K2CO3(10mL)와 에탄올(12mL)을 넣어준다. 반응물에 Pd(PPh3)4(0.46g, 0.4mmol)를 넣고, 80℃에서 환류시킨다. 반응 종료 후 물과 MC로 추출해준다. MgSO4로 잔여 수분을 제거 한 후에 EA:Hex을 사용하여 관크로마토그래피로 정제하여 아래 [화학식 12]의 유기화합물을 얻는다.In a round-bottom flask, 4-bromo-N-(4-bromophenyl)-N-(4-(5-phenylthiophen-2-yl)phenyl)aniline (0.56g, 1.0mmol) and 7-butoxy-N-(7- butoxybicyclo[4.2.0]octa-1,3,5-trien-3-yl)-N-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl ) Add bicyclo[4.2.0]octa-1,3,5-trien-3-amine (1.13 g, 2.0 mmol), and dissolve in THF (25 mL). After sufficient nitrogen flow, 4M K 2 CO 3 (10 mL) and ethanol (12 mL) are added. Pd(PPh 3 ) 4 (0.46 g, 0.4 mmol) was added to the reaction mass, and refluxed at 80 °C. After completion of the reaction, extraction is performed with water and MC. After removing the residual moisture with MgSO 4 , it is purified by column chromatography using EA:Hex to obtain the organic compound of the following [Formula 12].
[화학식 12][Formula 12]
<실시예 13><Example 13>
아래의 반응식을 통해 상기 [화학식 13]의 유기화합물을 합성하였다. The organic compound of [Formula 13] was synthesized through the following reaction scheme.
질소 분위기 하에서 500mL 둥근바닥 플라스크에, bis(4-(7-butoxybicyclo[4.2.0]octa-1,3,5-trien-3-yl)phenyl)amine(2.07g, 4mmol), 4,4'-(cyclohexane-1,1-diyl)bis(bromobenzene)(0.78g, 2mmol), Cuprous iodide(0.09g, 0.00047mol), potassium phosphate(6.4g, 0.03mol), trans-1,2-cyclohexane diamine(0.6mL, 0.0047mol)을 넣고, 1,4-dioxane(100mL)를 넣어 교반시킨다. 110 ℃에서 24시간 동안 환류시켜 반응을 진행한다. 반응 종료 후, 상온에서 식힌 후, EA/증류수로 추출하여 유기층을 분리시킨다. 컬럼크로마토그래피로 정제하여 아래 [화학식 13]의 유기화합물을 얻는다. In a 500mL round-bottom flask under nitrogen atmosphere, bis(4-(7-butoxybicyclo[4.2.0]octa-1,3,5-trien-3-yl)phenyl)amine (2.07g, 4mmol), 4,4' -(cyclohexane-1,1-diyl)bis(bromobenzene) (0.78g, 2mmol), Cuprous iodide (0.09g, 0.00047mol), potassium phosphate (6.4g, 0.03mol), trans-1,2-cyclohexane diamine ( 0.6 mL, 0.0047 mol) was added, and 1,4-dioxane (100 mL) was added and stirred. The reaction proceeds by refluxing at 110° C. for 24 hours. After completion of the reaction, after cooling to room temperature, the organic layer was separated by extraction with EA/distilled water. Purification by column chromatography to obtain an organic compound of the following [Formula 13].
[화학식 13][Formula 13]
<실시예 14><Example 14>
아래의 반응식을 통해 상기 [화학식 14]의 유기화합물을 합성하였다. The organic compound of [Formula 14] was synthesized through the following reaction scheme.
플라스크에 2,7,10,15-tetrabromotetraphenylene(0.31g, 0.5mmol), P(t-Bu)3(0.016g, 0.08mmol), Pd2(dba)3(0.042g, 0.045mmol)를 넣고, 톨루엔에 녹인 후 충분히 질소 퍼징을 실시한다. 그 후, 상기 중간체(f)(0.94g, 2.4mmol)과 NaOtBu (0.23g, 2.4mmol)를 부가한다. 그리고, 100℃에서 24시간 동안 반응시킨 후, 물과 methylene chloride을 넣어 반응을 종결한 후에 methylene chloride을 분리하고, 컬럼크로마토그래피로 정제하여 아래 [화학식 14]의 유기화합물을 얻는다.Put 2,7,10,15-tetrabromotetraphenylene (0.31 g, 0.5 mmol), P(t-Bu) 3 (0.016 g, 0.08 mmol), Pd 2 (dba) 3 (0.042 g, 0.045 mmol) in a flask, After dissolving in toluene, sufficiently perform nitrogen purging. Then, the intermediate (f) (0.94 g, 2.4 mmol) and NaOtBu (0.23 g, 2.4 mmol) are added. And, after reacting at 100° C. for 24 hours, after terminating the reaction by adding water and methylene chloride, methylene chloride is separated and purified by column chromatography to obtain an organic compound of the following [Formula 14].
[화학식 14][Formula 14]
Claims (27)
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은, 아래의 화학식을 갖는 것을 특징으로 하는 유기화합물.
The organic compound is an organic compound, characterized in that it has the following chemical formula.
상기 유기화합물은 유기전기소자용 유기박막 재료중 발광층 물질, 정공주입층 물질, 정공수송층 물질, 전자주입층 물질, 전자수송층 물질, 전자차단층 물질 및 정공차단층 물질로 이루어진 군으로부터 선택된 적어도 하나의 용도로 사용되는 것을 특징으로 하는 유기화합물.17. The method according to any one of claims 3, 5 to 7 and 10 to 16,
The organic compound is at least one selected from the group consisting of a light emitting layer material, a hole injection layer material, a hole transport layer material, an electron injection layer material, an electron transport layer material, an electron blocking layer material, and a hole blocking layer material among organic thin film materials for an organic electric device Organic compounds, characterized in that used for the purpose.
상기 잉크 조성물은 상기 청구항 3, 청구항 5 내지 청구항 7 및 청구항 10 내지 청구항 16중 선택된 어느 하나의 유기화합물을 포함하는 것을 특징으로 하는 잉크 조성물.An ink composition for forming an organic thin film disposed between a first electrode and a second electrode of an organic electric device, the ink composition comprising:
The ink composition is an ink composition comprising any one of the organic compound selected from claims 3, 5 to 7, and 10 to 16.
상기 잉크 조성물은 용매를 더 포함하는 용액 또는 현탁액인 것을 특징으로 하는 잉크 조성물.19. The method of claim 18,
The ink composition is an ink composition, characterized in that the solution or suspension further comprising a solvent.
상기 잉크 조성물은 안료 또는 염료를 더 포함하는 것을 특징으로 하는 잉크 조성물. 19. The method of claim 18,
The ink composition is an ink composition, characterized in that it further comprises a pigment or dye.
상기 잉크 조성물은 인광 도펀트 또는 형광 도펀트를 더 포함하는 것을 특징으로 하는 잉크 조성물. 19. The method of claim 18,
The ink composition further comprises a phosphorescent dopant or a fluorescent dopant.
상기 유기 박막층을 형성하기 위한 유기화합물이 상기 청구항 3, 청구항 5 내지 청구항 7 및 청구항 10 내지 청구항 16중 선택된 어느 하나의 유기화합물을 포함하는 것을 특징으로 하는 유기전기소자. In an organic electric device in which an organic thin film layer comprising at least a light emitting layer or a plurality of layers is sandwiched between a cathode and an anode,
An organic electric device, characterized in that the organic compound for forming the organic thin film layer comprises any one of the organic compound selected from claims 3, 5 to 7, and 10 to 16.
상기 유기 박막층을 형성하는 유기화합물의 말단의 벤조시클로부텐기(benzocyclobutene)간에 가교결합이 형성되는 것을 특징으로 하는 유기전기소자. 23. The method of claim 22,
An organic electric device, characterized in that a crosslink is formed between benzocyclobutene groups at the ends of the organic compound forming the organic thin film layer.
상기 유기 박막층은 발광층, 정공주입층, 정공수송층, 전자주입층, 전자수송층, 전자차단층 및 정공차단층으로 이루어진 군으로부터 선택된 적어도 하나인 것을 특징으로 하는 유기전기소자.23. The method of claim 22,
The organic thin film layer is an organic electric device, characterized in that at least one selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an electron blocking layer and a hole blocking layer.
양극, 정공주입층, 정공수송층, 발광층, 전자수송층, 전자주입층 및 음극이 이 순서대로 적층된 구조를 갖는 것을 특징으로 하는 유기전기소자. 25. The method of claim 24,
An organic electric device, characterized in that it has a structure in which an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode are stacked in this order.
상기 유기 박막층은 상기 유기화합물을 포함하는 잉크 조성물을 용액 공정에 의해 도포하고 건조시켜 성막하여 제조된 것을 특징으로 하는 유기전기소자. 25. The method of claim 24,
The organic thin film layer is an organic electric device, characterized in that it is manufactured by coating the ink composition containing the organic compound by a solution process and drying it to form a film.
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|---|---|---|---|---|
| JP2006156847A (en) | 2004-11-30 | 2006-06-15 | Fuji Photo Film Co Ltd | Organic electroluminescent element |
| WO2016026122A1 (en) | 2014-08-21 | 2016-02-25 | Dow Global Technologies Llc | Benzocyclobutenes derived compositions, and electronic devices containing the same |
-
2020
- 2020-02-28 KR KR1020200025291A patent/KR102346098B1/en active IP Right Grant
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| Publication number | Publication date |
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| KR20210109968A (en) | 2021-09-07 |
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