JP2017002287A - Polymer, composition for organic electroluminescent element, organic electroluminescent element, organic el display device and electronic el lighting - Google Patents
Polymer, composition for organic electroluminescent element, organic electroluminescent element, organic el display device and electronic el lighting Download PDFInfo
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- JP2017002287A JP2017002287A JP2016108860A JP2016108860A JP2017002287A JP 2017002287 A JP2017002287 A JP 2017002287A JP 2016108860 A JP2016108860 A JP 2016108860A JP 2016108860 A JP2016108860 A JP 2016108860A JP 2017002287 A JP2017002287 A JP 2017002287A
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- substituent
- aromatic hydrocarbon
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- 229920000642 polymer Polymers 0.000 title claims abstract description 136
- 239000000203 mixture Substances 0.000 title claims abstract description 58
- 238000002347 injection Methods 0.000 claims abstract description 100
- 239000007924 injection Substances 0.000 claims abstract description 100
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 94
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 87
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 39
- 239000010410 layer Substances 0.000 claims description 248
- -1 2-fluorenyl group Chemical group 0.000 claims description 108
- 125000001424 substituent group Chemical group 0.000 claims description 103
- 238000000034 method Methods 0.000 claims description 92
- 230000015572 biosynthetic process Effects 0.000 claims description 52
- 230000005525 hole transport Effects 0.000 claims description 48
- 125000003118 aryl group Chemical group 0.000 claims description 18
- 239000000758 substrate Substances 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 15
- 125000005647 linker group Chemical group 0.000 claims description 15
- 239000012044 organic layer Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 238000005286 illumination Methods 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000001047 cyclobutenyl group Chemical group C1(=CCC1)* 0.000 claims description 3
- 239000000243 solution Substances 0.000 abstract description 21
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 10
- 150000003512 tertiary amines Chemical class 0.000 abstract description 5
- 150000001875 compounds Chemical class 0.000 description 95
- 239000010408 film Substances 0.000 description 78
- 239000000463 material Substances 0.000 description 64
- 239000002904 solvent Substances 0.000 description 57
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 54
- 125000004432 carbon atom Chemical group C* 0.000 description 35
- 238000005401 electroluminescence Methods 0.000 description 22
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 18
- 230000000903 blocking effect Effects 0.000 description 14
- 229910052799 carbon Inorganic materials 0.000 description 14
- 238000004132 cross linking Methods 0.000 description 14
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 14
- 238000006116 polymerization reaction Methods 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 13
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 238000000576 coating method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 230000001771 impaired effect Effects 0.000 description 11
- 238000001771 vacuum deposition Methods 0.000 description 11
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 125000003545 alkoxy group Chemical group 0.000 description 10
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 9
- 150000001450 anions Chemical class 0.000 description 9
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 8
- 229910052782 aluminium Inorganic materials 0.000 description 8
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 8
- 239000004210 ether based solvent Substances 0.000 description 8
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 125000001624 naphthyl group Chemical group 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
- 125000003342 alkenyl group Chemical group 0.000 description 7
- 125000000304 alkynyl group Chemical group 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 7
- 239000011248 coating agent Substances 0.000 description 7
- 239000003759 ester based solvent Substances 0.000 description 7
- 239000011254 layer-forming composition Substances 0.000 description 7
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 6
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 6
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 125000002252 acyl group Chemical group 0.000 description 6
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 6
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 6
- 125000006165 cyclic alkyl group Chemical group 0.000 description 6
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 6
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 6
- 125000005843 halogen group Chemical group 0.000 description 6
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 6
- 239000003446 ligand Substances 0.000 description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 6
- 125000002950 monocyclic group Chemical group 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 125000004453 alkoxycarbonyl group Chemical group 0.000 description 5
- 125000004104 aryloxy group Chemical group 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 125000001309 chloro group Chemical group Cl* 0.000 description 5
- 229940125898 compound 5 Drugs 0.000 description 5
- 125000004093 cyano group Chemical group *C#N 0.000 description 5
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 229910052740 iodine Inorganic materials 0.000 description 5
- 150000008040 ionic compounds Chemical class 0.000 description 5
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000000962 organic group Chemical group 0.000 description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000008096 xylene Substances 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 4
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical group C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 125000004414 alkyl thio group Chemical group 0.000 description 4
- 150000001408 amides Chemical class 0.000 description 4
- 125000005110 aryl thio group Chemical group 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 4
- 229920001940 conductive polymer Polymers 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000010828 elution Methods 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 description 4
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 4
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 4
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 4
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 4
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical group C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 125000003373 pyrazinyl group Chemical group 0.000 description 4
- PBMFSQRYOILNGV-UHFFFAOYSA-N pyridazine Chemical group C1=CC=NN=C1 PBMFSQRYOILNGV-UHFFFAOYSA-N 0.000 description 4
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- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- CSNIZNHTOVFARY-UHFFFAOYSA-N 1,2-benzothiazole Chemical group C1=CC=C2C=NSC2=C1 CSNIZNHTOVFARY-UHFFFAOYSA-N 0.000 description 3
- KTZQTRPPVKQPFO-UHFFFAOYSA-N 1,2-benzoxazole Chemical group C1=CC=C2C=NOC2=C1 KTZQTRPPVKQPFO-UHFFFAOYSA-N 0.000 description 3
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 3
- MXVTXRCFKWSEAZ-UHFFFAOYSA-N 1,2-dihydrocyclobuta[a]naphthalene Chemical group C1=CC2=CC=CC=C2C2=C1CC2 MXVTXRCFKWSEAZ-UHFFFAOYSA-N 0.000 description 3
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 description 3
- IANQTJSKSUMEQM-UHFFFAOYSA-N 1-benzofuran Chemical group C1=CC=C2OC=CC2=C1 IANQTJSKSUMEQM-UHFFFAOYSA-N 0.000 description 3
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical group C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- BLMBNEVGYRXFNA-UHFFFAOYSA-N 1-methoxy-2,3-dimethylbenzene Chemical compound COC1=CC=CC(C)=C1C BLMBNEVGYRXFNA-UHFFFAOYSA-N 0.000 description 3
- AVRPFRMDMNDIDH-UHFFFAOYSA-N 1h-quinazolin-2-one Chemical group C1=CC=CC2=NC(O)=NC=C21 AVRPFRMDMNDIDH-UHFFFAOYSA-N 0.000 description 3
- UJCFZCTTZWHRNL-UHFFFAOYSA-N 2,4-Dimethylanisole Chemical compound COC1=CC=C(C)C=C1C UJCFZCTTZWHRNL-UHFFFAOYSA-N 0.000 description 3
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical group C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000004062 acenaphthenyl group Chemical group C1(CC2=CC=CC3=CC=CC1=C23)* 0.000 description 3
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 3
- 125000002777 acetyl group Chemical group [H]C([H])([H])C(*)=O 0.000 description 3
- 125000004442 acylamino group Chemical group 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- 125000003282 alkyl amino group Chemical group 0.000 description 3
- 125000005196 alkyl carbonyloxy group Chemical group 0.000 description 3
- 125000004390 alkyl sulfonyl group Chemical group 0.000 description 3
- 125000005577 anthracene group Chemical group 0.000 description 3
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- 125000001769 aryl amino group Chemical group 0.000 description 3
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- 125000003828 azulenyl group Chemical group 0.000 description 3
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical group C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 3
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 3
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 3
- 238000010538 cationic polymerization reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000013626 chemical specie Substances 0.000 description 3
- 125000005578 chrysene group Chemical group 0.000 description 3
- 125000003754 ethoxycarbonyl group Chemical group C(=O)(OCC)* 0.000 description 3
- ZTYYDUBWJTUMHW-UHFFFAOYSA-N furo[3,2-b]furan Chemical group O1C=CC2=C1C=CO2 ZTYYDUBWJTUMHW-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 125000002883 imidazolyl group Chemical group 0.000 description 3
- 125000001041 indolyl group Chemical group 0.000 description 3
- 238000010030 laminating Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical class 0.000 description 3
- 125000001160 methoxycarbonyl group Chemical group [H]C([H])([H])OC(*)=O 0.000 description 3
- 229940095102 methyl benzoate Drugs 0.000 description 3
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical group C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 125000005327 perimidinyl group Chemical group N1C(=NC2=CC=CC3=CC=CC1=C23)* 0.000 description 3
- RDOWQLZANAYVLL-UHFFFAOYSA-N phenanthridine Chemical group C1=CC=C2C3=CC=CC=C3C=NC2=C1 RDOWQLZANAYVLL-UHFFFAOYSA-N 0.000 description 3
- 150000005041 phenanthrolines Chemical class 0.000 description 3
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 3
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 3
- 229940049953 phenylacetate Drugs 0.000 description 3
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 150000004032 porphyrins Chemical class 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- 125000005581 pyrene group Chemical group 0.000 description 3
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Landscapes
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
- Electroluminescent Light Sources (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
本発明は重合体に関し、さらに詳しくは、有機電界発光素子の電荷輸送性材料として有用な重合体、該重合体を含有する有機電界発光素子用組成物、該組成物を用いて形成された層を含む有機電界発光素子、並びに、該有機電界発光素子を有する有機EL表示装置及び有機EL照明に関する。 The present invention relates to a polymer, and more particularly, a polymer useful as a charge transporting material for an organic electroluminescent device, a composition for an organic electroluminescent device containing the polymer, and a layer formed using the composition In addition, the present invention relates to an organic electroluminescence element including the organic electroluminescence element, an organic EL display device having the organic electroluminescence element, and organic EL illumination.
有機電界発光素子における有機層の形成方法としては、真空蒸着法と湿式成膜法が挙げられる。真空蒸着法は積層化が容易であるため、陽極及び/又は陰極からの電荷注入の改善、励起子の発光層封じ込めが容易であるという利点を有する。一方で、湿式成膜法は真空プロセスが要らず、大面積化が容易で、様々な機能をもった複数の材料を混合した塗布液を用いることにより、容易に、様々な機能をもった複数の材料を含有する層を形成できる等の利点がある。
しかしながら、湿式成膜法は積層化が困難であるため、真空蒸着法による素子に比べて駆動安定性に劣り、一部を除いて実用レベルに至っていないのが現状である。
Examples of the method for forming the organic layer in the organic electroluminescence device include a vacuum deposition method and a wet film formation method. Since the vacuum deposition method is easy to stack, it has an advantage that the charge injection from the anode and / or the cathode is improved, and the exciton light-emitting layer is easily contained. On the other hand, the wet film formation method does not require a vacuum process, is easy to increase in area, and can be easily applied to a plurality of materials having various functions by using a coating liquid in which a plurality of materials having various functions are mixed. There is an advantage that a layer containing these materials can be formed.
However, since the wet film forming method is difficult to stack, the driving stability is inferior to that of the element by the vacuum vapor deposition method, and the present state is that it has not reached a practical level except for a part.
そこで、湿式成膜法による積層化を行うために、架橋性基を有する電荷輸送性ポリマーが所望され、またその開発が行われている。例えば、特許文献1〜3には、特定の繰り返し単位を有する重合体を含有し、湿式成膜法によって、積層化された有機電界発光素子が開示されている。 Therefore, in order to perform lamination by a wet film forming method, a charge transporting polymer having a crosslinkable group is desired and developed. For example, Patent Documents 1 to 3 disclose organic electroluminescent elements that contain a polymer having a specific repeating unit and are stacked by a wet film forming method.
しかしながら、本発明者等の検討によると、特許文献1〜3に記載のこれらの素子は輝度が低く、駆動寿命が短いという問題点がある。そのため、電荷輸送性材料の電荷注入輸送能や耐久性の向上が求められる。 However, according to the study by the present inventors, these elements described in Patent Documents 1 to 3 have a problem that the luminance is low and the driving life is short. Therefore, improvement of charge injection transport ability and durability of the charge transport material is required.
そこで、本発明は、正孔注入輸送能が高く、耐久性の高い重合体及び該重合体を含む有機電界発光素子用組成物を提供することを課題とする。また本発明は、輝度が高く、駆動寿命が長い有機電界発光素子を提供することを課題とする。 Then, this invention makes it a subject to provide the polymer for organic electroluminescent elements containing a polymer with high hole injection transport ability and high durability, and this polymer. Another object of the present invention is to provide an organic electroluminescence device having high luminance and a long driving life.
本発明者らは、鋭意検討した結果、カルバゾール骨格と、未置換のフェニレン基と芳香族アミン構造とが連結した特定の繰り返し単位を有する重合体を用いることで、上記課題を解決し得ることを見出し、本発明を完成するに至った。 As a result of intensive studies, the present inventors have found that the above problem can be solved by using a polymer having a specific repeating unit in which a carbazole skeleton, an unsubstituted phenylene group and an aromatic amine structure are linked. The headline and the present invention were completed.
即ち、本発明の要旨は、次の[1]〜[16]のとおりである。
[1] 下記式(1)で表される繰り返し単位を有することを特徴とする重合体。
That is, the gist of the present invention is as follows [1] to [16].
[1] A polymer having a repeating unit represented by the following formula (1).
(式中、Ar1は、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基を表し、R1は、各々独立に、水素原子、置換基を有していてもよいアルキル基、芳香族炭化水素基又は芳香族複素環基を表す。) (In the formula, Ar 1 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and each R 1 may independently have a hydrogen atom or a substituent. Represents a good alkyl group, aromatic hydrocarbon group or aromatic heterocyclic group.)
[2]架橋性基を有する[1]に記載の重合体。
[3]Ar1が、置換基を有していても良い2−フルオレニル基である[1]又は[2]に記載の重合体。
[4]架橋性基が、芳香族環に縮環したシクロブテン環を含む基である[2]又は[3]に記載の重合体。
[5]上記式(1)で表される繰り返し単位とは別に、下記式(4)で示される繰り返し単位を有する[1]〜[4]のいずれか1に記載の重合体。
[2] The polymer according to [1], which has a crosslinkable group.
[3] The polymer according to [1] or [2], wherein Ar 1 is a 2-fluorenyl group which may have a substituent.
[4] The polymer according to [2] or [3], wherein the crosslinkable group is a group containing a cyclobutene ring condensed to an aromatic ring.
[5] The polymer according to any one of [1] to [4], having a repeating unit represented by the following formula (4) separately from the repeating unit represented by the above formula (1).
(式中、Ar3は、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基を表し、Ar4は、置換基を有していても良い二価の芳香族炭化水素基又は芳香族複素環基を表すが、該芳香族炭化水素基及び芳香族複素環基は、直接又は連結基を介して、複数個連結したものでも良い。)
[6] 前記Ar4が下記式(6)で表される連結基を介して複数個連結された芳香族炭化
水素基または芳香族複素環基である[5]に記載の重合体。
(In the formula, Ar 3 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and Ar 4 represents a divalent aromatic carbon group which may have a substituent. (It represents a hydrogen group or an aromatic heterocyclic group, and a plurality of the aromatic hydrocarbon group and aromatic heterocyclic group may be linked directly or via a linking group.)
[6] The polymer according to [5], wherein Ar 4 is an aromatic hydrocarbon group or an aromatic heterocyclic group linked together via a linking group represented by the following formula (6).
(式中、aは1〜10の整数を表す。R8及びR9は、各々独立して、水素原子又は置換基を有していてもよい、アルキル基、芳香族炭化水素基、又は芳香族複素環基を表す。R8、R9が複数個存在する場合、同じであっても異なっていても良い。)
[7]上記式(1)で表される繰り返し単位とは別に、下記式(7)で示される繰り返し単位を有する[1]〜[6]のいずれか1に記載の重合体。
Ar27及びAr28は、各々独立に、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar29〜Ar31は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Tは架橋性基を表す。
但し、Ar27及びAr28のいずれもが、直接結合であることはない。)
[8]上記式(1)で表される繰り返し単位とは別に、下記式(8)で示される繰り返し単位を有する[1]〜[6]のいずれか1に記載の重合体。
R15は、置換基を有していてもよい1〜24のアルキル基、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar32及びAr33は、各々独立に、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar34〜Ar38は、各々独立に、置換基を有していてもよい芳香族炭化水素基又芳香族複素環基を表し、
Tは架橋性基を表す。
但し、Ar32及びAr33のいずれもが、直接結合であることはない。)
[9]上記式(1)で表される繰り返し単位とは別に、下記式(9)で示される繰り返し単位を有する[1]〜[6]のいずれか1に記載の重合体。
Ar39、 Ar40、 Ar42、およびAr43は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar41は、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Tは架橋性基を表す。)
[10]重量平均分子量(Mw)が20,000以上であり、分散度(Mw/Mn)が2.5以下である[1]〜[9]のいずれか1に記載の重合体。
[11][1]〜[10]のいずれか1に記載の重合体を含有することを特徴とする有機電界発光素子用組成物。
[12]基板上に、陽極、陰極、及び該陽極と該陰極の間に有機層を有する有機電界発光素子であって、該有機層が、[11]に記載の有機電界発光素子用組成物を用いて、湿式成膜法で形成された層を含むことを特徴とする有機電界発光素子。
[13]前記湿式成膜法で形成された層が、正孔注入層及び正孔輸送層のうちの少なくとも一つである、[12]に記載の有機電界発光素子。
[14]陽極と陰極の間に正孔注入層、正孔輸送層及び発光層を含み、前記正孔注入層、正孔輸送層及び発光層は、全て湿式成膜法により形成されたものである、[12]又は[13]に記載の有機電界発光素子。
[15][12]〜[14]のいずれか1に記載の有機電界発光素子を有することを特徴とする有機EL表示装置。
[16][12]〜[14]のいずれか1に記載の有機電界発光素子を有することを特徴とする有機EL照明。
(In the formula, a represents an integer of 1 to 10. Each of R 8 and R 9 independently represents an alkyl group, an aromatic hydrocarbon group, or an aromatic group that may have a hydrogen atom or a substituent. Represents a heterocyclic group, and when a plurality of R 8 and R 9 are present, they may be the same or different.)
[7] The polymer according to any one of [1] to [6], having a repeating unit represented by the following formula (7) separately from the repeating unit represented by the above formula (1).
Ar 27 and Ar 28 each independently represents a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 29 to Ar 31 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group.
However, neither Ar 27 nor Ar 28 is a direct bond. )
[8] The polymer according to any one of [1] to [6], having a repeating unit represented by the following formula (8) separately from the repeating unit represented by the above formula (1).
R 15 represents an alkyl group of 1 to 24 which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 32 and Ar 33 each independently represent a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 34 to Ar 38 each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group.
However, neither Ar 32 nor Ar 33 is a direct bond. )
[9] The polymer according to any one of [1] to [6], having a repeating unit represented by the following formula (9) separately from the repeating unit represented by the above formula (1).
Ar 39 , Ar 40 , Ar 42 , and Ar 43 each independently represent an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group,
Ar 41 represents a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group. )
[10] The polymer according to any one of [1] to [9], which has a weight average molecular weight (Mw) of 20,000 or more and a dispersity (Mw / Mn) of 2.5 or less.
[11] A composition for an organic electroluminescent device comprising the polymer according to any one of [1] to [10].
[12] An organic electroluminescent device having an anode, a cathode, and an organic layer between the anode and the cathode on a substrate, wherein the organic layer is the composition for an organic electroluminescent device according to [11] And an organic electroluminescent element comprising a layer formed by a wet film formation method.
[13] The organic electroluminescence device according to [12], wherein the layer formed by the wet film formation method is at least one of a hole injection layer and a hole transport layer.
[14] A hole injection layer, a hole transport layer, and a light emitting layer are included between the anode and the cathode, and the hole injection layer, the hole transport layer, and the light emitting layer are all formed by a wet film forming method. The organic electroluminescent element according to [12] or [13].
[15] An organic EL display device comprising the organic electroluminescent element according to any one of [12] to [14].
[16] An organic EL illumination comprising the organic electroluminescence device as described in any one of [12] to [14].
本発明の重合体の主鎖に含まれるカルバゾール環は、2,7−位及び9−位以外には置換基を有さず、カルバゾール環の2,7−位には、夫々1つの置換基を有さないフェニレン基が結合する。このように、本発明の重合体は、置換基の立体障害によって、π共役系の広がりが、阻害されることがない主鎖構造を有するため、正孔注入輸送能及び耐久性に優れる。 The carbazole ring contained in the main chain of the polymer of the present invention has no substituent other than the 2,7-position and 9-position, and one substituent is present at each of the 2,7-position of the carbazole ring. A phenylene group having no bond is bonded. Thus, the polymer of the present invention has a main chain structure in which the spread of the π-conjugated system is not hindered by the steric hindrance of the substituent, and thus has excellent hole injecting and transporting ability and durability.
具体的には、本発明の重合体の主鎖に存在する2つの窒素原子は、カルバゾイル−2,7−ジイル基及び2つの4−フェニレン基を介して、互いに共役した位置に存在するため、本発明の重合体は、正孔輸送能に優れる。さらに、本発明の重合体は、2つの窒素原子の間に、カルバゾール環を構成するフェニレン環を含めて、4つのフェニレン環を有するため、フェニレン環が3つ以下に比べて、窒素原子間の相互作用が小さく、イオン化ポテンシャルが大きくなり、発光層への正孔注入に優れる。 Specifically, since two nitrogen atoms present in the main chain of the polymer of the present invention are present at positions conjugated with each other via a carbazoyl-2,7-diyl group and two 4-phenylene groups, The polymer of the present invention is excellent in hole transport ability. Furthermore, since the polymer of the present invention has four phenylene rings including a phenylene ring constituting a carbazole ring between two nitrogen atoms, the number of phenylene rings is less than three. Small interaction, high ionization potential, and excellent hole injection into the light emitting layer.
また、本発明の重合体の主鎖に存在するカルバゾール環及びその両側の2つのベンゼン環にLUMOが分布するため、電子や励起子に弱い窒素原子周辺には相対的にLUMOが分布しなくなるために耐久性に優れる。 Further, since LUMO is distributed in the carbazole ring present in the main chain of the polymer of the present invention and the two benzene rings on both sides thereof, LUMO is not distributed relatively around the nitrogen atom that is weak against electrons and excitons. Excellent durability.
また、本発明の主鎖にカルバゾール環を有する重合体は、分子の配座変化が乏しい剛直な構造であるため、励起子となった際も分子配座の変化によって励起子のエネルギーを熱的に消費することが少ない。すなわち、励起一重項エネルギー準位差(S1、HOMOとLUMOのエネルギー差)と励起三重項エネルギー準位差(T1)との差が小さい特長が考えられる。
有機EL素子においては各有機層間のエネルギー準位差が適性でないと、発光層へのキャリア注入が難しくなり、駆動電圧が上昇してしまう。または、発光層から隣接層へのキャリア漏洩が起こりやすくなり、素子効率が低下すると考えられる。
これに対して、本発明のように励起子のエネルギー消失が小さいキャリア輸送材料は、エネルギー準位差の変化が小さく、素子効率の点で好ましい。
In addition, since the polymer having a carbazole ring in the main chain of the present invention has a rigid structure in which the conformational change of the molecule is poor, even when it becomes an exciton, the exciton energy is thermally reduced by the change of the molecular conformation. Consume less. That is, it is considered that the difference between the excited singlet energy level difference (S 1 , energy difference between HOMO and LUMO) and the excited triplet energy level difference (T 1 ) is small.
In the organic EL element, if the energy level difference between the organic layers is not appropriate, it becomes difficult to inject carriers into the light emitting layer, and the drive voltage increases. Alternatively, it is considered that carrier leakage from the light emitting layer to the adjacent layer is likely to occur, and the element efficiency is lowered.
On the other hand, a carrier transport material having a small exciton energy loss as in the present invention has a small change in energy level difference and is preferable in terms of device efficiency.
また、本発明の重合体を含有する有機電界発光素子用組成物を用いて湿式成膜することにより得られる層は、クラック等が生じることがなく、平坦である。結果、該層を有する本発明の有機電界発光素子は、輝度が高く、駆動寿命が長い。 Moreover, the layer obtained by carrying out wet film-forming using the composition for organic electroluminescent elements containing the polymer of this invention does not produce a crack etc., but is flat. As a result, the organic electroluminescent element of the present invention having the layer has high luminance and a long driving life.
また、本発明の重合体は、電気化学的安定性に優れる為、該重合体を用いて形成された層を含む素子は、フラットパネル・ディスプレイ(例えばOAコンピュータ用や壁掛けテレビ)、車載表示素子、携帯電話表示や面発光体としての特徴を生かした光源(例えば、複写機の光源、液晶ディスプレイや計器類のバックライト光源)、表示板、標識灯への応用が考えられ、その技術的価値は大きいものである。 Further, since the polymer of the present invention is excellent in electrochemical stability, an element including a layer formed using the polymer is a flat panel display (for example, for OA computers or wall-mounted televisions), an in-vehicle display element. It can be applied to light sources (for example, light sources for copiers, backlight sources for liquid crystal displays and instruments), display boards, and indicator lamps that make use of the characteristics of cell phone displays and surface light emitters. Is a big one.
以下に本発明の実施の形態を詳細に説明するが、以下に記載する構成要件の説明は、本発明の実施態様の一例(代表例)であり、本発明はその要旨を超えない限り、これらの内容に特定されない。 Embodiments of the present invention will be described in detail below, but the description of the constituent elements described below is an example (representative example) of an embodiment of the present invention, and the present invention does not exceed the gist thereof. It is not specified in the contents.
<重合体>
本発明の重合体は、下記式(1)で表される繰り返し単位を有することに特徴をもつものである。
<Polymer>
The polymer of the present invention is characterized by having a repeating unit represented by the following formula (1).
(式中、Ar1は、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基を表し、R1は、水素原子、置換基を有していてもよいアルキル基、芳香族炭化水素基又は芳香族複素環基を表す。) (In the formula, Ar 1 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and R 1 represents a hydrogen atom, an alkyl group which may have a substituent, Represents an aromatic hydrocarbon group or an aromatic heterocyclic group.)
[繰り返し単位の置換基]
上記式(1)で表される繰り返し単位中のAr1、R1において、芳香族炭化水素基と
しては、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環等の、6員環の単環又は2〜5縮合環の1価の基が挙げられる。
[Substituent of repeating unit]
In Ar 1 and R 1 in the repeating unit represented by the above formula (1), examples of the aromatic hydrocarbon group include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, and pyrene ring. , Benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring and the like, monovalent groups of 6-membered monocyclic or 2-5 condensed rings.
芳香族複素環基としては、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シンノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環等の、5又は6員環の単環又は2〜4縮合環の1価の基が挙げられる。 Examples of the aromatic heterocyclic group include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, and a pyrrolopyrazole ring. , Pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, A quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring, etc. Monovalent Group, and the like.
R1で表されるアルキル基としては、例えば、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、sec−ブチル基、tert−ブチル基、n−ヘキシル基、n−オクチル基、シクロヘキシル基、ドデシル基等の、炭素数が通常1以上であり、通常24以下である、直鎖、分岐、又は環状のアルキル基が挙げられる。 Examples of the alkyl group represented by R 1 include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n Examples include a linear, branched, or cyclic alkyl group having a carbon number of usually 1 or more and usually 24 or less, such as a hexyl group, an n-octyl group, a cyclohexyl group, or a dodecyl group.
Ar1は、電荷輸送性が優れる点、耐久性に優れる点から、置換基を有していても良い芳香族炭化水素基が好ましく、中でも置換基を有していても良いベンゼン環又は、フルオレン環の1価の基、すなわち、置換基を有していても良いフェニル基又は、フルオレニル基がより好ましく、置換基を有していても良いフルオレニル基が更により好ましく、置換基を有していても良い2−フルオレニル基が特に好ましい。 Ar 1 is preferably an aromatic hydrocarbon group which may have a substituent from the viewpoint of excellent charge transportability and durability, and among them, a benzene ring or fluorene which may have a substituent. A monovalent group of the ring, that is, a phenyl group which may have a substituent or a fluorenyl group is more preferable, a fluorenyl group which may have a substituent is still more preferable, and has a substituent. The 2-fluorenyl group which may be used is particularly preferred.
R1は、溶解性が優れる点から、アルキル基が好ましく、中でもn−ブチル基、i−ブチル基、sec−ブチル基、tert−ブチル基、n−ヘキシル基、シクロヘキシル基、n−オクチル基、ドデシル基等の、炭素数が4以上、12以下である直鎖、分岐、又は環状のアルキル基が好ましく、炭素数が4以上、12以下の直鎖のアルキル基が更に好ましく、n−ヘキシル基が特に好ましい。 R 1 is preferably an alkyl group from the viewpoint of excellent solubility. Among them, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, A linear, branched, or cyclic alkyl group having 4 or more and 12 or less carbon atoms, such as a dodecyl group, is preferable, a linear alkyl group having 4 or more and 12 or less carbon atoms is more preferable, and an n-hexyl group Is particularly preferred.
Ar1又はR1で表される芳香族炭化水素基、芳香族複素環基、及び、アルキル基が有しても良い置換基としては、本重合体の特性を著しく低減させないものであれば、特に制限はないが、例えば、下記置換基群Zから選ばれる基が挙げられ、アルキル基、アルコキシ基、芳香族炭化水素基、芳香族複素環基が好ましく、アルキル基がより好ましい。
Ar1は、塗布溶媒への溶解性の点から、炭素数1〜24のアルキル基で置換されたフルオレニル基が好ましく、特に、炭素数4〜12のアルキル基で置換された2−フルオレニル基が好ましい。さらに、2−フルオレニル基の9位にアルキル基が置換された9−アルキル−2−フルオレニル基が好ましく、特に、アルキル基が2置換された9、9−ジアルキル−2−フルオレニル基が好ましい。アルキル基で置換されたフルオレニル基であることにより、溶媒に対する溶解性が向上し好ましい。
As the substituent that the aromatic hydrocarbon group, aromatic heterocyclic group, and alkyl group represented by Ar 1 or R 1 may have, as long as the properties of the present polymer are not significantly reduced, Although there is no restriction | limiting in particular, For example, the group chosen from the following substituent group Z is mentioned, An alkyl group, an alkoxy group, an aromatic hydrocarbon group, and an aromatic heterocyclic group are preferable, and an alkyl group is more preferable.
Ar 1 is preferably a fluorenyl group substituted with an alkyl group having 1 to 24 carbon atoms, and particularly a 2-fluorenyl group substituted with an alkyl group having 4 to 12 carbon atoms from the viewpoint of solubility in a coating solvent. preferable. Further, a 9-alkyl-2-fluorenyl group in which an alkyl group is substituted at the 9-position of the 2-fluorenyl group is preferable, and a 9,9-dialkyl-2-fluorenyl group in which the alkyl group is disubstituted is particularly preferable. A fluorenyl group substituted with an alkyl group is preferred because solubility in a solvent is improved.
[置換基群Z]
例えばメチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、sec−ブチル基、tert−ブチル基、n−ヘキシル基、シクロヘキシル基、ドデシル基等の、炭素数が通常1以上であり、好ましくは4以上であり、通常24以下、好ましくは12以下である、直鎖、分岐、又は環状のアルキル基;
例えばビニル基等の、炭素数が通常2以上であり、通常24以下、好ましくは12以下であるアルケニル基;
[Substituent group Z]
For example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl group, etc. A linear, branched or cyclic alkyl group having usually 1 or more carbon atoms, preferably 4 or more, and usually 24 or less, preferably 12 or less;
An alkenyl group having usually 2 or more carbon atoms and usually 24 or less, preferably 12 or less, such as a vinyl group;
例えばエチニル基等の、炭素数が通常2以上であり、通常24以下、好ましくは12以下であるアルキニル基;
例えばメトキシ基、エトキシ基等の、炭素数が通常1以上であり、通常24以下、好ましくは12以下であるアルコキシ基;
例えばフェノキシ基、ナフトキシ基、ピリジルオキシ基等の、炭素数が通常4以上、好ましくは5以上であり、通常36以下、好ましくは24であるアリールオキシ基;
An alkynyl group such as an ethynyl group, which usually has 2 or more carbon atoms and is usually 24 or less, preferably 12 or less;
For example, an alkoxy group having a carbon number of usually 1 or more and usually 24 or less, preferably 12 or less, such as a methoxy group or an ethoxy group;
For example, an aryloxy group having usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24, such as a phenoxy group, a naphthoxy group, or a pyridyloxy group;
例えばメトキシカルボニル基、エトキシカルボニル基等の、炭素数が通常2以上であり、通常24以下、好ましくは12以下であるアルコキシカルボニル基;
例えばジメチルアミノ基、ジエチルアミノ基等の、炭素数が通常2以上であり、通常24以下、好ましくは12以下であるジアルキルアミノ基;
例えばジフェニルアミノ基、ジトリルアミノ基、N−カルバゾリル基等の、炭素数が通常10以上、好ましくは12以上であり、通常36以下、好ましくは24以下のジアリールアミノ基;
For example, an alkoxycarbonyl group having 2 or more carbon atoms, usually 24 or less, preferably 12 or less, such as a methoxycarbonyl group or an ethoxycarbonyl group;
For example, a dialkylamino group having 2 or more carbon atoms and usually 24 or less, preferably 12 or less, such as a dimethylamino group or a diethylamino group;
For example, a diarylamino group having a carbon number of usually 10 or more, preferably 12 or more, usually 36 or less, preferably 24 or less, such as a diphenylamino group, a ditolylamino group, or an N-carbazolyl group;
例えばフェニルメチルアミノ基等の、炭素数が通常7であり、通常36以下、好ましくは24以下であるアリールアルキルアミノ基;
例えばアセチル基、ベンゾイル基等の、炭素数が通常2であり、通常24以下、好ましくは12であるアシル基;
例えばフッ素原子、塩素原子等のハロゲン原子;
例えばトリフルオロメチル基等の、炭素数が通常1以上であり、通常12以下、好ましくは6以下のハロアルキル基;
An arylalkylamino group having usually 7 carbon atoms, usually 36 or less, preferably 24 or less, such as a phenylmethylamino group;
For example, an acetyl group, a benzoyl group, etc., an acyl group having usually 2 carbon atoms and usually having 24 or less, preferably 12;
For example, a halogen atom such as a fluorine atom or a chlorine atom;
A haloalkyl group having usually 1 or more and usually 12 or less, preferably 6 or less, such as a trifluoromethyl group;
例えばメチルチオ基、エチルチオ基等の、炭素数が通常1以上であり、通常24以下、好ましくは12以下のアルキルチオ基;
例えばフェニルチオ基、ナフチルチオ基、ピリジルチオ基等の、炭素数が通常4以上、好ましくは5以上であり、通常36以下、好ましくは24以下であるアリールチオ基;
例えばトリメチルシリル基、トリフェニルシリル基等の、炭素数が通常2以上、好ましくは3以上であり、通常36以下、好ましくは24以下であるシリル基;
For example, an alkylthio group having a carbon number of usually 1 or more and usually 24 or less, preferably 12 or less, such as a methylthio group or an ethylthio group;
For example, an arylthio group having a carbon number of usually 4 or more, preferably 5 or more, usually 36 or less, preferably 24 or less, such as a phenylthio group, a naphthylthio group, or a pyridylthio group;
For example, a silyl group having a carbon number of usually 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as a trimethylsilyl group or a triphenylsilyl group;
例えばトリメチルシロキシ基、トリフェニルシロキシ基等の、炭素数が通常2以上、好ましくは3以上であり、通常36以下、好ましくは24以下であるシロキシ基;
シアノ基;
例えばフェニル基、ナフチル基等の、炭素数が通常6以上であり、通常36以下、好ましくは24以下である芳香族炭化水素基;
例えばチエニル基、ピリジル基等の、炭素数が通常3以上、好ましくは4以上であり、通常36以下、好ましくは24以下である芳香族複素環基。
For example, a siloxy group having 2 or more, preferably 3 or more, usually 36 or less, preferably 24 or less, such as trimethylsiloxy group or triphenylsiloxy group;
A cyano group;
For example, an aromatic hydrocarbon group having usually 6 or more carbon atoms, usually 36 or less, preferably 24 or less, such as a phenyl group or a naphthyl group;
For example, an aromatic heterocyclic group having 3 or more, preferably 4 or more, usually 36 or less, preferably 24 or less, such as thienyl group or pyridyl group.
また、上記各置換基はさらに置換基を有していてもよく、それら置換基としては、上記置換基(置換基群Z)と同じのものが挙げられるが、好ましくは更なる置換基は有さないか、炭素数6以下のアルキル基、炭素数6以下のアルコキシ基、またはフェニル基であり、さらに好ましくはさらなる置換基を有さないことである。 In addition, each of the above-described substituents may further have a substituent, and examples of the substituent include the same as the above-described substituent (substituent group Z), but preferably further substituents are present. Or an alkyl group having 6 or less carbon atoms, an alkoxy group having 6 or less carbon atoms, or a phenyl group, and more preferably having no further substituent.
[別の繰り返し単位]
本発明の重合体は、式(1)で表される繰り返し単位とは別の繰り返し単位を含んでいてもよい。
[Another repeating unit]
The polymer of this invention may contain the repeating unit different from the repeating unit represented by Formula (1).
別の繰り返し単位としては、電荷輸送性、耐久性の点で、式(4)で表される繰り返し単位が好ましい。尚、ここで、下記式(4)で表される繰り返し単位は、上記式(1)の
繰り返し単位中の一部の構造部分と一致しうるが、ここでは、あくまでも、式(1)で表される繰り返し単位以外の構造であることを意味する。
Another repeating unit is preferably a repeating unit represented by the formula (4) from the viewpoint of charge transportability and durability. Here, the repeating unit represented by the following formula (4) may coincide with a part of the structural portion in the repeating unit of the above formula (1), but here, it is represented by the formula (1) to the last. Means a structure other than the repeating unit.
(式中、Ar3は、置換基を有していても良い芳香族炭化水素基又は芳香族複素環基を表し、Ar4は、置換基を有していても良い二価の芳香族炭化水素基又は芳香族複素環基を表すが、該芳香族炭化水素基及び芳香族複素環基は、直接又は連結基を介して、複数個連結したものでも良い。) (In the formula, Ar 3 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent, and Ar 4 represents a divalent aromatic carbon group which may have a substituent. (It represents a hydrogen group or an aromatic heterocyclic group, and a plurality of the aromatic hydrocarbon group and aromatic heterocyclic group may be linked directly or via a linking group.)
Ar3及びAr4における芳香族炭化水素基及び芳香族炭化水素基としては、Ar3は前記Ar1と同様の基、Ar4は前記Ar1と同様の基であって2価である基、有していてもよい置換基は前記置換基群Zと同様の基が好ましいが、特に、電荷輸送性、耐久性の他、陽極側からの正孔注入に優れる点で、式(4)中のAr4が、下記式(5)で表される基であることが好ましい。 As the aromatic hydrocarbon group and the aromatic hydrocarbon group in Ar 3 and Ar 4 , Ar 3 is the same group as Ar 1 , Ar 4 is the same group as Ar 1 and is divalent, The substituent which may be present is preferably the same group as in the substituent group Z. In particular, in the formula (4), in addition to charge transportability and durability, the hole injection from the anode side is excellent. Ar 4 in the formula is preferably a group represented by the following formula (5).
(式中、mは1〜3の整数を表す。) (In the formula, m represents an integer of 1 to 3.)
前記式(4)において、芳香族炭化水素基及び芳香族複素環基が、連結基を介して複数個連結したものである場合の連結基としては、通常、二価の連結基であり、具体的には、例えば、−O−基、−C(=O)−基及び(置換基を有していていてもよい)−CH2−基から選ばれる基を任意の順番で1〜30個連結してなる基が挙げられる。
中でも、発光層への正孔注入に優れる点で、式(4)中のAr4が、下記式(6)で表される連結基を介して複数個連結された芳香族炭化水素基または芳香族複素環基であることが好ましい。
In the above formula (4), the linking group in the case where a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are linked via a linking group is usually a divalent linking group. Specifically, for example, 1 to 30 groups selected from an —O— group, a —C (═O) — group, and an (optionally substituted) —CH 2 — group in any order. Examples include a group formed by linking.
Among them, an aromatic hydrocarbon group or an aromatic group in which a plurality of Ar 4 in the formula (4) are linked via a linking group represented by the following formula (6) in terms of excellent hole injection into the light emitting layer. It is preferably a group heterocyclic group.
(式中、aは1〜10の整数を表す。電荷輸送性の観点から、aは好ましくは1〜6であり、さらに好ましくは1〜3であり、最も好ましくは1である。R8及びR9は、各々独立して、水素原子又は置換基を有していてもよい、アルキル基、芳香族炭化水素基、又は芳香族複素環基を表す。R8、R9が複数個存在する場合、同じであっても異なっていても良い。) (Wherein, a represents an integer of 1 to 10. From the viewpoint of charge transportability, a is preferably 1 to 6, more preferably 1 to 3, and most preferably 1. R 8 and R 9 each independently represents a hydrogen atom or an optionally substituted alkyl group, aromatic hydrocarbon group, or aromatic heterocyclic group, and a plurality of R 8 and R 9 are present. The case may be the same or different.)
R8、R9におけるアルキル基は前記R1と同様の基、芳香族炭化水素基、芳香族複素環基は前記Ar1と同様の基、これらの基が有していてもよい置換基はは前記置換基群Zと同様の基が好ましい。 The alkyl group in R 8 and R 9 is the same group as R 1 above, the aromatic hydrocarbon group, the aromatic heterocyclic group is the same group as Ar 1, and the substituents that these groups may have are Is preferably the same group as the substituent group Z.
[繰り返し単位の含有量]
本発明の重合体において、式(1)で表される繰り返し単位の含有量は特に制限されないが、通常重合体中に10モル%以上含まれ、30モル%以上含まれることが好ましく、40モル%以上含まれることがさらに好ましく、50モル%以上含まれることが特に好ましい。本発明の重合体は、繰り返し単位が、式(1)で表される繰り返し単位のみから構成されていてもよいが、有機電界発光素子とした場合の諸性能をバランスさせる目的から、式(1)とは別の繰り返し単位を有していてもよく、その場合、重合体中の式(1)で表される繰り返し単位の含有量は、通常、99モル%以下、好ましくは95モル%以下、さらに好ましくは90モル%以下である。
[Repeating unit content]
In the polymer of the present invention, the content of the repeating unit represented by the formula (1) is not particularly limited, but is usually 10 mol% or more, preferably 30 mol% or more, and preferably 40 mol% in the polymer. % Is more preferable, and 50 mol% or more is particularly preferable. In the polymer of the present invention, the repeating unit may be composed of only the repeating unit represented by the formula (1). However, for the purpose of balancing various performances when an organic electroluminescent device is used, the formula (1) ) May have another repeating unit, in which case the content of the repeating unit represented by the formula (1) in the polymer is usually 99 mol% or less, preferably 95 mol% or less. More preferably, it is 90 mol% or less.
[架橋性基]
本発明の重合体は、架橋性基を有することが好ましい。本発明の重合体における架橋性基は、式(1)で表される繰り返し単位とは別の繰り返し単位中に存在していても良く、式(1)中のAr1、R1の置換基として存在していても良い。
側鎖であるAr1に架橋性基を有することが、架橋反応が進行しやすいため好ましい。
[Crosslinkable group]
The polymer of the present invention preferably has a crosslinkable group. The crosslinkable group in the polymer of the present invention may be present in a repeating unit different from the repeating unit represented by the formula (1), and the substituents of Ar 1 and R 1 in the formula (1) May exist as
It is preferable that Ar 1 as a side chain has a crosslinkable group because the crosslinking reaction easily proceeds.
本発明の特徴である主鎖構造から遠い位置に架橋性基が存在し、高い正孔注入輸送能及び耐久性が更に向上する点で、式(1)で表される繰り返し単位とは別の繰り返し単位中に架橋性基が存在することが好ましい。別の繰り返し単位が前述の式(4)で表される場合、側鎖であるAr3に架橋性基を有することが、架橋基がトリアリールアミン構造から少なくとも一つの単結合を介して存在し、架橋性基が電荷輸送の妨げとなりにくいため、電荷輸送性がより向上する観点から好ましい。別の繰り返し単位が前述の式(6)で表される場合、sp3混成軌道の中心となる炭素原子に結合しているR8またはR9に架橋性基を有することが、電荷輸送性が向上する点および、温和な条件で不溶化する点で好ましい。 It is different from the repeating unit represented by the formula (1) in that a crosslinkable group is present at a position far from the main chain structure, which is a feature of the present invention, and the high hole injecting and transporting ability and durability are further improved It is preferable that a crosslinkable group is present in the repeating unit. When another repeating unit is represented by the above formula (4), the side chain Ar 3 has a crosslinkable group, and the crosslinkable group is present from the triarylamine structure through at least one single bond. Since the crosslinkable group is unlikely to hinder charge transport, it is preferable from the viewpoint of further improving charge transportability. When another repeating unit is represented by the above formula (6), the charge transportability is improved by having a crosslinkable group at R 8 or R 9 bonded to the carbon atom that is the center of the sp3 hybrid orbital. It is preferable in that it is insolubilized under mild conditions.
架橋性基を有することで、熱及び/又は活性エネルギー線の照射により起こる反応(難溶化反応)の前後で、有機溶媒に対する溶解性に大きな差を生じさせることができる。
架橋性基とは、熱及び/又は活性エネルギー線の照射により、該架橋性基の近傍に位置する他の分子を構成している基と反応して、新規な化学結合を生成する基のことをいう。この場合、反応する基は架橋性基と同一の基でも異なった基でもよい。
By having a crosslinkable group, it is possible to cause a large difference in solubility in an organic solvent before and after a reaction (slightly soluble reaction) caused by irradiation with heat and / or active energy rays.
A crosslinkable group is a group that reacts with a group constituting another molecule located in the vicinity of the crosslinkable group by irradiation with heat and / or active energy rays to form a new chemical bond. Say. In this case, the reacting group may be the same group as the crosslinkable group or a different group.
[架橋性基群T]
具体的な架橋性基としては、例えば、以下の架橋性基群Tに示す基が挙げられる。
[Crosslinkable group T]
Specific examples of the crosslinkable group include groups shown in the following crosslinkable group group T.
(式中、R3〜R5は、水素原子又はアルキル基を表す。R6、R7、R10は、水素原子、アルキル基又はアルコキシ基を表す。n、jは1〜5の整数、kは1〜7の整数である。nが2以上のとき、複数のR6は同じであっても異なっていてもよく、隣接するR6どうしが結合して環を形成してもよい。jが2以上のとき、複数のR7は同じであっても異なっていてもよく、隣接するR7どうしが結合して環を形成してもよい。kが2以上のとき、複数のR10は同じであっても異なっていてもよい。Ar2は置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表す。) (In the formula, R 3 to R 5 represent a hydrogen atom or an alkyl group. R 6 , R 7 and R 10 represent a hydrogen atom, an alkyl group or an alkoxy group. N and j are integers of 1 to 5, k is an integer of 1 to 7. When n is 2 or more, a plurality of R 6 may be the same or different, and adjacent R 6 may be bonded to form a ring. When j is 2 or more, a plurality of R 7 may be the same or different, and adjacent R 7 may be bonded to form a ring, and when k is 2 or more, a plurality of R 7 10 may be the same or different, and Ar 2 represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent.
R3〜R7、R10のアルキル基としては、通常、炭素数が6以下である直鎖又は分岐の鎖状アルキル基が好ましく、例えばメチル基、エチル基、n−プロピル基、2−プロピル基、n−ブチル基、イソブチル基等である。より好ましくはメチル基又はエチル基である。R3〜R7、R10の炭素数が6以下であれば、架橋反応を立体的に阻害することもなく、膜の不溶化が起こりやすい傾向にある。 As the alkyl group for R 3 to R 7 and R 10 , a linear or branched chain alkyl group having 6 or less carbon atoms is usually preferable, for example, methyl group, ethyl group, n-propyl group, 2-propyl group. Group, n-butyl group, isobutyl group and the like. More preferred is a methyl group or an ethyl group. If the number of carbon atoms of R 3 to R 7 and R 10 is 6 or less, the crosslinking reaction is not sterically hindered and the film tends to be insolubilized.
R6、R7、R10のアルコキシ基としては、通常、炭素数が6以下である直鎖又は分岐の鎖状アルコキシ基が好ましく、例えばメトキシ基、エトキシ基、n−プロポキシ基、2−プロポキシ基、n−ブトキシ基等である。より好ましくはメトキシ基、エトキシ基である。R6、R7、R10の炭素数が6以下であれば、架橋反応を立体的に阻害することもなく、膜の不溶化が起こりやすい傾向にある。 As the alkoxy group for R 6 , R 7 , and R 10 , a linear or branched chain alkoxy group having 6 or less carbon atoms is usually preferable. For example, methoxy group, ethoxy group, n-propoxy group, 2-propoxy group Group, n-butoxy group and the like. More preferred are a methoxy group and an ethoxy group. When R 6 , R 7 , and R 10 have 6 or less carbon atoms, the crosslinking reaction is not sterically hindered and the film tends to be insolubilized.
また、Ar2の置換基を有していてもよい芳香族炭化水素基としては、例えば、1個の遊離原子価を有する、ベンゼン環、ナフタレン環等の6員環の単環又は2〜5縮合環が挙
げられる。特に1個の遊離原子価を有するベンゼン環が好ましい。また、Ar2は、置換基を有していてもよい芳香族炭化水素基を2以上結合させた基であっても良い。このような基としては、ビフェニレン基、ターフェニレン基等が挙げられ、4,4’−ビフェニレン基が好ましい。
Ar2が有していてもよい置換基は前述の置換基群Zと同様である。
In addition, examples of the aromatic hydrocarbon group which may have a substituent of Ar 2 include, for example, a monocyclic 6-membered ring such as a benzene ring or a naphthalene ring having one free valence, or 2 to 5 A condensed ring is mentioned. In particular, a benzene ring having one free valence is preferable. Ar 2 may be a group in which two or more aromatic hydrocarbon groups which may have a substituent are bonded. Examples of such a group include a biphenylene group and a terphenylene group, and a 4,4′-biphenylene group is preferable.
The substituent that Ar 2 may have is the same as the substituent group Z described above.
架橋性基のうち、エポキシ基、オキセタン基等の環状エーテル基、ビニルエーテル基等のカチオン重合によって架橋反応する基が、反応性が高く、架橋による不溶化が容易な点で好ましい。中でも、カチオン重合の速度を制御しやすい点でオキセタン基がより好ましく、カチオン重合の際に素子の劣化をまねくおそれのあるヒドロキシル基が生成しにくい点でビニルエーテル基が好ましい。 Among the crosslinkable groups, a group that undergoes a crosslinking reaction by cationic polymerization such as a cyclic ether group such as an epoxy group or an oxetane group, or a vinyl ether group is preferable in terms of high reactivity and easy insolubilization by crosslinking. Among these, an oxetane group is more preferable in terms of easy control of the rate of cationic polymerization, and a vinyl ether group is preferable in that a hydroxyl group that may cause deterioration of the device during cationic polymerization is difficult to generate.
また、シンナモイル基などアリールビニルカルボニル基、1価の遊離原子価を有するベンゾシクロブテン環、1価の遊離原子価を有する1,2−ジヒドロシクロブタ〔a〕ナフタレン環等の環化付加反応する基が、素子の電気化学的安定性をさらに向上させる点で好ましい。 Cycloaddition reaction of aryl vinylcarbonyl group such as cinnamoyl group, benzocyclobutene ring having a monovalent free valence, 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence, etc. A group is preferred in that it further improves the electrochemical stability of the device.
また、架橋性基の中でも、架橋後の構造が特に安定な点で、1価の遊離原子価を有する芳香族環に縮環したシクロブテン環、1価の遊離原子価を有する1,2−ジヒドロシクロブタ〔a〕ナフタレン環を含む基が好ましく、中でもベンゾシクロブテン環または1価の遊離原子価を有する1,2−ジヒドロシクロブタ〔a〕ナフタレン環が更に好ましく、架橋反応温度が低い点で1価の遊離原子価を有する1,2−ジヒドロシクロブタ〔a〕ナフタレン環が特に好ましい。 Among the crosslinkable groups, a cyclobutene ring fused to an aromatic ring having a monovalent free valence and a 1,2-dihydro having a monovalent free valence are particularly advantageous in that the structure after crosslinking is particularly stable. A group containing a cyclobuta [a] naphthalene ring is preferred, and a benzocyclobutene ring or a 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence is more preferred, and the crosslinking reaction temperature is low. A 1,2-dihydrocyclobuta [a] naphthalene ring having a monovalent free valence is particularly preferred.
[架橋性基を有する繰り返し単位]
本発明の重合体は、下記式(7)で表される繰り返し単位を含むことが、電荷輸送性が向上する点で好ましい。
[Repeating unit having a crosslinkable group]
The polymer of the present invention preferably contains a repeating unit represented by the following formula (7) from the viewpoint of improving charge transportability.
(式(7)中、pは0以上、3以下の整数を表し、
Ar27及びAr28は、各々独立に、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar29〜Ar31は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Tは架橋性基を表す。
但し、Ar27及びAr28のいずれもが、直接結合であることはない。)
式(7)中の架橋性基Tは、トリアリールアミン構造から少なくとも一つの単結合を介
して存在し、架橋性基Tは電荷輸送の妨げとなりにくいため、電荷輸送性がより向上する。
本発明の重合体は、下記式(8)で表される繰り返し単位を含むことが、電荷輸送性が向上する点および、より温和な条件で不溶化する点で好ましい。
(In formula (7), p represents an integer of 0 or more and 3 or less,
Ar 27 and Ar 28 each independently represents a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 29 to Ar 31 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group.
However, neither Ar 27 nor Ar 28 is a direct bond. )
The crosslinkable group T in the formula (7) is present through at least one single bond from the triarylamine structure, and the crosslinkable group T is unlikely to hinder charge transport, so that the charge transportability is further improved.
The polymer of the present invention preferably contains a repeating unit represented by the following formula (8) from the viewpoint of improving the charge transportability and insolubilizing under milder conditions.
R15は、置換基を有していてもよい1〜24のアルキル基、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar32及びAr33は、各々独立に、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar34〜Ar38は、各々独立に、置換基を有していてもよい芳香族炭化水素基又芳香族複素環基を表し、
Tは式(7)と同様に架橋性基を表す。
但し、Ar32及びAr33のいずれもが、直接結合であることはない。)
式(8)中のsp3混成軌道の中心となる炭素原子は、π共役系に関与しないため、sp3混成軌道の中心となる炭素原子に結合する側鎖である架橋性基は電荷輸送の妨げとなりにくいため、電荷輸送性がより向上する。
sp3混成軌道の中心である原子は、sp2混成軌道の中心である原子に比べ、周りの結合の回転が起こりやすいため、重合体における架橋性基は効率よく反応するため、架橋性基の数が少なくても、又は、架橋反応の条件が穏和であっても有機溶剤に対して難溶とすることができる。
本発明の重合体は、下記式(9)で表される繰り返し単位を含むことが、電荷輸送性が向上する点で好ましい。
R 15 represents an alkyl group of 1 to 24 which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 32 and Ar 33 each independently represent a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 34 to Ar 38 each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group as in formula (7).
However, neither Ar 32 nor Ar 33 is a direct bond. )
In the formula (8), the carbon atom that is the center of the sp3 hybrid orbital does not participate in the π-conjugated system. Therefore, the crosslinkable group that is a side chain bonded to the carbon atom that is the center of the sp3 hybrid orbital hinders charge transport. Since it is difficult, charge transportability is further improved.
Since the atom that is the center of the sp3 hybrid orbital is more likely to rotate around the bond than the atom that is the center of the sp2 hybrid orbital, the crosslinkable group in the polymer reacts efficiently, so the number of crosslinkable groups is Even if the amount is small or the conditions for the crosslinking reaction are mild, it can be hardly soluble in the organic solvent.
The polymer of the present invention preferably contains a repeating unit represented by the following formula (9) from the viewpoint of improving charge transportability.
(式(9)中、rは0以上、3以下の整数を表し、
Ar39、 Ar40、 Ar42、およびAr43は、各々独立に、置換基を有して
いてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar41は、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Tは式(7)と同様に架橋性基を表す。)
式(9)中の架橋性基Tは、主鎖のアリーレン基から少なくとも一つの単結合を介して存在し、架橋性基は電荷輸送の妨げとなりにくいため、電荷輸送性がより向上する。
(In the formula (9), r represents an integer of 0 or more and 3 or less,
Ar 39 , Ar 40 , Ar 42 , and Ar 43 each independently represent an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group,
Ar 41 represents a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group as in formula (7). )
The crosslinkable group T in the formula (9) is present from the arylene group of the main chain through at least one single bond, and the crosslinkable group is unlikely to hinder charge transport, so that the charge transport property is further improved.
[Ar27〜Ar43]
式(7)〜(9)において、Ar27、Ar28、Ar32、Ar33及びAr41はそれぞれ、直接結合、置換基を有していてもよい2価の芳香族炭化水素基、又は置換基を有していてもよい2価の芳香族複素環基を表す。前記芳香族炭化水素基及び芳香族複素環基は、複数個、結合したものでもよい。
[Ar 27 ~Ar 43]
In formulas (7) to (9), Ar 27 , Ar 28 , Ar 32 , Ar 33 and Ar 41 are each a direct bond, a divalent aromatic hydrocarbon group which may have a substituent, or a substituent. Represents a divalent aromatic heterocyclic group which may have a group; A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.
Ar29、Ar30、Ar34、Ar35、Ar36及びAr40はそれぞれ、置換基を有していてもよい2価の芳香族炭化水素基、又は置換基を有していてもよい2価の芳香族複素環基を表す。前記芳香族炭化水素基及び芳香族複素環基は、複数個、結合したものでもよい。
Ar39は置換基を有していてもよい3価の芳香族炭化水素基、又は置換基を有していてもよい3価の芳香族複素環基を表す。前記芳香族炭化水素基及び芳香族複素環基は、複数個、結合したものでもよい。
Ar 29 , Ar 30 , Ar 34 , Ar 35 , Ar 36 and Ar 40 are each a divalent aromatic hydrocarbon group which may have a substituent, or a divalent which may have a substituent. Represents an aromatic heterocyclic group. A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.
Ar 39 represents a trivalent aromatic hydrocarbon group which may have a substituent, or a trivalent aromatic heterocyclic group which may have a substituent. A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.
Ar31、Ar37、Ar38、Ar42及びAr43はそれぞれ、置換基を有していてもよい1価の芳香族炭化水素基、又は置換基を有していてもよい1価の芳香族複素環基を表す。前記芳香族炭化水素基及び芳香族複素環基は、複数個、結合したものでもよい。
芳香族炭化水素基としては、炭素数6〜30が好ましく、例えば、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオランテン環、フルオレン環などの、6員環の単環又は2〜5縮合環の1価または2価の基が挙げられる。
Ar 31 , Ar 37 , Ar 38 , Ar 42 and Ar 43 are each a monovalent aromatic hydrocarbon group which may have a substituent or a monovalent aromatic which may have a substituent. Represents a heterocyclic group. A plurality of the aromatic hydrocarbon groups and aromatic heterocyclic groups may be bonded.
The aromatic hydrocarbon group preferably has 6 to 30 carbon atoms. For example, a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring , Fluoranthene ring, fluorene ring, monovalent or divalent group of 6-membered monocyclic ring or 2-5 condensed ring.
芳香族複素環基としては、炭素数3〜30が好ましく、例えば、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シンノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環などの、5又は6員環の単環又は2〜4縮合環の1価または2価の基が挙げられる。 The aromatic heterocyclic group preferably has 3 to 30 carbon atoms, for example, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, oxadiazole ring, indole ring, carbazole ring. , Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine 5- or 6-membered ring such as ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, cinnoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring Monovalent or divalent radical of a monocyclic or 2-4 fused ring may be mentioned.
電荷輸送性が優れる点、耐久性に優れる点から、芳香族炭化水素基が好ましく、ベンゼン環または、9,9’位に置換基を有するフルオレン環の1価または2価の基がさらに好ましく、1価のフルオレン環の場合はフェニル基、2フルオレニル基、2価の場合は1,3−フェニレン基、1,4−フェニレン基、9,9’位に置換基を有する2,7−フルオレニル基が最も好ましい。 From the viewpoint of excellent charge transportability and durability, an aromatic hydrocarbon group is preferable, and a monovalent or divalent group of a benzene ring or a fluorene ring having a substituent at the 9,9′-position is more preferable. In the case of a monovalent fluorene ring, phenyl group, 2 fluorenyl group, in the case of divalent 1,3-phenylene group, 1,4-phenylene group, 2,7-fluorenyl group having a substituent at the 9,9′-position Is most preferred.
フルオレン構造の9,9’位に有していてもよい置換基は、アルキル基、芳香族炭化水素基又は芳香族複素環基であり、さらにアルキル基、芳香族炭化水素基又は芳香族複素環基で置換されていてもよい。これらアルキル基、芳香族炭化水素基又は芳香族複素環基は前述の置換基群Zにて説明した構造が好ましい。
芳香族炭化水素基及び芳香族複素環基が複数個、結合した基である場合、電荷輸送性が優れる点、耐久性に優れる点から、それらの基が2〜6個連結されていることが好ましい。連結される芳香族炭化水素基及び芳香族複素環基は、1種であっても、複数種であってもよい。
The substituent which may be present at the 9,9′-position of the fluorene structure is an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic group, and further an alkyl group, an aromatic hydrocarbon group or an aromatic heterocyclic ring. It may be substituted with a group. These alkyl group, aromatic hydrocarbon group or aromatic heterocyclic group preferably has the structure described in the above-mentioned substituent group Z.
When a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are bonded to each other, 2 to 6 of these groups are linked from the viewpoint of excellent charge transportability and durability. preferable. The aromatic hydrocarbon group and aromatic heterocyclic group to be linked may be one kind or plural kinds.
また、芳香族炭化水素基及び芳香族複素環基が複数個、結合した基である場合、連結基を介して結合していてもよい。この場合、連結基としては、−CR16R17−、−O−、−CO−、−NR18−、及び−S−からなる群より選ばれる基、及びそれらを2〜10連結した基が好ましい。また、2以上連結される場合、連結基は1種であっても、複数種であってもよい。ここでR16〜R18は、各々独立して、水素原子又は置換基を有していてもよい炭素数1〜24のアルキル基、置換基を有していてもよい炭素数6〜30の芳香族炭化水素基、置換基を有していてもよい炭素数3〜30の芳香族複素環基を表す。好ましい芳香族炭化水素基は、前述の芳香族炭化水素基と同様である。好ましい芳香族複素環基は前述の芳香族複素環基と同様である。連結基としては、−CR16R17−、及び、2〜6連結した−CR16R17−が特に好ましく、−CR16R17−がより好ましい。
R16〜R18が芳香族炭化水素基、芳香族複素環基である場合、置換基を有していてもよく、有してもよい置換基としては本重合体の特性を著しく低減させないものであれば特に制限はないが、好ましくは前記置換基群Zから選ばれる基である。より好ましくは、置換基を有さない。
Further, when a plurality of aromatic hydrocarbon groups and aromatic heterocyclic groups are bonded, they may be bonded through a linking group. In this case, examples of the linking group include a group selected from the group consisting of —CR 16 R 17 —, —O—, —CO—, —NR 18 —, and —S—, and a group in which 2 to 10 thereof are linked. preferable. When two or more are connected, the linking group may be one kind or plural kinds. Here, R 16 to R 18 are each independently a hydrogen atom or an alkyl group having 1 to 24 carbon atoms which may have a substituent, and 6 to 30 carbon atoms which may have a substituent. An aromatic hydrocarbon group and a C3-C30 aromatic heterocyclic group which may have a substituent are represented. Preferred aromatic hydrocarbon groups are the same as the above-mentioned aromatic hydrocarbon groups. Preferred aromatic heterocyclic groups are the same as the aforementioned aromatic heterocyclic groups. As the linking group, —CR 16 R 17 — and 2 to 6 linked —CR 16 R 17 — are particularly preferable, and —CR 16 R 17 — is more preferable.
When R 16 to R 18 are an aromatic hydrocarbon group or an aromatic heterocyclic group, they may have a substituent, and the substituent that may have does not significantly reduce the properties of the present polymer. If it is, there will be no restriction | limiting in particular, Preferably it is group chosen from the said substituent group Z. More preferably, it has no substituent.
[R15]
式(8)において、R15は、水素原子、置換基を有していてもよい1〜24のアルキル基、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。アルキル基は、直鎖、分岐、又は環状の、炭素数が通常1以上であり、通常24以下のアルキル基であり、好ましくは12以下である。具体的には、メチル基、エチル基、n−プロピル基、i−プロピル基、n−ブチル基、i−ブチル基、sec−ブチル基、tert−ブチル基、n−ヘキシル基、シクロヘキシル基、ドデシル基があげられる。R15が置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基である場合、具体例、好ましい例は、Ar31、Ar37、Ar38、Ar42及びAr43と同様である。
式(7)〜(9)において、p、q及びrはそれぞれ、0以上、3以下の整数である。p、q及びrはそれぞれ、2以下が好ましい。
[R 15 ]
In Formula (8), R 15 has a hydrogen atom, an optionally substituted alkyl group having 1 to 24 alkyl groups, an optionally substituted aromatic hydrocarbon group or a substituent group. Represents an aromatic heterocyclic group which may be substituted. The alkyl group is a linear, branched, or cyclic alkyl group having usually 1 or more carbon atoms and usually 24 or less, preferably 12 or less. Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, tert-butyl group, n-hexyl group, cyclohexyl group, dodecyl Group. When R 15 is an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, specific examples and preferred examples are Ar 31 , Ar 37 , Ar 38 , Ar 42 and Ar 43 .
In the formulas (7) to (9), p, q, and r are each an integer of 0 or more and 3 or less. p, q and r are each preferably 2 or less.
[架橋性基の数]
本発明の重合体が有する架橋性基は、架橋することにより十分に不溶化し、その上に湿式成膜法で他の層を形成しやすくなる点では、多い方が好ましい。一方で、形成された層にクラックが生じ難く、未反応架橋性基が残りにくく、有機電界発光素子が長寿命になりやすい点では、架橋性基は少ないことが好ましい。
[Number of crosslinkable groups]
The crosslinkable group possessed by the polymer of the present invention is preferably larger in that it is sufficiently insolubilized by crosslinking, and other layers can be easily formed thereon by a wet film forming method. On the other hand, it is preferable that the number of crosslinkable groups is small from the viewpoint that cracks are not easily generated in the formed layer, unreacted crosslinkable groups hardly remain, and the organic electroluminescent element tends to have a long life.
本発明の重合体における、1つのポリマー鎖の中に存在する架橋性基は、好ましくは平均1以上、より好ましくは平均2以上であり、また好ましくは200以下、より好ましくは100以下である。
また、本発明の重合体が有する架橋性基の数は、重合体の分子量1000あたりの数で表すことができる。
本発明の重合体が有する架橋性基の数を、重合体の分子量1000あたりの数で表した場合、分子量1000あたり、通常3.0個以下、好ましくは2.0個以下、さらに好ましくは1.0以下であり、また通常0.01以上、好ましくは0.05以上である。
The crosslinkable group present in one polymer chain in the polymer of the present invention is preferably an average of 1 or more, more preferably an average of 2 or more, and preferably 200 or less, more preferably 100 or less.
The number of crosslinkable groups possessed by the polymer of the present invention can be represented by the number per 1000 molecular weight of the polymer.
When the number of crosslinkable groups of the polymer of the present invention is represented by the number per 1000 molecular weight of the polymer, it is usually 3.0 or less, preferably 2.0 or less, more preferably 1 per 1000 molecular weight. 0.0 or less, and usually 0.01 or more, preferably 0.05 or more.
架橋性基の数が上記範囲内であると、クラック等が起き難く、平坦な膜が得られ易い。
また、架橋密度が適度であるため、架橋反応後の層内に残る未反応の架橋性基が少なく、得られる素子の寿命に影響し難い。
さらに、架橋反応後の、有機溶媒に対する難溶性が十分であるため、湿式成膜法での多層積層構造が形成し易い。
When the number of crosslinkable groups is within the above range, cracks or the like hardly occur and a flat film can be easily obtained.
In addition, since the crosslinking density is moderate, there are few unreacted crosslinking groups remaining in the layer after the crosslinking reaction, and it is difficult to affect the life of the resulting device.
Furthermore, since the poor solubility in an organic solvent after the crosslinking reaction is sufficient, a multilayer laminated structure can be easily formed by a wet film forming method.
ここで、重合体の分子量1000あたりの架橋性基の数は、重合体からその末端基を除いて、合成時の仕込みモノマーのモル比と、構造式から算出することができる。
例えば、後述の実施例1で合成した重合体1の場合で説明すると、重合体1において、末端基を除いた繰り返し単位の分子量は平均559.7であり、また架橋性基は、1繰り返し単位当たり平均0.277個である。これを単純比例により計算すると、分子量1000あたりの架橋性基の数は、0.495個と算出される。
Here, the number of crosslinkable groups per 1000 molecular weight of the polymer can be calculated from the molar ratio of the charged monomers at the time of synthesis and the structural formula, excluding the terminal group from the polymer.
For example, in the case of the polymer 1 synthesized in Example 1 described later, in the polymer 1, the molecular weight of the repeating unit excluding the terminal group is 559.7 on average, and the crosslinkable group is 1 repeating unit. The average number is 0.277. When this is calculated by simple proportion, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.495.
[重合体の分子量]
本発明の重合体の重量平均分子量は、通常3,000,000以下、好ましくは1,000,000以下、より好ましくは500,000以下、さらに好ましくは200,000以下、特に好ましくは100,000以下であり、また通常2,500以上、好ましくは5,000以上、より好ましくは10,000以上、さらに好ましくは20,000以上、特に好ましくは30,000以上である。
[Molecular weight of polymer]
The weight average molecular weight of the polymer of the present invention is usually 3,000,000 or less, preferably 1,000,000 or less, more preferably 500,000 or less, still more preferably 200,000 or less, and particularly preferably 100,000. In addition, it is usually 2,500 or more, preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and particularly preferably 30,000 or more.
重合体の重量平均分子量が上記上限値を超えると、溶媒に対する溶解性が低下するため、成膜性が損なわれるおそれがある。また、重合体の重量平均分子量が上記下限値を下回ると、重合体のガラス転移温度、融点及び気化温度が低下するため、耐熱性が低下する場合がある。加えて、架橋反応後の塗膜の有機溶媒に対する不溶性が不十分である場合がある。 If the weight average molecular weight of the polymer exceeds the above upper limit, the solubility in a solvent is lowered, so that the film formability may be impaired. Moreover, since the glass transition temperature, melting | fusing point, and vaporization temperature of a polymer will fall when the weight average molecular weight of a polymer is less than the said lower limit, heat resistance may fall. In addition, the insolubility of the coating film after the crosslinking reaction in the organic solvent may be insufficient.
また、本発明の重合体における数平均分子量(Mn)は、通常2,500,000以下
、好ましくは750,000以下、より好ましくは400,000以下、特に好ましくは100,000以下であり、また通常2,000以上、好ましくは4,000以上、より好ましくは8,000以上、さらに好ましくは20,000以上である。
さらに、本発明の重合体における分散度(Mw/Mn)は、好ましくは3.5以下であり、さらに好ましくは2.5以下、特に好ましくは2.0以下である。尚、分散度は値が小さい程よいため、下限値は理想的には1である。該重合体の分散度が、上記上限値以下であると、精製が容易で、また溶媒に対する溶解性や電荷輸送能が良好である。
The number average molecular weight (Mn) in the polymer of the present invention is usually 2,500,000 or less, preferably 750,000 or less, more preferably 400,000 or less, and particularly preferably 100,000 or less. Usually, it is 2,000 or more, preferably 4,000 or more, more preferably 8,000 or more, and further preferably 20,000 or more.
Furthermore, the dispersity (Mw / Mn) in the polymer of the present invention is preferably 3.5 or less, more preferably 2.5 or less, and particularly preferably 2.0 or less. Since the degree of dispersion is preferably as small as possible, the lower limit is ideally 1. When the degree of dispersion of the polymer is not more than the above upper limit, purification is easy, and solubility in a solvent and charge transporting ability are good.
通常、重合体の重量平均分子量はSEC(サイズ排除クロマトグラフィー)測定により決定される。SEC測定では高分子量成分ほど溶出時間が短く、低分子量成分ほど溶出時間が長くなるが、分子量既知のポリスチレン(標準試料)の溶出時間から算出した校正曲線を用いて、サンプルの溶出時間を分子量に換算することによって、重量平均分子量が算出される。 Usually, the weight average molecular weight of a polymer is determined by SEC (size exclusion chromatography) measurement. In SEC measurement, the elution time is shorter for higher molecular weight components and the elution time is longer for lower molecular weight components, but using the calibration curve calculated from the elution time of polystyrene (standard sample) with a known molecular weight, the elution time of the sample is changed to the molecular weight. The weight average molecular weight is calculated by conversion.
[具体例]
本発明の重合体の具体例を以下に示すが、本発明の重合体はこれらに限定されるものではない。なお、化学式中の数字は繰返し単位のモル比を表す。
これらの重合体は、ランダム共重合体、交互共重合体、ブロック共重合体、又はグラフト共重合体等のいずれでもよく、単量体の配列順序には限定されない。
[Concrete example]
Specific examples of the polymer of the present invention are shown below, but the polymer of the present invention is not limited thereto. The numbers in the chemical formula represent the molar ratio of repeating units.
These polymers may be any of random copolymers, alternating copolymers, block copolymers, graft copolymers, and the like, and are not limited to the sequence of monomers.
[重合体の製造方法]
本発明の重合体の製造方法は特には制限されず、本発明の重合体が得られる限り任意である。例えば、Suzuki反応による重合方法、Grignard反応による重合方法、Yamamoto反応による重合方法、Ullmann反応による重合方法、Buchwald−Hartwig反応による重合方法等などによって製造できる。
[Method for producing polymer]
The method for producing the polymer of the present invention is not particularly limited, and is arbitrary as long as the polymer of the present invention is obtained. For example, it can be produced by a polymerization method using a Suzuki reaction, a polymerization method using a Grignard reaction, a polymerization method using a Yamamoto reaction, a polymerization method using an Ullmann reaction, a polymerization method using a Buchwald-Hartwig reaction, or the like.
Ullmann反応による重合方法及びBuchwald−Hartwig反応による重合方法の場合、例えば、式(1a)で表されるジハロゲン化アリール(XはI、Br、Cl、F等のハロゲン原子を示す。)と式(2a)で表される1級アミノアリールとを反応させることにより、本発明の重合体が合成される。 In the case of the polymerization method by the Ullmann reaction and the polymerization method by the Buchwald-Hartwig reaction, for example, an aryl halide having the formula (1a) (X represents a halogen atom such as I, Br, Cl, F, etc.) and a formula ( The polymer of the present invention is synthesized by reacting with the primary aminoaryl represented by 2a).
(式中、Xはハロゲン原子を示し、Ar1、R1は前記と同義である。) (In the formula, X represents a halogen atom, and Ar 1 and R 1 are as defined above.)
尚、前記の重合方法において、通常、N−アリール結合を形成する反応は、例えば炭酸カリウム、tert−ブトキシナトリウム、トリエチルアミン等の塩基存在下で行う。また、例えば銅やパラジウム錯体等の遷移金属触媒存在下で行うこともできる。 In the above polymerization method, the reaction for forming an N-aryl bond is usually performed in the presence of a base such as potassium carbonate, tert-butoxy sodium, triethylamine or the like. Moreover, it can also carry out in presence of transition metal catalysts, such as copper and a palladium complex, for example.
<有機電界発光素子材料>
本発明の重合体は、有機電界発光素子材料として特に好適に用いることができる。つまり、本発明の重合体は有機電界発光素子材料であることが好ましい。
本発明の重合体が有機電界発光素子材料として用いられる場合は、有機電界発素子における正孔注入層及び正孔輸送層の少なくとも一方を形成する材料、つまり電荷輸送性材料として用いることが好ましい。
<Organic electroluminescent material>
The polymer of the present invention can be particularly suitably used as an organic electroluminescent element material. That is, the polymer of the present invention is preferably an organic electroluminescent element material.
When the polymer of the present invention is used as an organic electroluminescent element material, it is preferably used as a material forming at least one of a hole injection layer and a hole transport layer in the organic electroluminescent element, that is, a charge transporting material.
電荷輸送性材料として用いる場合、本発明の重合体を1種類含有するものであってもよく、2種類以上を任意の組み合わせ及び任意の比率で含有するものであってもよい。
本発明の重合体を用いて有機電界発光素子の正孔注入層及び正孔輸送層の少なくとも一方を形成する場合、正孔注入層及び/又は正孔輸送層中の本発明の重合体の含有量は、通常1〜100質量%、好ましくは5〜100質量%、さらに好ましくは10〜100質量%である。上記の範囲であると、正孔注入層及び/又は正孔輸送層の電荷輸送性が向上し、駆動電圧が低減し、駆動安定性が向上するため好ましい。
When used as a charge transporting material, it may contain one type of the polymer of the present invention, or may contain two or more types in any combination and in any ratio.
When forming at least one of the hole injection layer and the hole transport layer of the organic electroluminescence device using the polymer of the present invention, the inclusion of the polymer of the present invention in the hole injection layer and / or the hole transport layer The amount is usually 1 to 100% by mass, preferably 5 to 100% by mass, and more preferably 10 to 100% by mass. The above range is preferable because the charge transport property of the hole injection layer and / or the hole transport layer is improved, the drive voltage is reduced, and the drive stability is improved.
本発明の重合体が、前記正孔注入層及び/又は正孔輸送層中で100質量%でない場合に、正孔注入層及び/又は正孔輸送層を構成する成分としては後述する正孔輸送性化合物等が挙げられる。
また、有機電界発光素子を簡便に製造することができることから、本発明の重合体は、湿式成膜法で形成される有機層に用いることが好ましい。
When the polymer of the present invention is not 100% by mass in the hole injection layer and / or hole transport layer, the component constituting the hole injection layer and / or hole transport layer will be described later. Compound.
Moreover, since an organic electroluminescent element can be manufactured simply, it is preferable to use the polymer of this invention for the organic layer formed by a wet film-forming method.
<有機電界発光素子用組成物>
本発明の有機電界発光素子用組成物は、本発明の重合体を含有するものである。なお、本発明の有機電界発光素子用組成物は、本発明の重合体を1種類含有するものであっても
よく、2種類以上を任意の組み合わせ及び任意の比率で含有するものであってもよい。
<Composition for organic electroluminescence device>
The composition for organic electroluminescent elements of the present invention contains the polymer of the present invention. In addition, the composition for organic electroluminescent elements of the present invention may contain one type of the polymer of the present invention, or may contain two or more types in any combination and in any ratio. Good.
[重合体の含有量]
本発明の有機電界発光素子用組成物中の本発明の重合体の含有量は、通常0.01〜70質量%、好ましくは0.1〜60質量%、さらに好ましくは0.5〜50質量%である。
上記範囲内であると、形成した有機層に欠陥が生じ難く、また膜厚ムラが生じ難いため好ましい。
本発明の有機電界発光素子用組成物は、本発明の重合体以外に溶媒等を含むことができる。
[Polymer content]
Content of the polymer of this invention in the composition for organic electroluminescent elements of this invention is 0.01-70 mass% normally, Preferably it is 0.1-60 mass%, More preferably, it is 0.5-50 mass. %.
Within the above range, it is preferable because defects are hardly generated in the formed organic layer and unevenness in film thickness is hardly generated.
The composition for organic electroluminescent elements of the present invention can contain a solvent and the like in addition to the polymer of the present invention.
[溶媒]
本発明の有機電界発光素子用組成物は、通常、溶媒を含有する。この溶媒は、本発明の重合体を溶解するものが好ましい。具体的には、本発明の重合体を、室温で通常0.05質量%以上、好ましくは0.5質量%以上、さらに好ましくは1質量%以上溶解する溶媒が好適である。
[solvent]
The composition for organic electroluminescent elements of the present invention usually contains a solvent. This solvent is preferably one that dissolves the polymer of the present invention. Specifically, a solvent that dissolves the polymer of the present invention at room temperature is usually 0.05% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more.
溶媒の具体例としては、トルエン、キシレン、メシチレン、シクロヘキシルベンゼン等の芳香族系溶媒;1,2−ジクロロエタン、クロロベンゼン、o−ジクロロベンゼン等の含ハロゲン溶媒;エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール−1−モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル、1,2−ジメトキシベンゼン、1,3−ジメトキシベンゼン、アニソール、フェネトール、2−メトキシトルエン、3−メトキシトルエン、4−メトキシトルエン、2,3−ジメチルアニソール、2,4−ジメチルアニソール等の芳香族エーテル等のエーテル系溶媒;酢酸エチル、酢酸n−ブチル、乳酸エチル、乳酸n−ブチル等の脂肪族エステル系溶媒;酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸イソプロピル、安息香酸プロピル、安息香酸n−ブチル等の芳香族エステル等のエステル系溶媒;等の有機溶媒、その他、後述の正孔注入層形成用組成物や正孔輸送層形成用組成物に用いられる有機溶媒が挙げられる。 Specific examples of the solvent include aromatic solvents such as toluene, xylene, mesitylene, cyclohexylbenzene; halogen-containing solvents such as 1,2-dichloroethane, chlorobenzene, o-dichlorobenzene; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene Aliphatic ethers such as glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, Ether solvents such as aromatic ethers such as 2,3-dimethylanisole and 2,4-dimethylanisole; aliphatic ester solvents such as ethyl acetate, n-butyl acetate, ethyl lactate and n-butyl lactate; phenyl acetate Organic solvents such as ester solvents such as aromatic esters such as phenyl propionate, methyl benzoate, ethyl benzoate, isopropyl benzoate, propyl benzoate, n-butyl benzoate; And organic solvents used for the composition for forming a hole and the composition for forming a hole transport layer.
なお、溶媒は、1種類を用いてもよく、2種類以上を任意の組み合わせ及び任意の比率で併用してもよい。
中でも、本発明の有機電界発光素子用組成物に含有される溶媒としては、20℃における表面張力が、通常40dyn/cm未満、好ましくは36dyn/cm以下、より好ましくは33dyn/cm以下である溶媒が好ましい。
In addition, 1 type may be used for a solvent and it may use 2 or more types together by arbitrary combinations and arbitrary ratios.
Among them, as a solvent contained in the composition for organic electroluminescent elements of the present invention, a solvent having a surface tension at 20 ° C. of usually less than 40 dyn / cm, preferably 36 dyn / cm or less, more preferably 33 dyn / cm or less. Is preferred.
本発明の有機電界発光素子用組成物を用いて湿式成膜法により塗膜を形成し、本発明の重合体を架橋させて有機層を形成する場合、溶媒と下地の親和性が高いことが好ましい。これは、膜質の均一性が有機電界発光素子の発光の均一性及び安定性に大きく影響するためである。従って、湿式成膜法に用いる有機電界発光素子用組成物には、よりレベリング性が高く均一な塗膜を形成しうるように表面張力が低いことが求められる。そこで前記のような低い表面張力を有する溶媒を使用することにより、本発明の重合体を含有する均一な層を形成することができ、ひいては均一な架橋層を形成することができることから、好ましい。 When a coating film is formed by a wet film-forming method using the composition for organic electroluminescent elements of the present invention, and the polymer of the present invention is crosslinked to form an organic layer, the affinity between the solvent and the base must be high. preferable. This is because the uniformity of film quality greatly affects the uniformity and stability of light emission of the organic electroluminescence device. Therefore, the composition for organic electroluminescent elements used for the wet film-forming method is required to have a low surface tension so that a uniform coating film with higher leveling property can be formed. Therefore, it is preferable to use a solvent having a low surface tension as described above because a uniform layer containing the polymer of the present invention can be formed, and a uniform crosslinked layer can be formed.
低表面張力の溶媒の具体例としては、前述したトルエン、キシレン、メシチレン、シクロヘキシルベンゼン等の芳香族系溶媒、安息香酸エチル等のエステル系溶媒、アニソール等のエーテル系溶媒、トリフルオロメトキシアニソール、ペンタフルオロメトキシベンゼン、3−(トリフルオロメチル)アニソール、エチル(ペンタフルオロベンゾエート)等が挙げられる。 Specific examples of the low surface tension solvent include the aforementioned aromatic solvents such as toluene, xylene, mesitylene and cyclohexylbenzene, ester solvents such as ethyl benzoate, ether solvents such as anisole, trifluoromethoxyanisole, penta Examples include fluoromethoxybenzene, 3- (trifluoromethyl) anisole, ethyl (pentafluorobenzoate), and the like.
また一方で、本発明の有機電界発光素子用組成物に含有される溶媒としては、25℃における蒸気圧が、通常10mmHg以下、好ましくは5mmHg以下であり、通常0.1mmHg以上であるものが好ましい。このような溶媒を使用することにより、有機電界発光素子を湿式成膜法により製造するプロセスに好適で、本発明の重合体の性質に適した有機電界発光素子用組成物を調製することができる。
このような溶媒の具体例としては、前述したトルエン、キシレン、メシチレン等の芳香族系溶媒、エーテル系溶媒及びエステル系溶媒が挙げられる。
On the other hand, as a solvent contained in the composition for organic electroluminescent elements of the present invention, a solvent having a vapor pressure at 25 ° C. of usually 10 mmHg or less, preferably 5 mmHg or less, and usually 0.1 mmHg or more is preferable. . By using such a solvent, a composition for an organic electroluminescent device suitable for the process of producing an organic electroluminescent device by a wet film forming method and suitable for the properties of the polymer of the present invention can be prepared. .
Specific examples of such a solvent include the aforementioned aromatic solvents such as toluene, xylene and mesitylene, ether solvents and ester solvents.
ところで、水分は有機電界発光素子の性能劣化を引き起こす可能性があり、中でも特に連続駆動時の輝度低下を促進する可能性がある。そこで、湿式成膜中に残留する水分をできる限り低減するために、前記の溶媒の中でも、25℃における水の溶解度が1質量%以下であるものが好ましく、0.1質量%以下である溶媒がより好ましい。
本発明の有機電界発光素子用組成物に含有される溶媒の含有量は、通常10質量%以上、好ましくは30質量%以上、より好ましくは50質量%以上、特に好ましくは80質量%以上である。溶媒の含有量が上記下限以上であることにより、形成される層の平坦さ及び均一さを良好にすることができる。
By the way, moisture may cause deterioration of the performance of the organic electroluminescent element, and in particular, may promote a decrease in luminance during continuous driving. Therefore, in order to reduce the moisture remaining during wet film formation as much as possible, among the above-mentioned solvents, those having a water solubility of 1% by mass or less at 25 ° C. are preferred, and a solvent having a content of 0.1% by mass or less Is more preferable.
The content of the solvent contained in the composition for organic electroluminescent elements of the present invention is usually 10% by mass or more, preferably 30% by mass or more, more preferably 50% by mass or more, and particularly preferably 80% by mass or more. . When the content of the solvent is not less than the above lower limit, the flatness and uniformity of the formed layer can be improved.
[電子受容性化合物]
本発明の有機電界発光素子用組成物は、正孔注入層を形成するために用いる場合、低抵抗化する点で、さらに電子受容性化合物を含有することが好ましい。
電子受容性化合物としては、酸化力を有し、本発明の重合体から一電子受容する能力を有する化合物が好ましい。具体的には、電子親和力が4eV以上である化合物が好ましく、5eV以上の化合物である化合物がさらに好ましい。
[Electron-accepting compound]
When the composition for organic electroluminescent elements of the present invention is used for forming a hole injection layer, it is preferable to further contain an electron-accepting compound from the viewpoint of reducing resistance.
As the electron-accepting compound, a compound having an oxidizing power and an ability to accept one electron from the polymer of the present invention is preferable. Specifically, a compound with an electron affinity of 4 eV or more is preferable, and a compound with a compound of 5 eV or more is more preferable.
このような電子受容性化合物としては、例えば、トリアリールホウ素化合物、ハロゲン化金属、ルイス酸、有機酸、オニウム塩、アリールアミンとハロゲン化金属との塩、及び、アリールアミンとルイス酸との塩よりなる群から選ばれる1種又は2種以上の化合物等が挙げられる。
具体的には、4−イソプロピル−4’−メチルジフェニルヨードニウムテトラキス(ペンタフルオロフェニル)ボラート、トリフェニルスルホニウムテトラフルオロボラート等の有機基の置換したオニウム塩(国際公開第2005/089024号);塩化鉄(III)(特開平11−251067号公報)、ペルオキソ二硫酸アンモニウム等の高原子価の無機化合物;テトラシアノエチレン等のシアノ化合物;トリス(ペンタフルオロフェニル)ボラン(特開2003−31365号公報)等の芳香族ホウ素化合物;フラーレン誘導体及びヨウ素等が挙げられる。
Examples of such electron-accepting compounds include triarylboron compounds, metal halides, Lewis acids, organic acids, onium salts, salts of arylamines and metal halides, and salts of arylamines and Lewis acids. 1 type, or 2 or more types of compounds chosen from the group which consists of are mentioned.
Specifically, onium salts substituted with organic groups such as 4-isopropyl-4′-methyldiphenyliodonium tetrakis (pentafluorophenyl) borate and triphenylsulfonium tetrafluoroborate (WO 2005/089024); chloride High valence inorganic compounds such as iron (III) (Japanese Patent Laid-Open No. 11-251067) and ammonium peroxodisulfate; Cyano compounds such as tetracyanoethylene; Tris (pentafluorophenyl) borane (Japanese Patent Laid-Open No. 2003-31365) Aromatic boron compounds such as: fullerene derivatives and iodine.
このような化合物として、長周期型周期表(以下、特に断り書きの無い限り「周期表」という場合には、長周期型周期表を指すものとする。)の第15〜17族に属する元素に、少なくとも一つの有機基が炭素原子で結合した構造を有するイオン化合物であることが好ましく、特に、下記式(2)で表される化合物であることが好ましい。 As such a compound, an element belonging to Groups 15 to 17 of a long-period periodic table (hereinafter, unless otherwise specified, the term “periodic table” refers to a long-period periodic table). In addition, an ionic compound having a structure in which at least one organic group is bonded by a carbon atom is preferable, and a compound represented by the following formula (2) is particularly preferable.
(式中、R13は、A1と炭素原子で結合する有機基を表し、R14は、任意の置換基を
表す。R13及びR14は、互いに結合して環を形成していてもよい。)
R13としては、A1との結合部分に炭素原子を有する有機基であれば、本発明の趣旨に反しない限り、その種類は特に制限されない。R13の分子量は、置換基を含めた値で、通常1000以下、好ましくは500以下の範囲である。
(In the formula, R 13 represents an organic group bonded to A 1 by a carbon atom, and R 14 represents an arbitrary substituent. R 13 and R 14 may be bonded to each other to form a ring. Good.)
The type of R 13 is not particularly limited as long as it is an organic group having a carbon atom at the bonding portion with A 1 as long as it is not contrary to the gist of the present invention. The molecular weight of R 13 is a value including a substituent, and is usually 1000 or less, preferably 500 or less.
R13の好ましい例としては、正電荷を非局在化させる点から、アルキル基、アルケニル基、アルキニル基、芳香族炭化水素基、芳香族複素環基が挙げられる。中でも、正電荷を非局在化させるとともに熱的に安定であることから、芳香族炭化水素基又は芳香族複素環基が好ましい。
アルキル基としては、直鎖状、分岐鎖状又は環状のアルキル基であって、その炭素数が通常1以上、また、通常12以下、好ましくは6以下のものが挙げられる。具体例としては、メチル基、エチル基、n−プロピル基、2−プロピル基、n−ブチル基、イソブチル基、tert−ブチル基、シクロヘキシル基等が挙げられる。
Preferred examples of R 13 include an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, and an aromatic heterocyclic group from the viewpoint of delocalizing positive charges. Among them, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable because it delocalizes positive charges and is thermally stable.
Examples of the alkyl group include linear, branched, or cyclic alkyl groups having a carbon number of usually 1 or more and usually 12 or less, preferably 6 or less. Specific examples include methyl group, ethyl group, n-propyl group, 2-propyl group, n-butyl group, isobutyl group, tert-butyl group, cyclohexyl group and the like.
アルケニル基としては、炭素数が通常2以上、通常12以下、好ましくは6以下のものが挙げられる。具体例としては、ビニル基、アリル基、1−ブテニル基等が挙げられる。
アルキニル基としては、炭素数が通常2以上、通常12以下、好ましくは6以下のものが挙げられる。具体例としては、エチニル基、プロパルギル基等が挙げられる。
芳香族炭化水素基としては、1個の遊離原子価を有する、5員環若しくは6員環の単環又は2〜5縮合環であり、正電荷を当該基上により非局在化させられる基が挙げられる。その具体例としては、1個の遊離原子価を有する、ベンゼン環、ナフタレン環、アントラセン環、フェナントレン環、ペリレン環、テトラセン環、ピレン環、ベンズピレン環、クリセン環、トリフェニレン環、アセナフテン環、フルオレン環等が挙げられる。
Examples of the alkenyl group include those having usually 2 or more, usually 12 or less, preferably 6 or less. Specific examples include a vinyl group, an allyl group, and a 1-butenyl group.
Examples of the alkynyl group include those having usually 2 or more, usually 12 or less, preferably 6 or less. Specific examples include ethynyl group and propargyl group.
The aromatic hydrocarbon group is a 5-membered or 6-membered monocyclic ring or a 2-5 condensed ring having one free valence, and a positive charge is more delocalized on the group. Is mentioned. Specific examples thereof include a benzene ring, naphthalene ring, anthracene ring, phenanthrene ring, perylene ring, tetracene ring, pyrene ring, benzpyrene ring, chrysene ring, triphenylene ring, acenaphthene ring and fluorene ring having one free valence. Etc.
芳香族複素環基としては、1個の遊離原子価を有する、5員環若しくは6員環の単環又は2〜4縮合環であり、正電荷を当該基上により非局在化させられる基が挙げられる。その具体例としては、1個の遊離原子価を有する、フラン環、ベンゾフラン環、チオフェン環、ベンゾチオフェン環、ピロール環、ピラゾール環、トリアゾール環、イミダゾール環、オキサジアゾール環、インドール環、カルバゾール環、ピロロイミダゾール環、ピロロピラゾール環、ピロロピロール環、チエノピロール環、チエノチオフェン環、フロピロール環、フロフラン環、チエノフラン環、ベンゾイソオキサゾール環、ベンゾイソチアゾール環、ベンゾイミダゾール環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環、シノリン環、キノキサリン環、フェナントリジン環、ベンゾイミダゾール環、ペリミジン環、キナゾリン環、キナゾリノン環、アズレン環等が挙げられる。 The aromatic heterocyclic group is a 5-membered or 6-membered monocyclic ring or a 2-4 condensed ring having one free valence, and a positive charge is delocalized on the group. Is mentioned. Specific examples thereof include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, a triazole ring, an imidazole ring, an oxadiazole ring, an indole ring, and a carbazole ring having one free valence. , Pyrroloimidazole ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furopyrrole ring, furofuran ring, thienofuran ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine Ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, sinoline ring, quinoxaline ring, phenanthridine ring, benzimidazole ring, perimidine ring, quinazoline ring, quinazolinone ring, azulene ring and the like.
R14は、本発明の趣旨に反しない限り特に制限されない。R14の分子量は、置換基を含めた値で、通常1000以下、好ましくは500以下の範囲である。
R14の例としては、アルキル基、アルケニル基、アルキニル基、芳香族炭化水素基、芳香族複素環基、アミノ基、アルコキシ基、アリールオキシ基、アシル基、アルコキシカルボニル基、アリールオキシカルボニル基、アルキルカルボニルオキシ基、アルキルチオ基、アリールチオ基、スルホニル基、アルキルスルホニル基、アリールスルホニル基、スルホニルオキシ基、シアノ基、水酸基、チオール基、シリル基等が挙げられる。
R 14 is not particularly limited as long as it is not contrary to the gist of the present invention. The molecular weight of R 14 is a value including a substituent, and is usually 1000 or less, preferably 500 or less.
Examples of R 14 include alkyl groups, alkenyl groups, alkynyl groups, aromatic hydrocarbon groups, aromatic heterocyclic groups, amino groups, alkoxy groups, aryloxy groups, acyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, Examples thereof include an alkylcarbonyloxy group, an alkylthio group, an arylthio group, a sulfonyl group, an alkylsulfonyl group, an arylsulfonyl group, a sulfonyloxy group, a cyano group, a hydroxyl group, a thiol group, and a silyl group.
中でも、R13と同様、電子受容性が大きい点から、A1との結合部分に炭素原子を有する有機基が好ましく、例としては、アルキル基、アルケニル基、アルキニル基、芳香族炭化水素基、芳香族複素環基が好ましい。特に、電子受容性が大きいとともに熱的に安定であることから、芳香族炭化水素基又は芳香族複素環基が好ましい。
R14のアルキル基、アルケニル基、アルキニル基、芳香族炭化水素基、芳香族複素環基としては、R13について先に説明したものと同様のものが挙げられる。
Among them, like R 13 , an organic group having a carbon atom at the bonding portion to A 1 is preferable because of its high electron accepting property. Examples include an alkyl group, an alkenyl group, an alkynyl group, an aromatic hydrocarbon group, Aromatic heterocyclic groups are preferred. In particular, an aromatic hydrocarbon group or an aromatic heterocyclic group is preferable because it has a large electron accepting property and is thermally stable.
Alkyl group, an alkenyl group of R 14, alkynyl group, aromatic hydrocarbon group, the aromatic heterocyclic group include the same as those described for R 13 above.
アミノ基としては、アルキルアミノ基、アリールアミノ基、アシルアミノ基等が挙げられる。
アルキルアミノ基としては、炭素数が通常1以上、また、通常12以下、好ましくは6以下のアルキル基を1つ以上有するアルキルアミノ基が挙げられる。具体例としては、メチルアミノ基、ジメチルアミノ基、ジエチルアミノ基、ジベンジルアミノ基等が挙げられる。
Examples of the amino group include an alkylamino group, an arylamino group, and an acylamino group.
Examples of the alkylamino group include alkylamino groups having one or more alkyl groups usually having 1 or more carbon atoms and usually 12 or less, preferably 6 or less carbon atoms. Specific examples include methylamino group, dimethylamino group, diethylamino group, dibenzylamino group and the like.
アリールアミノ基としては、炭素数が通常3以上、好ましくは4以上、また、通常25以下、好ましくは15以下の芳香族炭化水素基又は芳香族複素環基を1つ以上有するアリールアミノ基が挙げられる。具体例としては、フェニルアミノ基、ジフェニルアミノ基、トリルアミノ基、ピリジルアミノ基、チエニルアミノ基等が挙げられる。
アシルアミノ基としては、炭素数が通常2以上、また、通常25以下、好ましくは15以下のアシル基を1つ以上有するアシルアミノ基が挙げられる。具体例としては、アセチルアミノ基、ベンゾイルアミノ基等が挙げられる。
Examples of the arylamino group include arylamino groups having at least one aromatic hydrocarbon group or aromatic heterocyclic group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. It is done. Specific examples include phenylamino group, diphenylamino group, tolylamino group, pyridylamino group, thienylamino group and the like.
The acylamino group includes an acylamino group having one or more acyl groups having usually 2 or more carbon atoms and usually 25 or less, preferably 15 or less carbon atoms. Specific examples include an acetylamino group and a benzoylamino group.
アルコキシ基としては、炭素数が通常1以上、また、通常12以下、好ましくは6以下のアルコキシ基が挙げられる。具体例としては、メトキシ基、エトキシ基、ブトキシ基等が挙げられる。
アリールオキシ基としては、炭素数が通常3以上、好ましくは4以上、また、通常25以下、好ましくは15以下の芳香族炭化水素基又は芳香族複素環基を有するアリールオキシ基が挙げられる。具体例としては、フェニルオキシ基、ナフチルオキシ基、ピリジルオキシ基、チエニルオキシ基等が挙げられる。
The alkoxy group includes an alkoxy group having usually 1 or more carbon atoms and usually 12 or less, preferably 6 or less. Specific examples include a methoxy group, an ethoxy group, and a butoxy group.
Examples of the aryloxy group include aryloxy groups having an aromatic hydrocarbon group or an aromatic heterocyclic group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. Specific examples include phenyloxy group, naphthyloxy group, pyridyloxy group, thienyloxy group and the like.
アシル基としては、炭素数が通常1以上、また、通常25以下、好ましくは15以下のアシル基が挙げられる。具体例としては、ホルミル基、アセチル基、ベンゾイル基等が挙げられる。
アルコキシカルボニル基としては、炭素数が通常2以上、また、通常10以下、好ましくは7以下のアルコキシカルボニル基が挙げられる。具体例としては、メトキシカルボニル基、エトキシカルボニル基等が挙げられる。
Examples of the acyl group include acyl groups having usually 1 or more carbon atoms and usually 25 or less, preferably 15 or less. Specific examples include formyl group, acetyl group, benzoyl group and the like.
The alkoxycarbonyl group includes an alkoxycarbonyl group having usually 2 or more carbon atoms and usually 10 or less, preferably 7 or less. Specific examples include a methoxycarbonyl group and an ethoxycarbonyl group.
アリールオキシカルボニル基としては、炭素数が通常3以上、好ましくは4以上、また、通常25以下、好ましくは15以下の芳香族炭化水素基又は芳香族複素環基を有するものが挙げられる。具体例としては、フェノキシカルボニル基、ピリジルオキシカルボニル基等が挙げられる。
アルキルカルボニルオキシ基としては、炭素数が通常2以上、また、通常10以下、好ましくは7以下のアルキルカルボニルオキシ基が挙げられる。具体例としては、アセトキシ基、トリフルオロアセトキシ基等が挙げられる。
Examples of the aryloxycarbonyl group include those having an aromatic hydrocarbon group or an aromatic heterocyclic group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 15 or less. Specific examples include a phenoxycarbonyl group and a pyridyloxycarbonyl group.
Examples of the alkylcarbonyloxy group include alkylcarbonyloxy groups having usually 2 or more carbon atoms and usually 10 or less, preferably 7 or less. Specific examples include an acetoxy group and a trifluoroacetoxy group.
アルキルチオ基としては、炭素数が通常1以上、また、通常12以下、好ましくは6以下のアルキルチオ基が挙げられる。具体例としては、メチルチオ基、エチルチオ基等が挙げられる。
アリールチオ基としては、炭素数が通常3以上、好ましくは4以上、また、通常25以下、好ましくは14以下のアリールチオ基が挙げられる。具体例としては、フェニルチオ基、ナフチルチオ基、ピリジルチオ基等が挙げられる。
The alkylthio group includes an alkylthio group having usually 1 or more carbon atoms and usually 12 or less, preferably 6 or less. Specific examples include a methylthio group and an ethylthio group.
The arylthio group includes an arylthio group having usually 3 or more, preferably 4 or more, and usually 25 or less, preferably 14 or less. Specific examples include a phenylthio group, a naphthylthio group, and a pyridylthio group.
アルキルスルホニル基及びアリールスルホニル基の具体例としては、メシル基、トシル基等が挙げられる。
スルホニルオキシ基の具体例としては、メシルオキシ基、トシルオキシ基等が挙げられる。
シリル基の具体例としては、トリメチルシリル基、トリフェニルシリル基等が挙げられる。
Specific examples of the alkylsulfonyl group and the arylsulfonyl group include a mesyl group and a tosyl group.
Specific examples of the sulfonyloxy group include a mesyloxy group and a tosyloxy group.
Specific examples of the silyl group include a trimethylsilyl group and a triphenylsilyl group.
以上、R13及びR14として例示した基は、本発明の趣旨に反しない限りにおいて、更に他の置換基によって置換されていてもよい。置換基の種類は特に制限されないが、例としては、上記R13及びR14、としてそれぞれ例示した基の他、ハロゲン原子、シアノ基、チオシアノ基、ニトロ基等が挙げられる。中でも、イオン化合物(電子受容性化合物)の耐熱性及び電子受容性の妨げにならない観点から、アルキル基、アルケニル基、アルキニル基、アルコキシ基、アリールオキシ基、芳香族炭化水素基、芳香族複素環基が好ましい。 As described above, the groups exemplified as R 13 and R 14 may be further substituted with other substituents as long as not departing from the gist of the present invention. The type of the substituent is not particularly limited, and examples thereof include a halogen atom, a cyano group, a thiocyano group, a nitro group, and the like in addition to the groups exemplified as R 13 and R 14 . Among these, from the viewpoint of not hindering the heat resistance and electron acceptability of the ionic compound (electron accepting compound), an alkyl group, an alkenyl group, an alkynyl group, an alkoxy group, an aryloxy group, an aromatic hydrocarbon group, an aromatic heterocyclic ring. Groups are preferred.
式(2)中、A1は、周期表の第17族に属する元素であることが好ましく、電子受容性及び入手容易性の観点から、周期表の第5周期以前(第3〜第5周期)の元素が好ましい。即ち、A1としてはヨウ素原子、臭素原子、塩素原子のうち何れかが好ましい。
特に、電子受容性、化合物の安定性の面から、式(2)におけるA1が臭素原子又はヨウ素原子であるイオン化合物が好ましく、ヨウ素原子であるイオン化合物が最も好ましい。
In Formula (2), A 1 is preferably an element belonging to Group 17 of the periodic table, and from the viewpoint of electron acceptability and availability, the period before the fifth period (third to fifth periods). Element) is preferred. That is, as A1, any one of an iodine atom, a bromine atom, and a chlorine atom is preferable.
In particular, from the viewpoint of electron acceptability and stability of the compound, an ionic compound in which A 1 in Formula (2) is a bromine atom or an iodine atom is preferable, and an ionic compound in which an iodine atom is used is most preferable.
式(2)中、Z1 n1−は、対アニオンを表す。対アニオンの種類は特に制限されず、単原子イオンであっても錯イオンであってもよい。但し、対アニオンのサイズが大きいほど負電荷が非局在化し、それに伴い正電荷も非局在化して電子受容能が大きくなるため、単原子イオンよりも錯イオンの方が好ましい。
n1は、対アニオンZ1 n1−のイオン価に相当する任意の正の整数である。n1の値は特に制限されないが、1又は2であることが好ましく、1であることが最も好ましい。
In formula (2), Z 1 n1- represents a counter anion. The type of the counter anion is not particularly limited, and may be a monoatomic ion or a complex ion. However, the larger the size of the counter anion, the more the negative charge is delocalized, and the positive charge is also delocalized thereby increasing the electron accepting ability. Therefore, the complex ion is preferable to the monoatomic ion.
n 1 is an arbitrary positive integer corresponding to the ionic value of the counter anion Z 1 n1− . The value of n 1 is not particularly limited, but is preferably 1 or 2, and most preferably 1.
Z1 n1−の具体例としては、水酸化物イオン、フッ化物イオン、塩化物イオン、臭化物イオン、ヨウ化物イオン、シアン化物イオン、硝酸イオン、亜硝酸イオン、硫酸イオン、亜硫酸イオン、過塩素酸イオン、過臭素酸イオン、過ヨウ素酸イオン、塩素酸イオン、亜塩素酸イオン、次亜塩素酸イオン、リン酸イオン、亜リン酸イオン、次亜リン酸イオン、ホウ酸イオン、イソシアン酸イオン、硫化水素イオン、テトラフルオロホウ酸イオン、ヘキサフルオロリン酸イオン、ヘキサクロロアンチモン酸イオン;酢酸イオン、トリフルオロ酢酸イオン、安息香酸イオン等のカルボン酸イオン;メタンスルホン酸、トリフルオロメタンスルホン酸イオン等のスルホン酸イオン;メトキシイオン、t−ブトキシイオン等のアルコキシイオン等が挙げられる。中でも、テトラフルオロホウ素酸イオン及びヘキサフルオロホウ素酸イオンが好ましい。 Specific examples of Z 1 n1- include hydroxide ion, fluoride ion, chloride ion, bromide ion, iodide ion, cyanide ion, nitrate ion, nitrite ion, sulfate ion, sulfite ion, perchloric acid. Ion, perbromate ion, periodate ion, chlorate ion, chlorite ion, hypochlorite ion, phosphate ion, phosphite ion, hypophosphite ion, borate ion, isocyanate ion, Hydrogen sulfide ion, tetrafluoroborate ion, hexafluorophosphate ion, hexachloroantimonate ion; carboxylate ion such as acetate ion, trifluoroacetate ion, benzoate ion; sulfone such as methanesulfonic acid, trifluoromethanesulfonate ion Acid ions; alkoxy ions such as methoxy ion and t-butoxy ion It is. Of these, tetrafluoroborate ions and hexafluoroborate ions are preferable.
また、対アニオンZ1 n1−としては、化合物の安定性、溶媒への溶解性の点及び、サイズが大きいという点で、負電荷が非局在化し、それに伴い正電荷も非局在化して電子受容能が大きくなるため、下記式(3)で表される錯イオンが特に好ましい。 Further, as the counter anion Z 1 n1− , the negative charge is delocalized and the positive charge is also delocalized in view of the stability of the compound, the solubility in the solvent, and the large size. A complex ion represented by the following formula (3) is particularly preferable because the electron accepting ability is increased.
(式中、E3は、各々独立に、長周期型周期表の第13族に属する元素を表し、Ar5〜
Ar8は、各々独立に、芳香族炭化水素基又は芳香族複素環基を表す。)
E3としては、ホウ素原子、アルミニウム原子、ガリウム原子が好ましく、化合物の安定性、合成及び精製のし易さの点から、ホウ素原子がより好ましい。
Ar5〜Ar8の芳香族炭化水素基、芳香族複素環基の例示としては、R13について先に例示したものと同様の、1個の遊離原子価を有する、5員環若しくは6員環の単環又は2〜4縮合環が挙げられる。中でも、化合物の安定性、耐熱性の点から、1個の遊離原子価を有する、ベンゼン環、ナフタレン環、ピリジン環、ピラジン環、ピリダジン環、ピリミジン環、トリアジン環、キノリン環、イソキノリン環が好ましい。
(In the formula, each E 3 independently represents an element belonging to Group 13 of the long-period periodic table, Ar 5 to
Ar 8 each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group. )
E 3 is preferably a boron atom, an aluminum atom, or a gallium atom, and more preferably a boron atom from the viewpoint of stability of the compound, ease of synthesis and purification.
Examples of the aromatic hydrocarbon group and the aromatic heterocyclic group represented by Ar 5 to Ar 8 include a 5-membered ring or a 6-membered ring having one free valence similar to those exemplified above for R 13. Or a 1 to 4 condensed ring. Among them, a benzene ring, naphthalene ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring and isoquinoline ring having one free valence are preferable from the viewpoint of stability and heat resistance of the compound. .
Ar5〜Ar8として例示した芳香族炭化水素基、芳香族複素環基は、本発明の趣旨に反しない限りにおいて、更に別の置換基によって置換されていてもよい。置換基の種類は特に制限されず、任意の置換基が適用可能であるが、電子吸引性の基であることが好ましい。
Ar5〜Ar8が有してもよい置換基として好ましい電子吸引性の基を例示するならば、フッ素原子、塩素原子、臭素原子等のハロゲン原子;シアノ基;チオシアノ基;ニトロ基;メシル基等のアルキルスルホニル基;トシル基等のアリールスルホニル基;ホルミル基、アセチル基、ベンゾイル基等の、炭素数が通常1以上、通常12以下、好ましくは6以下のアシル基;メトキシカルボニル基、エトキシカルボニル基等の、炭素数が通常2以上、通常10以下、好ましくは7以下のアルコキシカルボニル基;フェノキシカルボニル基、ピリジルオキシカルボニル基等の、炭素数が通常3以上、好ましくは4以上、通常25以下、好ましくは15以下の芳香族炭化水素基又は芳香族複素環基を有するアリールオキシカルボニル基;アミノカルボニル基;アミノスルホニル基;トリフルオロメチル基、ペンタフルオロエチル基等の、炭素数が通常1以上、通常10以下、好ましくは6以下の直鎖状、分岐鎖状又は環状のアルキル基にフッ素原子、塩素原子等のハロゲン原子が置換したハロアルキル基等が挙げられる。
The aromatic hydrocarbon group and aromatic heterocyclic group exemplified as Ar 5 to Ar 8 may be further substituted with another substituent as long as not departing from the gist of the present invention. The type of the substituent is not particularly limited, and any substituent can be applied, but an electron-withdrawing group is preferable.
Illustrative examples of preferred electron-withdrawing groups as the substituent that Ar 5 to Ar 8 may have include halogen atoms such as fluorine atom, chlorine atom and bromine atom; cyano group; thiocyano group; nitro group; mesyl group Alkylsulfonyl groups such as tosyl group; arylsulfonyl groups such as tosyl group; acyl groups such as formyl group, acetyl group, benzoyl group and the like, usually having 1 or more, usually 12 or less, preferably 6 or less; methoxycarbonyl group, ethoxycarbonyl An alkoxycarbonyl group having 2 or more carbon atoms, usually 10 or less, preferably 7 or less; a phenoxycarbonyl group, a pyridyloxycarbonyl group or the like, and usually having 3 or more carbon atoms, preferably 4 or more and usually 25 or less. An aryloxycarbonyl group having an aromatic hydrocarbon group or an aromatic heterocyclic group of preferably 15 or less; Bonyl group; aminosulfonyl group; trifluoromethyl group, pentafluoroethyl group, etc., a fluorine atom in a linear, branched or cyclic alkyl group having usually 1 or more, usually 10 or less, preferably 6 or less carbon atoms And a haloalkyl group substituted with a halogen atom such as a chlorine atom.
中でも、Ar5〜Ar8のうち少なくとも1つの基が、フッ素原子又は塩素原子を置換基として1つ又は2つ以上有することがより好ましい。特に、負電荷を効率よく非局在化する点、及び、適度な昇華性を有する点から、Ar5〜Ar8の水素原子がすべてフッ素原子で置換されたパーフルオロアリール基であることが最も好ましい。パーフルオロアリール基の具体例としては、ペンタフルオロフェニル基、ヘプタフルオロ−2−ナフチル基、テトラフルオロ−4−ピリジル基等が挙げられる。 Especially, it is more preferable that at least one group among Ar 5 to Ar 8 has one or two or more fluorine atoms or chlorine atoms as a substituent. In particular, it is most preferably a perfluoroaryl group in which all of the hydrogen atoms Ar 5 to Ar 8 are substituted with fluorine atoms from the viewpoint of efficiently delocalizing negative charges and having an appropriate sublimation property. preferable. Specific examples of the perfluoroaryl group include a pentafluorophenyl group, a heptafluoro-2-naphthyl group, and a tetrafluoro-4-pyridyl group.
本発明における電子受容性化合物の分子量は、通常100〜5000、好ましくは300〜3000、更に好ましくは400〜2000である。
上記範囲内であると、正電荷及び負電荷が十分に非局在化し、電子受容能が良好で、また電荷輸送の妨げになり難い点で好ましい。
以下に、本発明に好適な前記式(2)に記載の電子受容性化合物の具体例を下記表1に示すが、本発明はこれらに限定されるものではない。
The molecular weight of the electron-accepting compound in the present invention is usually 100 to 5000, preferably 300 to 3000, and more preferably 400 to 2000.
Within the above range, the positive charge and the negative charge are sufficiently delocalized, the electron accepting ability is good, and it is preferable that the charge transport is not hindered.
Specific examples of the electron-accepting compound represented by the formula (2) suitable for the present invention are shown in the following Table 1, but the present invention is not limited thereto.
本発明の有機電界発光素子用組成物は、上記のような電子受容性化合物の1種を単独で含んでいてもよく、また2種以上を任意の組み合わせ、及び比率で含んでいてもよい。
本発明の有機電界発光素子用組成物が電子受容性化合物を含む場合、本発明の有機電界発光素子用組成物の電子受容性化合物の含有量は、通常0.0005質量%以上、好ましくは0.001質量%以上であり、通常20質量%以下、好ましくは10質量%以下である。また、有機電界発光素子用組成物中の本発明の重合体に対する電子受容性化合物の割合は、通常0.5質量%以上、好ましくは1質量%以上、より好ましくは3質量%以上であり、通常80質量%以下、好ましくは60質量%以下、さらに好ましくは40質量%以下である。
The composition for organic electroluminescent elements of the present invention may contain one of the electron accepting compounds as described above alone, or may contain two or more kinds in any combination and ratio.
When the composition for organic electroluminescent elements of the present invention contains an electron accepting compound, the content of the electron accepting compound in the composition for organic electroluminescent elements of the present invention is usually 0.0005% by mass or more, preferably 0. 0.001% by mass or more, usually 20% by mass or less, preferably 10% by mass or less. The ratio of the electron-accepting compound to the polymer of the present invention in the composition for organic electroluminescent elements is usually 0.5% by mass or more, preferably 1% by mass or more, more preferably 3% by mass or more, Usually, it is 80 mass% or less, Preferably it is 60 mass% or less, More preferably, it is 40 mass% or less.
有機電界発光素子用組成物中の電子受容性化合物の含有量が上記下限以上であると重合体から電子受容体が電子を受容し、形成した有機層が低抵抗化するため好ましく、上記上限以下であると形成した有機層に欠陥が生じ難く、また膜厚ムラが生じ難いため好ましい。 The content of the electron-accepting compound in the composition for organic electroluminescent elements is preferably not less than the above lower limit because the electron acceptor accepts electrons from the polymer and the formed organic layer is reduced in resistance. It is preferable that the organic layer formed is less likely to have defects and is less likely to cause film thickness unevenness.
[カチオンラジカル化合物]
本発明の有機電界発光素子用組成物は、更にカチオンラジカル化合物を含有していてもよい。
カチオンラジカル化合物としては、正孔輸送性化合物から一電子取り除いた化学種であるカチオンラジカルと、対アニオンとからなるイオン化合物が好ましい。但し、カチオンラジカルが正孔輸送性の高分子化合物由来である場合、カチオンラジカルは高分子化合物の繰り返し単位から一電子取り除いた構造となる。
[Cation radical compound]
The composition for organic electroluminescent elements of the present invention may further contain a cation radical compound.
As the cation radical compound, an ionic compound composed of a cation radical which is a chemical species obtained by removing one electron from a hole transporting compound and a counter anion is preferable. However, when the cation radical is derived from a hole transporting polymer compound, the cation radical has a structure in which one electron is removed from the repeating unit of the polymer compound.
また、カチオンラジカルとしては、後述の正孔輸送性化合物から一電子取り除いた化学種であることが好ましい。正孔輸送性化合物として好ましい化合物から一電子取り除いた化学種であることが、非晶質性、可視光の透過率、耐熱性、及び溶解性等の点から好適である。 Further, the cation radical is preferably a chemical species obtained by removing one electron from a hole transporting compound described later. A chemical species obtained by removing one electron from a compound preferable as a hole transporting compound is preferable in terms of amorphousness, visible light transmittance, heat resistance, solubility, and the like.
ここで、カチオンラジカル化合物は、後述の正孔輸送性化合物と前述の電子受容性化合物を混合することにより生成させることができる。即ち、正孔輸送性化合物と電子受容性化合物とを混合することにより、正孔輸送性化合物から電子受容性化合物へと電子移動が起こり、正孔輸送性化合物のカチオンラジカルと対アニオンとからなるカチオンイオン化合物が生成する。 Here, the cation radical compound can be generated by mixing a hole transporting compound described later and the above-described electron accepting compound. That is, by mixing the hole-transporting compound and the electron-accepting compound, electron transfer occurs from the hole-transporting compound to the electron-accepting compound, and consists of a cation radical and a counter anion of the hole-transporting compound. A cation ion compound is formed.
本発明の有機電界発光素子用組成物がカチオンラジカル化合物を含む場合、本発明の有機電界発光素子用組成物のカチオンラジカル化合物の含有量は、通常0.0005質量%以上、好ましくは0.001質量%以上であり、通常40質量%以下、好ましくは20質量%以下である。カチオンラジカル化合物の含有量が下限以上であると形成した有機層が低抵抗化するため好ましく、上限以下であると形成した有機層に欠陥が生じ難く、また膜厚ムラが生じ難いため好ましい。 When the composition for organic electroluminescent elements of the present invention contains a cation radical compound, the content of the cation radical compound in the composition for organic electroluminescent elements of the present invention is usually 0.0005% by mass or more, preferably 0.001. It is 40 mass% or less normally, Preferably it is 20 mass% or less. When the content of the cation radical compound is not less than the lower limit, the formed organic layer is preferably reduced in resistance, and when it is not more than the upper limit, the formed organic layer is less likely to have defects and is not likely to cause film thickness unevenness.
なお、本発明の有機電界発光素子用組成物には、上記の成分以外に、後述の正孔注入層形成用組成物や正孔輸送層形成用組成物に含まれる成分を、後述の含有量で含有していてもよい。 In addition to the above-mentioned components, the composition for organic electroluminescence device of the present invention contains the components contained in the composition for forming a hole injection layer and the composition for forming a hole transport layer, which will be described later. It may contain.
<有機電界発光素子>
本発明の有機電界発光素子は、基板上に、陽極及び陰極と、該陽極と該陰極の間に有機層を有する有機電界発光素子において、該有機層が、本発明の重合体を含む本発明の有機電界発光素子用組成物を用いて湿式成膜法により形成された層を含むことを特徴とする。
本発明の有機電界発光素子において、湿式成膜法により形成された層は、正孔注入層及び正孔輸送層の少なくとも一方であることが好ましく、特に、この有機層が正孔注入層、正孔輸送層及び発光層を備え、これら正孔注入層、正孔輸送層及び発光層の全てが湿式成膜法により形成された層であることが好ましい。
<Organic electroluminescent device>
The organic electroluminescent device of the present invention is an organic electroluminescent device having an anode and a cathode and an organic layer between the anode and the cathode on a substrate, wherein the organic layer contains the polymer of the present invention. And a layer formed by a wet film formation method using the composition for organic electroluminescence elements.
In the organic electroluminescence device of the present invention, the layer formed by the wet film formation method is preferably at least one of a hole injection layer and a hole transport layer. A hole transport layer and a light-emitting layer are provided, and all of the hole injection layer, the hole transport layer and the light-emitting layer are preferably formed by a wet film formation method.
本発明において湿式成膜法とは、成膜方法、即ち、塗布方法として、例えば、スピンコート法、ディップコート法、ダイコート法、バーコート法、ブレードコート法、ロールコート法、スプレーコート法、キャピラリーコート法、インクジェット法、ノズルプリンティング法、スクリーン印刷法、グラビア印刷法、フレキソ印刷法等の湿式で成膜させる方法を採用し、この塗布膜を乾燥させて膜形成を行う方法をいう。これらの成膜方法の中でも、スピンコート法、スプレーコート法、インクジェット法、ノズルプリンティング法等が好ましい。 In the present invention, the wet film forming method is a film forming method, that is, a coating method, for example, spin coating method, dip coating method, die coating method, bar coating method, blade coating method, roll coating method, spray coating method, capillary A method of forming a film by employing a wet film formation method such as a coating method, an ink jet method, a nozzle printing method, a screen printing method, a gravure printing method, or a flexographic printing method, and drying the coated film. Among these film forming methods, spin coating, spray coating, ink jet, nozzle printing, and the like are preferable.
本発明の有機電界発光素子の構造の一例として、図1に有機電界発光素子10の構造例の模式図(断面)を示す。図1において、1は基板、2は陽極、3は正孔注入層、4は正孔輸送層、5は発光層、6は正孔阻止層、7は電子輸送層、8は電子注入層、9は陰極を各々表す。
以下、本発明の有機電界発光素子の層構成及びその一般的形成方法等の実施の形態の一例を、図1を参照して説明する。
As an example of the structure of the organic electroluminescent element of the present invention, FIG. 1 shows a schematic diagram (cross section) of a structural example of the organic electroluminescent element 10. In FIG. 1, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light emitting layer, 6 is a hole blocking layer, 7 is an electron transport layer, 8 is an electron injection layer, 9 represents each cathode.
Hereinafter, an example of an embodiment of the layer configuration of the organic electroluminescent element of the present invention and a general formation method thereof will be described with reference to FIG.
[基板]
基板1は、有機電界発光素子の支持体となるものであり、通常、石英やガラスの板、金属板や金属箔、プラスチックフィルムやシート等が用いられる。これらのうち、ガラス板や、ポリエステル、ポリメタクリレート、ポリカーボネート、ポリスルホン等の透明な合成樹脂の板が好ましい。基板は、外気による有機電界発光素子の劣化が起こり難いことからガスバリア性の高い材質とするのが好ましい。このため、特に合成樹脂製の基板等のようにガスバリア性の低い材質を用いる場合は、基板の少なくとも片面に緻密なシリコン酸化膜等を設けてガスバリア性を上げるのが好ましい。
[substrate]
The substrate 1 serves as a support for the organic electroluminescent element, and a quartz or glass plate, a metal plate or a metal foil, a plastic film or a sheet is usually used. Of these, glass plates and transparent synthetic resin plates such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. The substrate is preferably made of a material having a high gas barrier property since the organic electroluminescence device is hardly deteriorated by the outside air. For this reason, in particular, when a material having a low gas barrier property such as a synthetic resin substrate is used, it is preferable to provide a dense silicon oxide film or the like on at least one surface of the substrate to improve the gas barrier property.
[陽極]
陽極2は、発光層5側の層に正孔を注入する機能を担う。
陽極2は、通常、アルミニウム、金、銀、ニッケル、パラジウム、白金等の金属;インジウム及び/又はスズの酸化物等の金属酸化物;ヨウ化銅等のハロゲン化金属;カーボンブラック及びポリ(3−メチルチオフェン)、ポリピロール、ポリアニリン等の導電性高分子等により構成される。
[anode]
The anode 2 has a function of injecting holes into the layer on the light emitting layer 5 side.
The anode 2 is usually made of a metal such as aluminum, gold, silver, nickel, palladium, or platinum; a metal oxide such as an oxide of indium and / or tin; a metal halide such as copper iodide; a carbon black and a poly (3 -Methylthiophene), polypyrrole, polyaniline and other conductive polymers.
陽極2の形成は、通常、スパッタリング法、真空蒸着法等の乾式法により行われることが多い。また、銀等の金属微粒子、ヨウ化銅等の微粒子、カーボンブラック、導電性の金属酸化物微粒子、導電性高分子微粉末等を用いて陽極を形成する場合には、適当なバインダー樹脂溶液に分散させて、基板上に塗布することにより形成することもできる。また、導電性高分子の場合は、電解重合により直接基板上に薄膜を形成したり、基板上に導電性高分子を塗布して陽極を形成することもできる(Appl.Phys.Lett.,60巻,2711頁,1992年)。 In general, the anode 2 is often formed by a dry method such as a sputtering method or a vacuum deposition method. In addition, when forming an anode using fine metal particles such as silver, fine particles such as copper iodide, carbon black, conductive metal oxide fine particles, and conductive polymer fine powder, an appropriate binder resin solution is used. It can also be formed by dispersing and coating on a substrate. In the case of a conductive polymer, a thin film can be directly formed on a substrate by electrolytic polymerization, or an anode can be formed by applying a conductive polymer on a substrate (Appl. Phys. Lett., 60). Volume, 2711, 1992).
陽極2は、通常、単層構造であるが、適宜、積層構造としてもよい。陽極2が積層構造である場合、1層目の陽極上に異なる導電材料を積層してもよい。
陽極2の厚みは、必要とされる透明性と材質等に応じて決めればよい。特に高い透明性が必要とされる場合は、可視光の透過率が60%以上となる厚みが好ましく、80%以上となる厚みが更に好ましい。陽極2の厚みは、通常5nm以上、好ましくは10nm以上であり、また、通常1000nm以下、好ましくは500nm以下とするのが好ましい。一方、透明性が不要な場合は、陽極2の厚みは必要な強度等に応じて任意に厚みとすればよく、この場合、陽極2は基板と同一の厚みでもよい。
陽極2の表面に他の層を成膜する場合は、成膜前に、紫外線/オゾン、酸素プラズマ、アルゴンプラズマ等の処理を施すことにより、陽極2上の不純物を除去すると共に、そのイオン化ポテンシャルを調整して正孔注入性を向上させておくことが好ましい。
The anode 2 usually has a single layer structure, but may have a laminated structure as appropriate. When the anode 2 has a laminated structure, different conductive materials may be laminated on the first anode.
The thickness of the anode 2 may be determined according to required transparency and material. In particular, when high transparency is required, a thickness at which visible light transmittance is 60% or more is preferable, and a thickness at which 80% or more is more preferable. The thickness of the anode 2 is usually 5 nm or more, preferably 10 nm or more, and is usually 1000 nm or less, preferably 500 nm or less. On the other hand, when transparency is unnecessary, the thickness of the anode 2 may be arbitrarily set according to the required strength, and in this case, the anode 2 may have the same thickness as the substrate.
In the case where another layer is formed on the surface of the anode 2, impurities on the anode 2 are removed by performing treatments such as ultraviolet / ozone, oxygen plasma, and argon plasma before the film formation, and the ionization potential thereof. It is preferable to improve the hole injection property by adjusting.
[正孔注入層]
陽極2側から発光層5側に正孔を輸送する機能を担う層は、通常、正孔注入輸送層又は正孔輸送層と呼ばれる。そして、陽極2側から発光層5側に正孔を輸送する機能を担う層が2層以上ある場合に、より陽極側に近い方の層を正孔注入層3と呼ぶことがある。正孔注入層3は、陽極2から発光層5側に正孔を輸送する機能を強化する点で、形成することが好ましい。正孔注入層3を形成する場合、通常、正孔注入層3は、陽極2上に形成される。
[Hole injection layer]
The layer responsible for transporting holes from the anode 2 side to the light emitting layer 5 side is usually called a hole injection transport layer or a hole transport layer. When there are two or more layers responsible for transporting holes from the anode 2 side to the light emitting layer 5 side, the layer closer to the anode side may be referred to as the hole injection layer 3. The hole injection layer 3 is preferably formed from the viewpoint of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5 side. When forming the hole injection layer 3, the hole injection layer 3 is usually formed on the anode 2.
正孔注入層3の膜厚は、通常1nm以上、好ましくは5nm以上、また、通常1000nm以下、好ましくは500nm以下である。
正孔注入層の形成方法は、真空蒸着法でも、湿式成膜法でもよい。成膜性が優れる点で
は、湿式成膜法により形成することが好ましい。
正孔注入層3は、正孔輸送性化合物を含むことが好ましく、正孔輸送性化合物と電子受容性化合物とを含むことがより好ましい。更には、正孔注入層中にカチオンラジカル化合物を含むことが好ましく、カチオンラジカル化合物と正孔輸送性化合物とを含むことが特に好ましい。
The thickness of the hole injection layer 3 is usually 1 nm or more, preferably 5 nm or more, and usually 1000 nm or less, preferably 500 nm or less.
The formation method of the hole injection layer may be a vacuum deposition method or a wet film formation method. In terms of excellent film forming properties, it is preferable to form the film by a wet film forming method.
The hole injection layer 3 preferably contains a hole transporting compound, and more preferably contains a hole transporting compound and an electron accepting compound. Further, the hole injection layer preferably contains a cation radical compound, and particularly preferably contains a cation radical compound and a hole transporting compound.
以下に、一般的な正孔注入層の形成方法について説明するが、本発明の有機電界発光素子において、正孔注入層は、本発明の有機電界発光素子用組成物を用いて湿式成膜法により形成されることが好ましい。 Hereinafter, a general method for forming a hole injection layer will be described. In the organic electroluminescence device of the present invention, the hole injection layer is formed by a wet film formation method using the composition for an organic electroluminescence device of the present invention. It is preferably formed by.
[正孔輸送性化合物]
正孔注入層形成用組成物は、通常、正孔注入層3となる正孔輸送性化合物を含有する。また、湿式成膜法の場合は、通常、更に溶媒も含有する。正孔注入層形成用組成物は、正孔輸送性が高く、注入された正孔を効率よく輸送できるのが好ましい。このため、正孔移動度が大きく、トラップとなる不純物が製造時や使用時等に発生し難いことが好ましい。また、安定性に優れ、イオン化ポテンシャルが小さく、可視光に対する透明性が高いことが好ましい。特に、正孔注入層が発光層と接する場合は、発光層からの発光を消光しないものや発光層とエキサイプレックスを形成して、発光効率を低下させないものが好ましい。
[Hole transporting compound]
The composition for forming a hole injection layer usually contains a hole transporting compound that becomes the hole injection layer 3. Moreover, in the case of the wet film-forming method, a solvent is usually further contained. It is preferable that the composition for forming a hole injection layer has high hole transportability and can efficiently transport injected holes. For this reason, it is preferable that the hole mobility is high and impurities that become traps are less likely to be generated during production or use. Moreover, it is preferable that it is excellent in stability, has a small ionization potential, and has high transparency to visible light. In particular, when the hole injection layer is in contact with the light emitting layer, those that do not quench the light emitted from the light emitting layer or those that form an exciplex with the light emitting layer and do not decrease the light emission efficiency are preferable.
正孔輸送性化合物としては、陽極から正孔注入層への電荷注入障壁の観点から、4.5eV〜6.0eVのイオン化ポテンシャルを有する化合物が好ましい。正孔輸送性化合物の例としては、芳香族アミン系化合物、フタロシアニン系化合物、ポルフィリン系化合物、オリゴチオフェン系化合物、ポリチオフェン系化合物、ベンジルフェニル系化合物、フルオレン基で3級アミンを連結した化合物、ヒドラゾン系化合物、シラザン系化合物、キナクリドン系化合物等が挙げられる。 The hole transporting compound is preferably a compound having an ionization potential of 4.5 eV to 6.0 eV from the viewpoint of a charge injection barrier from the anode to the hole injection layer. Examples of hole transporting compounds include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, compounds in which tertiary amines are linked by a fluorene group, hydrazones Compounds, silazane compounds, quinacridone compounds, and the like.
上述の例示化合物のうち、非晶質性及び可視光透過性の点から、芳香族アミン化合物が好ましく、芳香族三級アミン化合物が特に好ましい。ここで、芳香族三級アミン化合物とは、芳香族三級アミン構造を有する化合物であって、芳香族三級アミン由来の基を有する化合物も含む。 Of the above-described exemplary compounds, an aromatic amine compound is preferable and an aromatic tertiary amine compound is particularly preferable from the viewpoint of amorphousness and visible light transmittance. Here, the aromatic tertiary amine compound is a compound having an aromatic tertiary amine structure, and includes a compound having a group derived from an aromatic tertiary amine.
芳香族三級アミン化合物の種類は、特に制限されないが、表面平滑化効果により均一な発光を得やすい点から、重量平均分子量が1000以上、1000000以下の高分子化合物(繰り返し単位が連なる重合型化合物)を用いることが好ましい。芳香族三級アミン高分子化合物の好ましい例としては、本発明の重合体の他に、下記式(10)で表される繰り返し単位を有する高分子化合物等が挙げられる。 The type of the aromatic tertiary amine compound is not particularly limited, but is a polymer compound having a weight average molecular weight of 1,000 or more and 1,000,000 or less (a polymerizable compound in which repeating units are linked) from the viewpoint of easily obtaining uniform light emission due to the surface smoothing effect. ) Is preferably used. Preferable examples of the aromatic tertiary amine polymer compound include a polymer compound having a repeating unit represented by the following formula (10) in addition to the polymer of the present invention.
(式中、Ar11及びAr12は、それぞれ独立して、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。Ar13〜Ar15は、それぞれ独立して、置換基を有していてもよい芳香族炭化水素基又は置換基を有してい
てもよい芳香族複素環基を表す。Yは、下記に示す連結基群の中から選ばれる連結基を表す。また、Ar11〜Ar15のうち、同一のN原子に結合する二つの基は互いに結合して環を形成してもよい。)
(In the formula, Ar 11 and Ar 12 each independently represent an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. Ar 13 -Ar 15 each independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent, and Y represents a linking group shown below. And represents a linking group selected from the group, and among Ar 11 to Ar 15 , two groups bonded to the same N atom may be bonded to each other to form a ring.
(式中、Ar16〜Ar26は、それぞれ独立して、置換基を有していてもよい芳香族炭化水素基又は置換基を有していてもよい芳香族複素環基を表す。R11及びR12は、それぞれ独立して、水素原子又は任意の置換基を表す。)
Ar16〜Ar26の芳香族炭化水素基及び芳香族複素環基としては、高分子化合物の溶解性、耐熱性、正孔注入輸送性の点から、1個又は2個の遊離原子価を有する、ベンゼン環、ナフタレン環、フェナントレン環、チオフェン環、ピリジン環が好ましく、1個又は2個の遊離原子価を有する、ベンゼン環、ナフタレン環がさらに好ましい。
(In the formula, each of Ar 16 to Ar 26 independently represents an aromatic hydrocarbon group which may have a substituent or an aromatic heterocyclic group which may have a substituent. R 11 And R 12 each independently represents a hydrogen atom or an arbitrary substituent.)
The aromatic hydrocarbon group and aromatic heterocyclic group of Ar 16 to Ar 26 have one or two free valences from the viewpoint of the solubility, heat resistance, and hole injecting / transporting property of the polymer compound. , A benzene ring, a naphthalene ring, a phenanthrene ring, a thiophene ring, and a pyridine ring are preferable, and a benzene ring and a naphthalene ring having one or two free valences are more preferable.
式(10)で表される繰り返し単位を有する芳香族三級アミン高分子化合物の具体例としては、国際公開第2005/089024号に記載のもの等が挙げられる。
正孔注入層3には、正孔輸送性化合物の酸化により、正孔注入層の導電率を向上させることができるため、前述の電子受容性化合物や、前述のカチオンラジカル化合物を含有していることが好ましい。
Specific examples of the aromatic tertiary amine polymer compound having a repeating unit represented by the formula (10) include those described in International Publication No. 2005/089024.
The hole injection layer 3 contains the above-described electron-accepting compound or the above-described cation radical compound because the conductivity of the hole-injection layer can be improved by oxidation of the hole-transporting compound. It is preferable.
PEDOT/PSS(Adv.Mater.,2000年,12巻,481頁)やエメラルジン塩酸塩(J.Phys.Chem.,1990年,94巻,7716頁)等の高分子化合物由来のカチオンラジカル化合物は、酸化重合(脱水素重合)することによっても生成する。
ここでいう酸化重合は、モノマーを酸性溶液中で、ペルオキソ二硫酸塩等を用いて化学的に、又は、電気化学的に酸化するものである。この酸化重合(脱水素重合)の場合、モノマーが酸化されることにより高分子化されるとともに、酸性溶液由来のアニオンを対アニオンとする、高分子の繰り返し単位から一電子取り除かれたカチオンラジカルが生成する。
Cationic radical compounds derived from polymer compounds such as PEDOT / PSS (Adv. Mater., 2000, 12, 481) and emeraldine hydrochloride (J. Phys. Chem., 1990, 94, 7716) It is also produced by oxidative polymerization (dehydrogenation polymerization).
Oxidative polymerization here refers to oxidation of a monomer chemically or electrochemically with peroxodisulfate in an acidic solution. In the case of this oxidative polymerization (dehydrogenation polymerization), the monomer is polymerized by oxidation, and a cation radical that is removed from the polymer repeating unit by using an anion derived from an acidic solution as a counter anion is removed. Generate.
[湿式成膜法による正孔注入層の形成]
湿式成膜法により正孔注入層3を形成する場合、通常、正孔注入層となる材料を可溶な溶媒(正孔注入層用溶媒)と混合して成膜用の組成物(正孔注入層形成用組成物)を調製し、この正孔注入層形成用組成物を正孔注入層の下層に該当する層(通常は、陽極)上に塗布して成膜し、乾燥させることにより形成する。
[Formation of hole injection layer by wet film formation method]
When the hole injection layer 3 is formed by a wet film formation method, a material for forming the hole injection layer is usually mixed with a soluble solvent (a solvent for the hole injection layer) to form a film-forming composition (hole An injection layer forming composition), and applying the hole injection layer forming composition onto a layer (usually an anode) corresponding to the lower layer of the hole injection layer, forming a film, and then drying. Form.
正孔注入層形成用組成物中における正孔輸送性化合物の濃度は、本発明の効果を著しく損なわない限り任意であるが、膜厚の均一性の点では、低い方が好ましく、また、一方、正孔注入層に欠陥が生じ難い点では、高い方が好ましい。具体的には、0.01質量%以上であるのが好ましく、0.1質量%以上であるのが更に好ましく、0.5質量%以上であるのが特に好ましく、また、一方、70質量%以下であるのが好ましく、60質量%以
下であるのが更に好ましく、50質量%以下であるのが特に好ましい。
The concentration of the hole transporting compound in the composition for forming a hole injection layer is arbitrary as long as the effects of the present invention are not significantly impaired, but in terms of film thickness uniformity, the lower one is preferable. From the viewpoint that defects are less likely to occur in the hole injection layer, a higher value is preferable. Specifically, it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, particularly preferably 0.5% by mass or more, and on the other hand, 70% by mass. The content is preferably less than 60% by mass, more preferably 60% by mass or less, and particularly preferably 50% by mass or less.
溶媒としては、例えば、エーテル系溶媒、エステル系溶媒、芳香族炭化水素系溶媒、アミド系溶媒等が挙げられる。
エーテル系溶媒としては、例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール−1−モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル及び1,2−ジメトキシベンゼン、1,3−ジメトキシベンゼン、アニソール、フェネトール、2−メトキシトルエン、3−メトキシトルエン、4−メトキシトルエン、2,3−ジメチルアニソール、2,4−ジメチルアニソール等の芳香族エーテル等が挙げられる。
Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, and the like.
Examples of ether solvents include aliphatic ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA), 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, and anisole. , Aromatic ethers such as phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole and 2,4-dimethylanisole.
エステル系溶媒としては、例えば、酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n−ブチル等の芳香族エステル等が挙げられる。
芳香族炭化水素系溶媒としては、例えば、トルエン、キシレン、シクロヘキシルベンゼン、3−イソプロピルビフェニル、1,2,3,4−テトラメチルベンゼン、1,4−ジイソプロピルベンゼン、シクロヘキシルベンゼン、メチルナフタレン等が挙げられる。
Examples of the ester solvent include aromatic esters such as phenyl acetate, phenyl propionate, methyl benzoate, ethyl benzoate, propyl benzoate, and n-butyl benzoate.
Examples of the aromatic hydrocarbon solvent include toluene, xylene, cyclohexylbenzene, 3-isopropylbiphenyl, 1,2,3,4-tetramethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene, methylnaphthalene and the like. It is done.
アミド系溶媒としては、例えば、N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等が挙げられる。
これらの他、ジメチルスルホキシド等も用いることができる。
正孔注入層3の湿式成膜法による形成は、通常、正孔注入層形成用組成物を調製後に、これを、正孔注入層3の下層に該当する層(通常は、陽極2)上に塗布成膜し、乾燥することにより行われる。
正孔注入層3は、通常、成膜後に、加熱や減圧乾燥等により塗布膜を乾燥させる。
Examples of the amide solvent include N, N-dimethylformamide and N, N-dimethylacetamide.
In addition to these, dimethyl sulfoxide and the like can also be used.
Formation of the hole injection layer 3 by a wet film formation method is usually performed after preparing a composition for forming a hole injection layer, and then forming the composition on a layer (usually the anode 2) corresponding to the lower layer of the hole injection layer 3 The film is formed by coating and drying.
In general, the hole injection layer 3 is dried by heating or drying under reduced pressure after film formation.
[真空蒸着法による正孔注入層の形成]
真空蒸着法により正孔注入層3を形成する場合には、通常、正孔注入層3の構成材料(前述の正孔輸送性化合物、電子受容性化合物等)の1種類又は2種類以上を真空容器内に設置された坩堝に入れ(2種類以上の材料を用いる場合は、通常各々を別々の坩堝に入れ)、真空容器内を真空ポンプで10−4Pa程度まで排気した後、坩堝を加熱して(2種類以上の材料を用いる場合は、通常各々の坩堝を加熱して)、坩堝内の材料の蒸発量を制御しながら蒸発させ(2種類以上の材料を用いる場合は、通常各々独立に蒸発量を制御しながら蒸発させ)、坩堝に向き合って置かれた基板上の陽極上に正孔注入層を形成する。なお、2種類以上の材料を用いる場合は、それらの混合物を坩堝に入れ、加熱、蒸発させて正孔注入層を形成することもできる。
[Formation of hole injection layer by vacuum evaporation]
When the hole injection layer 3 is formed by vacuum vapor deposition, one or more of the constituent materials of the hole injection layer 3 (the above-described hole transporting compound, electron accepting compound, etc.) are usually vacuumed. Put in a crucible installed in the container (when using two or more kinds of materials, usually put each in separate crucibles), evacuate the vacuum container to about 10 -4 Pa with a vacuum pump, then heat the crucible (When using two or more types of materials, each crucible is usually heated) and evaporated while controlling the amount of evaporation of the material in the crucible (when using two or more types of materials, each is usually independent. The hole injection layer is formed on the anode on the substrate placed facing the crucible. When two or more kinds of materials are used, the hole injection layer can be formed by putting the mixture in a crucible and heating and evaporating the mixture.
蒸着時の真空度は、本発明の効果を著しく損なわない限り限定されないが、通常0.1×10−6Torr(0.13×10−4Pa)以上、9.0×10−6Torr(12.0×10−4Pa)以下である。蒸着速度は、本発明の効果を著しく損なわない限り限定されないが、通常0.1Å/秒以上、5.0Å/秒以下である。蒸着時の成膜温度は、本発明の効果を著しく損なわない限り限定されないが、好ましくは10℃以上、50℃以下で行われる。
なお、正孔注入層3は、後述の正孔輸送層4と同様に架橋されていてもよい。
The degree of vacuum at the time of vapor deposition is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 × 10 −6 Torr (0.13 × 10 −4 Pa) or more and 9.0 × 10 −6 Torr ( 12.0 × 10 −4 Pa) or less. The deposition rate is not limited as long as the effect of the present invention is not significantly impaired, but is usually 0.1 to 5.0 liters / second or more. The film forming temperature at the time of vapor deposition is not limited as long as the effects of the present invention are not significantly impaired, but it is preferably performed at 10 ° C. or higher and 50 ° C. or lower.
The hole injection layer 3 may be cross-linked similarly to the hole transport layer 4 described later.
[正孔輸送層]
正孔輸送層4は、陽極2側から発光層5側に正孔を輸送する機能を担う層である。正孔輸送層4は、本発明の有機電界発光素子では、必須の層では無いが、陽極2から発光層5に正孔を輸送する機能を強化する点では、この層を形成することが好ましい。正孔輸送層4を形成する場合、通常、正孔輸送層4は、陽極2と発光層5の間に形成される。また、
上述の正孔注入層3がある場合は、正孔注入層3と発光層5の間に形成される。
[Hole transport layer]
The hole transport layer 4 is a layer having a function of transporting holes from the anode 2 side to the light emitting layer 5 side. The hole transport layer 4 is not an essential layer in the organic electroluminescence device of the present invention, but it is preferable to form this layer in terms of enhancing the function of transporting holes from the anode 2 to the light emitting layer 5. . When forming the hole transport layer 4, the hole transport layer 4 is usually formed between the anode 2 and the light emitting layer 5. Also,
When the hole injection layer 3 described above is present, the hole injection layer 3 is formed between the hole injection layer 3 and the light emitting layer 5.
正孔輸送層4の膜厚は、通常5nm以上、好ましくは10nm以上であり、また、一方、通常300nm以下、好ましくは100nm以下である。
正孔輸送層4の形成方法は、真空蒸着法でも、湿式成膜法でもよい。成膜性が優れる点では、湿式成膜法により形成することが好ましい。
以下に一般的な正孔輸送層の形成方法について説明するが、本発明の有機電界発光素子において、正孔輸送層は、本発明の有機電界発光素子用組成物を用いて湿式成膜法により形成されることが好ましい。
The film thickness of the hole transport layer 4 is usually 5 nm or more, preferably 10 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
The formation method of the hole transport layer 4 may be a vacuum deposition method or a wet film formation method. In terms of excellent film forming properties, it is preferable to form the film by a wet film forming method.
Hereinafter, a general method for forming a hole transport layer will be described. In the organic electroluminescence device of the present invention, the hole transport layer is formed by a wet film formation method using the composition for organic electroluminescence device of the present invention. Preferably it is formed.
正孔輸送層4は、通常、正孔輸送性化合物を含有する。正孔輸送層4に含まれる正孔輸送性化合物としては、前途の化合物が挙げられるが、さらに具体的には、本発明の重合体の他に、4,4’−ビス[N−(1−ナフチル)−N−フェニルアミノ]ビフェニルで代表される、2個以上の3級アミンを含み2個以上の縮合芳香族環が窒素原子に置換した芳香族ジアミン(特開平5−234681号公報)、4,4’,4’’−トリス(1−ナフチルフェニルアミノ)トリフェニルアミン等のスターバースト構造を有する芳香族アミン化合物(J.Lumin.,72−74巻、985頁、1997年)、トリフェニルアミンの四量体から成る芳香族アミン化合物(Chem.Commun.,2175頁、1996年)、2,2’,7,7’−テトラキス−(ジフェニルアミノ)−9,9’−スピロビフルオレン等のスピロ化合物(Synth.Metals,91巻、209頁、1997年)、4,4’−N,N’−ジカルバゾールビフェニル等のカルバゾール誘導体等が好ましいものとして挙げられる。また、例えばポリビニルカルバゾール、ポリビニルトリフェニルアミン(特開平7−53953号公報)、テトラフェニルベンジジンを含有するポリアリーレンエーテルサルホン(Polym.Adv.Tech.,7巻、33頁、1996年)等も好ましく使用できる。 The hole transport layer 4 usually contains a hole transport compound. Examples of the hole transporting compound contained in the hole transporting layer 4 include the compounds described above. More specifically, in addition to the polymer of the present invention, 4,4′-bis [N- (1 -Naphthyl) -N-phenylamino] biphenyl, an aromatic diamine containing two or more tertiary amines and having two or more condensed aromatic rings substituted with nitrogen atoms (Japanese Patent Laid-Open No. 5-234811) , 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine and other aromatic amine compounds having a starburst structure (J. Lumin., 72-74, 985, 1997), Aromatic amine compounds consisting of tetramers of triphenylamine (Chem. Commun., 2175, 1996), 2,2 ′, 7,7′-tetrakis- (diphenylamino) -9,9′-spi Spiro compounds such as bifluorene (Synth.Metals, 91 vol, 209 pp., 1997), 4,4'-N, such as a carbazole derivative such as N'- dicarbazole biphenyl as preferred. Also, for example, polyvinyl carbazole, polyvinyl triphenylamine (Japanese Patent Laid-Open No. 7-53953), polyarylene ether sulfone (Polym. Adv. Tech., 7, 33, 1996) containing tetraphenylbenzidine, etc. It can be preferably used.
[湿式成膜法による正孔輸送層の形成]
湿式成膜法で正孔輸送層を形成する場合は、通常、上述の正孔注入層を湿式成膜法で形成する場合と同様にして、正孔注入層形成用組成物の代わりに正孔輸送層形成用組成物を用いて形成させる。
湿式成膜法で正孔輸送層を形成する場合は、通常、正孔輸送層形成用組成物は、更に溶媒を含有する。正孔輸送層形成用組成物に用いる溶媒は、上述の正孔注入層形成用組成物で用いる溶媒と同様の溶媒を使用することができる。
正孔輸送層形成用組成物中における正孔輸送性化合物の濃度は、正孔注入層形成用組成物中における正孔輸送性化合物の濃度と同様の範囲とすることができる。
正孔輸送層の湿式成膜法による形成は、前述の正孔注入層成膜法と同様に行うことができる。
[Formation of hole transport layer by wet film formation method]
When forming a hole transport layer by a wet film formation method, in general, in the same manner as in the case of forming the above-described hole injection layer by a wet film formation method, holes are used instead of the hole injection layer forming composition. It forms using the composition for transport layer formation.
When the hole transport layer is formed by a wet film formation method, the hole transport layer forming composition usually further contains a solvent. As the solvent used for the composition for forming a hole transport layer, the same solvent as the solvent used for the composition for forming a hole injection layer described above can be used.
The concentration of the hole transporting compound in the composition for forming a hole transport layer can be in the same range as the concentration of the hole transporting compound in the composition for forming a hole injection layer.
Formation of the hole transport layer by a wet film formation method can be performed in the same manner as the hole injection layer film formation method described above.
[真空蒸着法による正孔輸送層の形成]
真空蒸着法で正孔輸送層を形成する場合についても、通常、上述の正孔注入層を真空蒸着法で形成する場合と同様にして、正孔注入層形成用組成物の代わりに正孔輸送層形成用組成物を用いて形成させることができる。蒸着時の真空度、蒸着速度及び温度等の成膜条件などは、前記正孔注入層の真空蒸着時と同様の条件で成膜することができる。
[Formation of hole transport layer by vacuum evaporation]
When the hole transport layer is formed by the vacuum deposition method, the hole transport layer is usually used instead of the hole injection layer forming composition in the same manner as in the case of forming the hole injection layer by the vacuum deposition method. It can form using the composition for layer formation. The film formation conditions such as the degree of vacuum at the time of vapor deposition, the vapor deposition rate and the temperature can be formed under the same conditions as those for the vacuum vapor deposition of the hole injection layer.
[発光層]
発光層5は、一対の電極間に電界が与えられた時に、陽極2から注入される正孔と陰極9から注入される電子が再結合することにより励起され、発光する機能を担う層である。発光層5は、陽極2と陰極9の間に形成される層であり、発光層は、陽極の上に正孔注入層がある場合は、正孔注入層と陰極の間に形成され、陽極の上に正孔輸送層がある場合は、正孔輸送層と陰極の間に形成される。
[Light emitting layer]
The light emitting layer 5 is a layer having a function of emitting light when excited by recombination of holes injected from the anode 2 and electrons injected from the cathode 9 when an electric field is applied between a pair of electrodes. . The light-emitting layer 5 is a layer formed between the anode 2 and the cathode 9, and the light-emitting layer is formed between the hole injection layer and the cathode when there is a hole injection layer on the anode. When there is a hole transport layer on the surface, it is formed between the hole transport layer and the cathode.
発光層5の膜厚は、本発明の効果を著しく損なわない限り任意であるが、膜に欠陥が生じ難い点では厚い方が好ましく、また、一方、薄い方が低駆動電圧としやすい点で好ましい。このため、3nm以上であるのが好ましく、5nm以上であるのが更に好ましく、また、一方、通常200nm以下であるのが好ましく、100nm以下であるのが更に好ましい。
発光層5は、少なくとも、発光の性質を有する材料(発光材料)を含有するとともに、好ましくは、電荷輸送性を有する材料(電荷輸送性材料)とを含有する。
The film thickness of the light emitting layer 5 is arbitrary as long as the effects of the present invention are not significantly impaired. However, a thicker film is preferable in that the film is less likely to be defective. On the other hand, a thinner film is preferable in terms of easy driving voltage. . For this reason, it is preferably 3 nm or more, more preferably 5 nm or more, and on the other hand, it is usually preferably 200 nm or less, and more preferably 100 nm or less.
The light emitting layer 5 contains at least a material having a light emitting property (light emitting material) and preferably contains a material having a charge transporting property (charge transporting material).
[発光材料]
発光材料は、所望の発光波長で発光し、本発明の効果を損なわない限りは特に制限はなく、公知の発光材料を適用可能である。発光材料は、蛍光発光材料でも、燐光発光材料でもよいが、発光効率が良好である材料が好ましく、内部量子効率の観点から燐光発光材料が好ましい。
[Luminescent material]
The light emitting material emits light at a desired light emission wavelength, and is not particularly limited as long as the effect of the present invention is not impaired, and a known light emitting material can be applied. The light emitting material may be a fluorescent light emitting material or a phosphorescent light emitting material, but a material having good light emission efficiency is preferred, and a phosphorescent light emitting material is preferred from the viewpoint of internal quantum efficiency.
蛍光発光材料としては、例えば、以下の材料が挙げられる。
青色発光を与える蛍光発光材料(青色蛍光発光材料)としては、例えば、ナフタレン、ペリレン、ピレン、アントラセン、クマリン、クリセン、p−ビス(2−フェニルエテニル)ベンゼン及びそれらの誘導体等が挙げられる。
緑色発光を与える蛍光発光材料(緑色蛍光発光材料)としては、例えば、キナクリドン誘導体、クマリン誘導体、Al(C9H6NO)3等のアルミニウム錯体等が挙げられる。
Examples of the fluorescent light emitting material include the following materials.
Examples of the fluorescent light-emitting material that gives blue light emission (blue fluorescent light-emitting material) include naphthalene, perylene, pyrene, anthracene, coumarin, chrysene, p-bis (2-phenylethenyl) benzene, and derivatives thereof.
Examples of the fluorescent light-emitting material that gives green light emission (green fluorescent light-emitting material) include quinacridone derivatives, coumarin derivatives, aluminum complexes such as Al (C 9 H 6 NO) 3, and the like.
黄色発光を与える蛍光発光材料(黄色蛍光発光材料)としては、例えば、ルブレン、ペリミドン誘導体等が挙げられる。
赤色発光を与える蛍光発光材料(赤色蛍光発光材料)としては、例えば、DCM(4−(dicyanomethylene)−2−methyl−6−(p−dimethylaminostyryl)−4H−pyran)系化合物、ベンゾピラン誘導体、ローダミン誘導体、ベンゾチオキサンテン誘導体、アザベンゾチオキサンテン等が挙げられる。
Examples of the fluorescent light-emitting material that gives yellow light (yellow fluorescent light-emitting material) include rubrene and perimidone derivatives.
Examples of fluorescent light-emitting materials (red fluorescent light-emitting materials) that emit red light include, for example, DCM (4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran) -based compounds, benzopyran derivatives, rhodamine derivatives. Benzothioxanthene derivatives, azabenzothioxanthene and the like.
また、燐光発光材料としては、例えば、長周期型周期表の第7〜11族から選ばれる金属を含む有機金属錯体等が挙げられる。周期表の第7〜11族から選ばれる金属として、好ましくは、ルテニウム、ロジウム、パラジウム、銀、レニウム、オスミウム、イリジウム、白金、金等が挙げられる。
有機金属錯体の配位子としては、(ヘテロ)アリールピリジン配位子、(ヘテロ)アリールピラゾール配位子等の(ヘテロ)アリール基とピリジン、ピラゾール、フェナントロリン等が連結した配位子が好ましく、特にフェニルピリジン配位子、フェニルピラゾール配位子が好ましい。ここで、(ヘテロ)アリールとは、アリール基又はヘテロアリール基を表す。
Examples of the phosphorescent material include organometallic complexes containing a metal selected from Groups 7 to 11 of the long-period periodic table. Preferred examples of the metal selected from Groups 7 to 11 of the periodic table include ruthenium, rhodium, palladium, silver, rhenium, osmium, iridium, platinum, and gold.
As the ligand of the organometallic complex, a ligand in which a (hetero) aryl group such as a (hetero) arylpyridine ligand or (hetero) arylpyrazole ligand and a pyridine, pyrazole, phenanthroline, or the like is connected is preferable. In particular, a phenylpyridine ligand and a phenylpyrazole ligand are preferable. Here, (hetero) aryl represents an aryl group or a heteroaryl group.
好ましい燐光発光材料として、具体的には、例えば、トリス(2−フェニルピリジン)イリジウム、トリス(2−フェニルピリジン)ルテニウム、トリス(2−フェニルピリジン)パラジウム、ビス(2−フェニルピリジン)白金、トリス(2−フェニルピリジン)オスミウム、トリス(2−フェニルピリジン)レニウム等のフェニルピリジン錯体及びオクタエチル白金ポルフィリン、オクタフェニル白金ポルフィリン、オクタエチルパラジウムポルフィリン、オクタフェニルパラジウムポルフィリン等のポルフィリン錯体等が挙げられる。 Specific examples of preferred phosphorescent materials include tris (2-phenylpyridine) iridium, tris (2-phenylpyridine) ruthenium, tris (2-phenylpyridine) palladium, bis (2-phenylpyridine) platinum, and tris. Examples thereof include phenylpyridine complexes such as (2-phenylpyridine) osmium and tris (2-phenylpyridine) rhenium, and porphyrin complexes such as octaethylplatinum porphyrin, octaphenylplatinum porphyrin, octaethyl palladium porphyrin, and octaphenyl palladium porphyrin.
高分子系の発光材料としては、ポリ(9,9−ジオクチルフルオレン−2,7−ジイル
)、ポリ[(9,9−ジオクチルフルオレン−2,7−ジイル)−co−(4,4’−(N−(4−sec−ブチルフェニル))ジフェニルアミン)]、ポリ[(9,9−ジオクチルフルオレン−2,7−ジイル)−co−(1,4−ベンゾ−2{2,1’−3}−トリアゾール)]等のポリフルオレン系材料、ポリ[2−メトキシ−5−(2−ヘチルヘキシルオキシ)−1,4−フェニレンビニレン]等のポリフェニレンビニレン系材料が挙げられる。
Polymeric light-emitting materials include poly (9,9-dioctylfluorene-2,7-diyl), poly [(9,9-dioctylfluorene-2,7-diyl) -co- (4,4′- (N- (4-sec-butylphenyl)) diphenylamine)], poly [(9,9-dioctylfluorene-2,7-diyl) -co- (1,4-benzo-2 {2,1'-3 } -Triazole)] and the like, and polyphenylene vinylene materials such as poly [2-methoxy-5- (2-hexylhexyloxy) -1,4-phenylenevinylene].
[電荷輸送性材料]
電荷輸送性材料は、正電荷(正孔)又は負電荷(電子)輸送性を有する材料であり、本発明の効果を損なわない限り、特に制限はなく、公知の発光材料を適用可能である。
電荷輸送性材料は、従来、有機電界発光素子の発光層に用いられている化合物等を用いることができ、特に、発光層のホスト材料として使用されている化合物が好ましい。
[Charge transport materials]
The charge transport material is a material having a positive charge (hole) or negative charge (electron) transport property, and is not particularly limited as long as the effect of the present invention is not impaired, and a known light emitting material can be applied.
As the charge transporting material, a compound or the like conventionally used in a light emitting layer of an organic electroluminescence device can be used, and a compound used as a host material of the light emitting layer is particularly preferable.
電荷輸送性材料としては、具体的には、本発明の重合体を含む芳香族アミン系化合物、フタロシアニン系化合物、ポルフィリン系化合物、オリゴチオフェン系化合物、ポリチオフェン系化合物、ベンジルフェニル系化合物、フルオレン基で3級アミンを連結した化合物、ヒドラゾン系化合物、シラザン系化合物、シラナミン系化合物、ホスファミン系化合物、キナクリドン系化合物等の正孔注入層の正孔輸送性化合物として例示した化合物等が挙げられる他、アントラセン系化合物、ピレン系化合物、カルバゾール系化合物、ピリジン系化合物、フェナントロリン系化合物、オキサジアゾール系化合物、シロール系化合物等の電子輸送性化合物等が挙げられる。 Specific examples of the charge transporting material include aromatic amine compounds, phthalocyanine compounds, porphyrin compounds, oligothiophene compounds, polythiophene compounds, benzylphenyl compounds, and fluorene groups including the polymer of the present invention. In addition to the compounds exemplified as the hole transporting compound of the hole injection layer, such as a compound in which a tertiary amine is linked, a hydrazone compound, a silazane compound, a silanamine compound, a phosphamine compound, a quinacridone compound, and the like And electron transporting compounds such as benzene compounds, pyrene compounds, carbazole compounds, pyridine compounds, phenanthroline compounds, oxadiazole compounds, silole compounds, and the like.
また、例えば、4,4’−ビス[N−(1−ナフチル)−N−フェニルアミノ]ビフェニルで代表される2個以上の3級アミンを含み2個以上の縮合芳香族環が窒素原子に置換した芳香族ジアミン(特開平5−234681号公報)、4,4’,4’’−トリス(1−ナフチルフェニルアミノ)トリフェニルアミン等のスターバースト構造を有する芳香族アミン系化合物(J.Lumin.,72−74巻、985頁、1997年)、トリフェニルアミンの四量体から成る芳香族アミン系化合物(Chem.Commun.,2175頁、1996年)、2,2’,7,7’−テトラキス−(ジフェニルアミノ)−9,9’−スピロビフルオレン等のフルオレン系化合物(Synth.Metals,91巻、209頁、1997年)、4,4’−N,N’−ジカルバゾールビフェニル等のカルバゾール系化合物等の正孔輸送層の正孔輸送性化合物として例示した化合物等も好ましく用いることができる。 In addition, for example, two or more condensed aromatic rings including two or more tertiary amines typified by 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl have nitrogen atoms. Aromatic amine compounds having a starburst structure such as substituted aromatic diamines (Japanese Patent Laid-Open No. 5-234681), 4,4 ′, 4 ″ -tris (1-naphthylphenylamino) triphenylamine (J. Lumin., 72-74, 985, 1997), an aromatic amine compound comprising a tetramer of triphenylamine (Chem. Commun., 2175, 1996), 2, 2 ′, 7, 7 Fluorene compounds such as' -tetrakis- (diphenylamino) -9,9'-spirobifluorene (Synth. Metals, 91, 209, 1997), 4, '-N, N'compounds exemplified as hole-transporting compound of the positive hole transport layer of the carbazole-based compounds such as di-biphenyl, or the like can be preferably used.
また、この他、2−(4−ビフェニリル)−5−(p−ターシャルブチルフェニル)−1,3,4−オキサジアゾール(tBu−PBD)、2,5−ビス(1−ナフチル)−1,3,4−オキサジアゾール(BND)等のオキサジアゾール系化合物、2,5−ビス(6’−(2’,2’’−ビピリジル))−1,1−ジメチル−3,4−ジフェニルシロール(PyPySPyPy)等のシロール系化合物、バソフェナントロリン(BPhen)、2,9−ジメチル−4,7−ジフェニル−1,10−フェナントロリン(BCP、バソクプロイン)等のフェナントロリン系化合物等も挙げられる。 In addition, 2- (4-biphenylyl) -5- (p-tertiarybutylphenyl) -1,3,4-oxadiazole (tBu-PBD), 2,5-bis (1-naphthyl)- Oxadiazole compounds such as 1,3,4-oxadiazole (BND), 2,5-bis (6 ′-(2 ′, 2 ″ -bipyridyl))-1,1-dimethyl-3,4 Examples thereof include silole compounds such as diphenylsilole (PyPySPyPy) and phenanthroline compounds such as bathophenanthroline (BPhen) and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP, bathocuproin).
[湿式成膜法による発光層の形成]
発光層の形成方法は、真空蒸着法でも、湿式成膜法でもよいが、成膜性に優れることから、湿式成膜法が好ましく、スピンコート法及びインクジェット法が更に好ましい。特に、本発明の有機電界発光素子用組成物を用いて、発光層の下層となる正孔注入層又は正孔輸送層を形成すると、湿式成膜法による積層化が容易であるため、湿式成膜法を採用することが好ましい。湿式成膜法により発光層を形成する場合は、通常、上述の正孔注入層を湿式成膜法で形成する場合と同様にして、正孔注入層形成用組成物の代わりに、発光層となる材料を可溶な溶媒(発光層用溶媒)と混合して調製した発光層形成用組成物を用いて
形成する。
[Formation of light-emitting layer by wet film formation method]
The method for forming the light emitting layer may be a vacuum deposition method or a wet film formation method, but a wet film formation method is preferable and a spin coating method and an ink jet method are more preferable because of excellent film forming properties. In particular, when a hole injection layer or a hole transport layer, which is a lower layer of a light emitting layer, is formed using the composition for an organic electroluminescent element of the present invention, it is easy to form a layer by a wet film formation method. It is preferable to employ a membrane method. When the light emitting layer is formed by a wet film forming method, the light emitting layer is usually used instead of the hole injection layer forming composition in the same manner as in the case of forming the hole injection layer by the wet film forming method. The light-emitting layer forming composition prepared by mixing the material to be mixed with a soluble solvent (light-emitting layer solvent) is used.
溶媒としては、例えば、正孔注入層の形成について挙げたエーテル系溶媒、エステル系溶媒、芳香族炭化水素系溶媒、アミド系溶媒の他、アルカン系溶媒、ハロゲン化芳香族炭化水素系溶媒、脂肪族アルコール系溶媒、脂環族アルコール系溶媒、脂肪族ケトン系溶媒及び脂環族ケトン系溶媒等が挙げられる。以下に溶媒の具体例を挙げるが、本発明の効果を損なわない限り、これらに限定されるものではない。 Examples of the solvent include ether solvents, ester solvents, aromatic hydrocarbon solvents, amide solvents, alkane solvents, halogenated aromatic hydrocarbon solvents, fats, and the like mentioned for the formation of the hole injection layer. An aromatic alcohol solvent, an alicyclic alcohol solvent, an aliphatic ketone solvent, an alicyclic ketone solvent, and the like. Although the specific example of a solvent is given to the following, as long as the effect of this invention is not impaired, it is not limited to these.
例えば、エチレングリコールジメチルエーテル、エチレングリコールジエチルエーテル、プロピレングリコール−1−モノメチルエーテルアセタート(PGMEA)等の脂肪族エーテル系溶媒;1,2−ジメトキシベンゼン、1,3−ジメトキシベンゼン、アニソール、フェネトール、2−メトキシトルエン、3−メトキシトルエン、4−メトキシトルエン、2,3−ジメチルアニソール、2,4−ジメチルアニソール、ジフェニルエーテル等の芳香族エーテル系溶媒;酢酸フェニル、プロピオン酸フェニル、安息香酸メチル、安息香酸エチル、安息香酸プロピル、安息香酸n−ブチル等の芳香族エステル系溶媒;トルエン、キシレン、メシチレン、シクロヘキシルベンゼン、テトラリン、3−イロプロピルビフェニル、1,2,3,4−テトラメチルベンゼン、1,4−ジイソプロピルベンゼン、シクロヘキシルベンゼン、メチルナフタレン等の芳香族炭化水素系溶媒;N,N−ジメチルホルムアミド、N,N−ジメチルアセトアミド等のアミド系溶媒;n−デカン、シクロヘキサン、エチルシクロヘキサン、デカリン、ビシクロヘキサン等のアルカン系溶媒;クロロベンゼン、ジクロロベンゼン、トリクロロベンゼン等のハロゲン化芳香族炭化水素系溶媒;ブタノール、ヘキサノール等の脂肪族アルコール系溶媒;シクロヘキサノール、シクロオクタノール等の脂環族アルコール系溶媒;メチルエチルケトン、ジブチルケトン等の脂肪族ケトン系溶媒;シクロヘキサノン、シクロオクタノン、フェンコン等の脂環族ケトン系溶媒等が挙げられる。これらのうち、アルカン系溶媒及び芳香族炭化水素系溶媒が特に好ましい。 For example, aliphatic ether solvents such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, propylene glycol-1-monomethyl ether acetate (PGMEA); 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole, phenetole, 2 -Aromatic ether solvents such as methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole, diphenyl ether; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic ester solvents such as ethyl, propyl benzoate, n-butyl benzoate; toluene, xylene, mesitylene, cyclohexylbenzene, tetralin, 3-iropropylbiphenyl, 1,2,3,4-te Aromatic hydrocarbon solvents such as lamethylbenzene, 1,4-diisopropylbenzene, cyclohexylbenzene and methylnaphthalene; amide solvents such as N, N-dimethylformamide and N, N-dimethylacetamide; n-decane, cyclohexane, Alkane solvents such as ethylcyclohexane, decalin and bicyclohexane; Halogenated aromatic hydrocarbon solvents such as chlorobenzene, dichlorobenzene and trichlorobenzene; Aliphatic alcohol solvents such as butanol and hexanol; Fats such as cyclohexanol and cyclooctanol Examples include cyclic alcohol solvents; aliphatic ketone solvents such as methyl ethyl ketone and dibutyl ketone; and alicyclic ketone solvents such as cyclohexanone, cyclooctanone, and Fencon. Of these, alkane solvents and aromatic hydrocarbon solvents are particularly preferred.
[正孔阻止層]
発光層5と後述の電子注入層8との間に、正孔阻止層6を設けてもよい。正孔阻止層6は、発光層5の上に、発光層5の陰極9側の界面に接するように積層される層である。
この正孔阻止層6は、陽極2から移動してくる正孔を陰極9に到達するのを阻止する役割と、陰極9から注入された電子を効率よく発光層5の方向に輸送する役割とを有する。正孔阻止層6を構成する材料に求められる物性としては、電子移動度が高く正孔移動度が低いこと、エネルギーギャップ(HOMO、LUMOの差)が大きいこと、励起三重項準位(T1)が高いことが挙げられる。
[Hole blocking layer]
A hole blocking layer 6 may be provided between the light emitting layer 5 and an electron injection layer 8 described later. The hole blocking layer 6 is a layer laminated on the light emitting layer 5 so as to be in contact with the interface of the light emitting layer 5 on the cathode 9 side.
The hole blocking layer 6 has a role of blocking holes moving from the anode 2 from reaching the cathode 9 and a role of efficiently transporting electrons injected from the cathode 9 toward the light emitting layer 5. Have The physical properties required for the material constituting the hole blocking layer 6 include high electron mobility, low hole mobility, a large energy gap (difference between HOMO and LUMO), and excited triplet level (T1). Is high.
このような条件を満たす正孔阻止層の材料としては、例えば、ビス(2−メチル−8−キノリノラト)(フェノラト)アルミニウム、ビス(2−メチル−8−キノリノラト)(トリフェニルシラノラト)アルミニウム等の混合配位子錯体、ビス(2−メチル−8−キノラト)アルミニウム−μ−オキソ−ビス−(2−メチル−8−キノリラト)アルミニウム二核金属錯体等の金属錯体、ジスチリルビフェニル誘導体等のスチリル化合物(特開平11−242996号公報)、3−(4−ビフェニルイル)−4−フェニル−5−(4−tert−ブチルフェニル)−1,2,4−トリアゾール等のトリアゾール誘導体(特開平7−41759号公報)、バソクプロイン等のフェナントロリン誘導体(特開平10−79297号公報)等が挙げられる。更に、国際公開第2005/022962号に記載の2,4,6位が置換されたピリジン環を少なくとも1個有する化合物も、正孔阻止層の材料として好ましい。 Examples of the material for the hole blocking layer satisfying such conditions include bis (2-methyl-8-quinolinolato) (phenolato) aluminum, bis (2-methyl-8-quinolinolato) (triphenylsilanolato) aluminum, and the like. Mixed metal complexes such as bis (2-methyl-8-quinolato) aluminum-μ-oxo-bis- (2-methyl-8-quinolinato) aluminum binuclear metal complexes, distyrylbiphenyl derivatives, etc. Triazole derivatives (Japanese Patent Laid-Open No. 11-242996), triazole derivatives such as 3- (4-biphenylyl) -4-phenyl-5- (4-tert-butylphenyl) -1,2,4-triazole 7-41759), phenanthroline derivatives such as bathocuproine (JP-A-10-79297) and the like. That. Furthermore, a compound having at least one pyridine ring substituted at the 2,4,6-position described in International Publication No. 2005/022962 is also preferable as a material for the hole blocking layer.
正孔阻止層6の形成方法に制限はない。従って、湿式成膜法、蒸着法や、その他の方法で形成できる。
正孔阻止層6の膜厚は、本発明の効果を著しく損なわない限り任意であるが、通常0.3nm以上、好ましくは0.5nm以上であり、また、通常100nm以下、好ましくは50nm以下である。
There is no restriction | limiting in the formation method of the hole-blocking layer 6. FIG. Therefore, it can be formed by a wet film forming method, a vapor deposition method, or other methods.
The thickness of the hole blocking layer 6 is arbitrary as long as the effect of the present invention is not significantly impaired, but is usually 0.3 nm or more, preferably 0.5 nm or more, and usually 100 nm or less, preferably 50 nm or less. is there.
[電子輸送層]
電子輸送層7は素子の電流効率をさらに向上させることを目的として、発光層5と電子注入層8との間に設けられる。
電子輸送層7は、電界を与えられた電極間において陰極9から注入された電子を効率よく発光層5の方向に輸送することができる化合物より形成される。電子輸送層7に用いられる電子輸送性化合物としては、陰極9又は電子注入層8からの電子注入効率が高く、かつ、高い電子移動度を有し、注入された電子を効率よく輸送することができる化合物であることが必要である。
[Electron transport layer]
The electron transport layer 7 is provided between the light emitting layer 5 and the electron injection layer 8 for the purpose of further improving the current efficiency of the device.
The electron transport layer 7 is formed of a compound that can efficiently transport electrons injected from the cathode 9 between electrodes to which an electric field is applied in the direction of the light emitting layer 5. As an electron transporting compound used for the electron transport layer 7, the electron injection efficiency from the cathode 9 or the electron injection layer 8 is high, and it has high electron mobility and can efficiently transport the injected electrons. It must be a compound that can be made.
電子輸送層に用いる電子輸送性化合物としては、具体的には、例えば、8−ヒドロキシキノリンのアルミニウム錯体等の金属錯体(特開昭59−194393号公報)、10−ヒドロキシベンゾ[h]キノリンの金属錯体、オキサジアゾール誘導体、ジスチリルビフェニル誘導体、シロール誘導体、3−ヒドロキシフラボン金属錯体、5−ヒドロキシフラボン金属錯体、ベンズオキサゾール金属錯体、ベンゾチアゾール金属錯体、トリスベンズイミダゾリルベンゼン(米国特許第5645948号明細書)、キノキサリン化合物(特開平6−207169号公報)、フェナントロリン誘導体(特開平5−331459号公報)、2−t−ブチル−9,10−N,N’−ジシアノアントラキノンジイミン、n型水素化非晶質炭化シリコン、n型硫化亜鉛、n型セレン化亜鉛等が挙げられる。
電子輸送層7の膜厚は、通常1nm以上、好ましくは5nm以上であり、また、通常300nm以下、好ましくは100nm以下である。
電子輸送層7は、前記と同様にして湿式成膜法、或いは真空蒸着法により正孔阻止層6上に積層することにより形成される。通常は、真空蒸着法が用いられる。
Specific examples of the electron transporting compound used in the electron transporting layer include, for example, metal complexes such as an aluminum complex of 8-hydroxyquinoline (Japanese Patent Laid-Open No. 59-194393), 10-hydroxybenzo [h] quinoline Metal complexes, oxadiazole derivatives, distyryl biphenyl derivatives, silole derivatives, 3-hydroxyflavone metal complexes, 5-hydroxyflavone metal complexes, benzoxazole metal complexes, benzothiazole metal complexes, trisbenzimidazolylbenzene (US Pat. No. 5,645,948) Description), quinoxaline compound (JP-A-6-207169), phenanthroline derivative (JP-A-5-331459), 2-t-butyl-9,10-N, N′-dicyanoanthraquinonediimine, n-type Hydrogenated amorphous silicon carbide, n-type sulfur Zinc halide, n-type zinc selenide, etc. are mentioned.
The thickness of the electron transport layer 7 is usually 1 nm or more, preferably 5 nm or more, and is usually 300 nm or less, preferably 100 nm or less.
The electron transport layer 7 is formed by laminating on the hole blocking layer 6 by a wet film formation method or a vacuum deposition method in the same manner as described above. Usually, a vacuum deposition method is used.
[電子注入層]
電子注入層8は、陰極9から注入された電子を効率よく、電子輸送層7又は発光層5へ注入する役割を果たす。
電子注入を効率よく行うには、電子注入層8を形成する材料は、仕事関数の低い金属が好ましい。例としては、ナトリウムやセシウム等のアルカリ金属、バリウムやカルシウム等のアルカリ土類金属等が用いられる。その膜厚は通常0.1nm以上、5nm以下が好ましい。
[Electron injection layer]
The electron injection layer 8 plays a role of efficiently injecting electrons injected from the cathode 9 into the electron transport layer 7 or the light emitting layer 5.
In order to perform electron injection efficiently, the material for forming the electron injection layer 8 is preferably a metal having a low work function. Examples include alkali metals such as sodium and cesium, and alkaline earth metals such as barium and calcium. The film thickness is usually preferably from 0.1 nm to 5 nm.
更に、バソフェナントロリン等の含窒素複素環化合物や8−ヒドロキシキノリンのアルミニウム錯体等の金属錯体に代表される有機電子輸送材料に、ナトリウム、カリウム、セシウム、リチウム、ルビジウム等のアルカリ金属をドープする(特開平10−270171号公報、特開2002−100478号公報、特開2002−100482号公報等に記載)ことも、電子注入・輸送性が向上し優れた膜質を両立させることが可能となるため好ましい。 Furthermore, an organic electron transport material represented by a metal complex such as a nitrogen-containing heterocyclic compound such as bathophenanthroline or an aluminum complex of 8-hydroxyquinoline is doped with an alkali metal such as sodium, potassium, cesium, lithium, or rubidium ( (Described in JP-A-10-270171, JP-A-2002-1000047, JP-A-2002-1000048, etc.) also improves electron injection / transport and makes it possible to achieve both excellent film quality. preferable.
電子注入層8の膜厚は、通常5nm以上、好ましくは10nm以上であり、また通常200nm以下、好ましくは100nm以下の範囲である。
電子注入層8は、湿式成膜法或いは真空蒸着法により、発光層5又はその上の正孔阻止層6や電子輸送層7上に積層することにより形成される。
湿式成膜法の場合の詳細は、前述の発光層の場合と同様である。
The film thickness of the electron injection layer 8 is usually 5 nm or more, preferably 10 nm or more, and is usually 200 nm or less, preferably 100 nm or less.
The electron injection layer 8 is formed by laminating the light emitting layer 5 or the hole blocking layer 6 or the electron transport layer 7 thereon by a wet film formation method or a vacuum deposition method.
The details in the case of the wet film forming method are the same as those in the case of the light emitting layer described above.
[陰極]
陰極9は、発光層5側の層(電子注入層又は発光層など)に電子を注入する役割を果た
す。
陰極9の材料としては、前記の陽極2に使用される材料を用いることが可能であるが、効率良く電子注入を行なう上では、仕事関数の低い金属を用いることが好ましく、例えば、スズ、マグネシウム、インジウム、カルシウム、アルミニウム、銀等の金属又はそれらの合金等が用いられる。具体例としては、例えば、マグネシウム−銀合金、マグネシウム−インジウム合金、アルミニウム−リチウム合金等の低仕事関数の合金電極等が挙げられる。
[cathode]
The cathode 9 plays a role of injecting electrons into a layer (such as an electron injection layer or a light emitting layer) on the light emitting layer 5 side.
As the material of the cathode 9, the material used for the anode 2 can be used. However, in order to perform electron injection efficiently, it is preferable to use a metal having a low work function. , Metals such as indium, calcium, aluminum and silver, or alloys thereof. Specific examples include low work function alloy electrodes such as magnesium-silver alloy, magnesium-indium alloy, and aluminum-lithium alloy.
素子の安定性の点では、陰極の上に、仕事関数が高く、大気に対して安定な金属層を積層して、低仕事関数の金属からなる陰極を保護することが好ましい。積層する金属としては、例えば、アルミニウム、銀、銅、ニッケル、クロム、金、白金等の金属が挙げられる。
陰極の膜厚は通常、陽極と同様である。
From the viewpoint of device stability, it is preferable to protect a cathode made of a metal having a low work function by laminating a metal layer having a high work function and stable to the atmosphere on the cathode. Examples of the metal to be laminated include metals such as aluminum, silver, copper, nickel, chromium, gold, and platinum.
The thickness of the cathode is usually the same as that of the anode.
[その他の層]
本発明の有機電界発光素子は、本発明の効果を著しく損なわなければ、更に他の層を有していてもよい。すなわち、陽極と陰極との間に、上述の他の任意の層を有していてもよい。
[Other layers]
The organic electroluminescent element of the present invention may further have other layers as long as the effects of the present invention are not significantly impaired. That is, any other layer described above may be provided between the anode and the cathode.
[その他の素子構成]
本発明の有機電界発光素子は、上述の説明とは逆の構造、即ち、基板上に陰極、電子注入層、電子輸送層、正孔阻止層、発光層、正孔輸送層、正孔注入層、陽極の順に積層することも可能である。
本発明の有機電界発光素子を有機電界発光装置に適用する場合は、単一の有機電界発光素子として用いても、複数の有機電界発光素子がアレイ状に配置された構成にして用いても、陽極と陰極がX−Yマトリックス状に配置された構成にして用いてもよい。
[Other element configurations]
The organic electroluminescent device of the present invention has a structure opposite to that described above, that is, a cathode, an electron injection layer, an electron transport layer, a hole blocking layer, a light emitting layer, a hole transport layer, and a hole injection layer on the substrate. It is also possible to laminate in the order of the anode.
When the organic electroluminescent element of the present invention is applied to an organic electroluminescent device, it may be used as a single organic electroluminescent element, or may be used in a configuration in which a plurality of organic electroluminescent elements are arranged in an array, The anode and the cathode may be used in a configuration in which they are arranged in an XY matrix.
<有機EL表示装置>
本発明の有機EL表示装置(有機電界発光素子表示装置)は、上述の本発明の有機電界発光素子を用いたものである。本発明の有機EL表示装置の型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。
例えば、「有機ELディスプレイ」(オーム社、平成16年8月20日発行、時任静士、安達千波矢、村田英幸著)に記載されているような方法で、本発明の有機EL表示装置を形成することができる。
<Organic EL display device>
The organic EL display device (organic electroluminescent element display device) of the present invention uses the above-described organic electroluminescent element of the present invention. There is no restriction | limiting in particular about the model and structure of the organic electroluminescent display apparatus of this invention, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.
For example, the organic EL display device of the present invention can be obtained by the method described in “Organic EL display” (Ohm, published on Aug. 20, 2004, Shizushi Tokito, Chiba Adachi, Hideyuki Murata). Can be formed.
<有機EL照明>
本発明の有機EL照明(有機電界発光素子照明)は、上述の本発明の有機電界発光素子を用いたものである。本発明の有機EL照明の型式や構造については特に制限はなく、本発明の有機電界発光素子を用いて常法に従って組み立てることができる。
<Organic EL lighting>
The organic EL illumination (organic electroluminescence element illumination) of the present invention uses the above-described organic electroluminescence element of the present invention. There is no restriction | limiting in particular about the model and structure of the organic EL illumination of this invention, It can assemble in accordance with a conventional method using the organic electroluminescent element of this invention.
以下、実施例を示して本発明について更に具体的に説明する。ただし、本発明は以下の実施例に限定されるものではなく、本発明はその要旨を逸脱しない限り任意に変更して実施できる。 Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples, and the present invention can be arbitrarily modified and implemented without departing from the gist thereof.
<実施例1>
[モノマー(化合物5)の合成]
以下の反応式に従い、化合物5を合成した。
<Example 1>
[Synthesis of Monomer (Compound 5)]
Compound 5 was synthesized according to the following reaction formula.
窒素気流中、2,7−ジブロモカルバゾール(化合物1)を10.47g(32.22mmol)、1−ブロモヘキサン(化合物2)を7.98g(48.32mmol)、ジメチルスルホキシド(200ml)、テトラブチルアンモニウムブロミド(2.2g)からなる混合物に水酸化ナトリウム6.4gを純水15mlに溶解した水溶液をゆっくり滴下し、その後70℃で3時間反応した。室温まで放冷した後、純水(200ml)をゆっくり加え、15分間撹拌後、酢酸エチル(200ml)を加え、分液し、水層を酢酸エチル(100ml×2回)で抽出し、有機層を合わせ、硫酸マグネシウムで乾燥後、濃縮した。さらに、シリカゲルカラムクロマトグラフィー(n−ヘキサン/酢酸エチル=6/1)で精製することにより、無色固体の化合物3(12.2g)を得た。 In a nitrogen stream, 10.47 g (32.22 mmol) of 2,7-dibromocarbazole (Compound 1), 7.98 g (48.32 mmol) of 1-bromohexane (Compound 2), dimethyl sulfoxide (200 ml), tetrabutyl An aqueous solution prepared by dissolving 6.4 g of sodium hydroxide in 15 ml of pure water was slowly added dropwise to a mixture composed of ammonium bromide (2.2 g), and then reacted at 70 ° C. for 3 hours. After allowing to cool to room temperature, pure water (200 ml) was slowly added, and after stirring for 15 minutes, ethyl acetate (200 ml) was added, liquid separation was performed, and the aqueous layer was extracted with ethyl acetate (100 ml × 2 times). Were combined, dried over magnesium sulfate and concentrated. Further, purification by silica gel column chromatography (n-hexane / ethyl acetate = 6/1) gave Compound 3 (12.2 g) as a colorless solid.
窒素気流下、500mlフラスコにジメチルスルホキシドを200ml、化合物3を12.1g(29.57mmol)、ビス(ピナコラト)ジボロンを16.5g(65.06mmol)、酢酸カリウムを17.4g(177.42mmol)入れ、60℃で30分間攪拌した。その後、1,1’−ビス(ジフェニルホスフィノ)フェロセン-パラジウム(II)ジクロリド-ジクロロメタン〔PdCl2(dppf)CH2Cl2〕1.21g(1.48mmol)を加え、85℃で6時間反応した。放冷し内温が40℃時に200mlの純水をゆっくり加え、10分間撹拌し、析出物を減圧濾過した。ろ取物はトルエンで再溶解して、無水硫酸マグネシウムで乾燥、活性白土で処理後、ろ過、得た溶液を濃縮してメタノールにより無色固体の化合物4を得た(収量11.9g)。 Under a nitrogen stream, 200 ml of dimethyl sulfoxide, 12.1 g (29.57 mmol) of compound 3, 16.5 g (65.06 mmol) of bis (pinacolato) diboron, and 17.4 g (177.42 mmol) of potassium acetate were added to a 500 ml flask. And stirred at 60 ° C. for 30 minutes. Thereafter, 1.21 g (1.48 mmol) of 1,1′-bis (diphenylphosphino) ferrocene-palladium (II) dichloride-dichloromethane [PdCl 2 (dppf) CH 2 Cl 2 ] was added and reacted at 85 ° C. for 6 hours. did. The mixture was allowed to cool, 200 ml of pure water was slowly added when the internal temperature was 40 ° C., the mixture was stirred for 10 minutes, and the precipitate was filtered under reduced pressure. The filtered product was redissolved with toluene, dried over anhydrous magnesium sulfate, treated with activated clay, filtered, and the obtained solution was concentrated to give colorless solid compound 4 with methanol (yield 11.9 g).
(43.81mmol)、りん酸カリウム水溶液(2M、すなわち2モル/リットル濃度)48mlを入れて加熱し、30分間攪拌した。その後ビス(トリフェニルホスフィン)パラジウム(II)ジクロリド0.31g(0.44mmol)を加え、6時間還流した。反応液に水を入れ、トルエンで抽出し、MgSO4および活性白土で処理した。吸着シリカゲルカラムクロマトグラフィー(展開溶媒:n−ヘキサン:塩化メチレン=3:1)により精製し、無色固体の化合物5を得た(収量6.9g、収率58.9%)。
(43.81 mmol) and 48 ml of an aqueous potassium phosphate solution (2 M, ie, 2 mol / liter concentration) were added and heated and stirred for 30 minutes. Thereafter, 0.31 g (0.44 mmol) of bis (triphenylphosphine) palladium (II) dichloride was added and refluxed for 6 hours. Water was added to the reaction solution, extracted with toluene, and treated with MgSO 4 and activated clay. Purification by adsorption silica gel column chromatography (developing solvent: n-hexane: methylene chloride = 3: 1) gave Compound 5 as a colorless solid (yield 6.9 g, yield 58.9%).
[重合体1の合成]
以下の反応式に従い、重合体1を合成した。
[Synthesis of Polymer 1]
Polymer 1 was synthesized according to the following reaction formula.
化合物5(0.80g、1.43mmol)、4,4‘−ジブロモビフェニル(0.108g、0.347mmol)、2−アミノ−9,9−ジヘキシルフルオレン(0.90g、2.57mmol)、4−(3−アミノフェニル)ベンゾシクロブテン(0.192g、0.983mmol)、tert−ブトキシナトリウム(1.056g、11.0mmol)、トルエン(48g)をフラスコに仕込み、系内を十分に窒素置換して、60℃まで加温した(溶液A)。別のフラスコに仕込んだトリス(ジベンジリデンアセトン)ジパラジウム錯体(0.0261g、0.0285mmol)のトルエン14.7g溶液に、[4−(N,N−ジメチルアミノ)フェニル]ジ−tert−ブチルホスフィン(0.16g、0.60mmol)を加え、60℃まで加温した(溶液B)。窒素気流中、溶液Aに溶液Bを添加し、1.0時間、加熱還流反応した。各モノマーが消失したことを確認
し、4,4‘−ジブロモビフェニル(0.525g、1.68mmol)を添加した。1時間加熱還流後、ブロモベンゼン(0.228g、1.45mmol)を添加し、2時間加熱還流した。反応液を放冷し、トルエン50ml添加してエタノール/水(200ml/40ml)溶液に滴下し、粗ポリマーを得た。
Compound 5 (0.80 g, 1.43 mmol), 4,4′-dibromobiphenyl (0.108 g, 0.347 mmol), 2-amino-9,9-dihexylfluorene (0.90 g, 2.57 mmol), 4 -(3-Aminophenyl) benzocyclobutene (0.192 g, 0.983 mmol), tert-butoxy sodium (1.056 g, 11.0 mmol) and toluene (48 g) were charged into the flask, and the system was sufficiently purged with nitrogen And heated to 60 ° C. (solution A). To a solution of tris (dibenzylideneacetone) dipalladium complex (0.0261 g, 0.0285 mmol) charged in another flask in 14.7 g of toluene, [4- (N, N-dimethylamino) phenyl] di-tert-butyl was added. Phosphine (0.16 g, 0.60 mmol) was added and warmed to 60 ° C. (Solution B). In a nitrogen stream, solution B was added to solution A, and heated to reflux for 1.0 hour. After confirming disappearance of each monomer, 4,4′-dibromobiphenyl (0.525 g, 1.68 mmol) was added. After heating at reflux for 1 hour, bromobenzene (0.228 g, 1.45 mmol) was added and heated to reflux for 2 hours. The reaction solution was allowed to cool, 50 ml of toluene was added, and the solution was added dropwise to an ethanol / water (200 ml / 40 ml) solution to obtain a crude polymer.
この粗ポリマーをトルエンに溶解し、アセトンで再沈殿させ、析出したポリマーをトルエンに再溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、重合体1を得た(1.2g)。得られた重合体1の分子量、分散度は次のとおりであった。
重量平均分子量(Mw)=45700
数平均分子量(Mn)=30300
分散度(Mw/Mn)=1.51
This crude polymer was dissolved in toluene and reprecipitated with acetone. The precipitated polymer was redissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain polymer 1 (1.2 g). The molecular weight and dispersion degree of the obtained polymer 1 were as follows.
Weight average molecular weight (Mw) = 45700
Number average molecular weight (Mn) = 30300
Dispersity (Mw / Mn) = 1.51
<実施例2>
[重合体2の合成]
以下の反応式に従い、重合体2を合成した。
<Example 2>
[Synthesis of Polymer 2]
Polymer 2 was synthesized according to the following reaction formula.
化合物5(2.116g、3.77mmol)、2−アミノ−9,9−ジヘキシルフルオレン(2.635g、7.54mmol)、tert−ブトキシナトリウム(2.793g、29.1mmol)、トルエン(42.3g)をフラスコに仕込み、系内を十分に窒素置換して、60℃まで加温した(溶液A)。別のフラスコに仕込んだトリス(ジベンジリデンアセトン)ジパラジウム錯体(0.069g、0.075mmol)のトルエン3.88g溶液に、[4−(N,N−ジメチルアミノ)フェニル]ジ−tert−ブチルホスフィン(0.160g、0.60mmol)を加え、60℃まで加温した(溶液B)。窒素気流中、溶液Aに溶液Bを添加し、1.0時間、加熱還流反応した。各モノマーが消失したことを確認し、化合物6(1.411g、1.77mmol)を添加した。1時間加熱還流後、化合物7(0.751g、1.04mmol)を添加した。さらに1時間後、化合物6(0.3136g、0.394mmol)を添加した。1時間後、ブロモベンゼン(0.888g、5.66mmol)を添加し、2時間加熱還流した。反応液を放冷し、トルエン50ml添加してエタノール/水(200ml/40ml)溶液に滴下し
、粗ポリマーを得た。
Compound 5 (2.116 g, 3.77 mmol), 2-amino-9,9-dihexylfluorene (2.635 g, 7.54 mmol), sodium tert-butoxy (2.793 g, 29.1 mmol), toluene (42.42). 3 g) was charged into a flask, the inside of the system was sufficiently replaced with nitrogen, and the mixture was heated to 60 ° C. (solution A). To a solution of tris (dibenzylideneacetone) dipalladium complex (0.069 g, 0.075 mmol) charged in another flask with 3.88 g of toluene was added [4- (N, N-dimethylamino) phenyl] di-tert-butyl. Phosphine (0.160 g, 0.60 mmol) was added and warmed to 60 ° C. (Solution B). In a nitrogen stream, solution B was added to solution A, and heated to reflux for 1.0 hour. After confirming disappearance of each monomer, Compound 6 (1.411 g, 1.77 mmol) was added. After heating at reflux for 1 hour, compound 7 (0.751 g, 1.04 mmol) was added. After an additional hour, compound 6 (0.3136 g, 0.394 mmol) was added. After 1 hour, bromobenzene (0.888 g, 5.66 mmol) was added and heated to reflux for 2 hours. The reaction solution was allowed to cool, 50 ml of toluene was added, and the solution was added dropwise to an ethanol / water (200 ml / 40 ml) solution to obtain a crude polymer.
この粗ポリマーをトルエンに溶解し、アセトンで再沈殿させ、析出したポリマーをトルエンに再溶解させ、希塩酸にて洗浄し、アンモニア含有エタノールにて再沈殿した。濾取したポリマーをカラムクロマトグラフィーにより精製し、重合体2を得た(3.7g)。得られた重合体2の分子量、分散度は次のとおりであった。
重量平均分子量(Mw)=36900
数平均分子量(Mn)=27700
分散度(Mw/Mn)=1.33
末端基を除いた繰り返し単位の分子量は平均846であり、また架橋性基は、1繰り返し単位当たり平均0.148個である。これを単純比例により計算すると、分子量1000あたりの架橋性基の数は、0.175個と算出される。
This crude polymer was dissolved in toluene and reprecipitated with acetone. The precipitated polymer was redissolved in toluene, washed with dilute hydrochloric acid, and reprecipitated with ammonia-containing ethanol. The polymer collected by filtration was purified by column chromatography to obtain polymer 2 (3.7 g). The molecular weight and dispersion degree of the obtained polymer 2 were as follows.
Weight average molecular weight (Mw) = 36900
Number average molecular weight (Mn) = 27700
Dispersity (Mw / Mn) = 1.33
The molecular weight of the repeating unit excluding the terminal group is 846 on average, and the average number of crosslinkable groups is 0.148 per repeating unit. When this is calculated by simple proportion, the number of crosslinkable groups per 1000 molecular weight is calculated to be 0.175.
1 基板
2 陽極
3 正孔注入層
4 正孔輸送層
5 発光層
6 正孔阻止層
7 電子輸送層
8 電子注入層
9 陰極
10 有機電界発光素子
DESCRIPTION OF SYMBOLS 1 Substrate 2 Anode 3 Hole injection layer 4 Hole transport layer 5 Light emitting layer 6 Hole blocking layer 7 Electron transport layer 8 Electron injection layer 9 Cathode 10 Organic electroluminescent device
Claims (16)
基を有していてもよい、アルキル基、芳香族炭化水素基、又は芳香族複素環基を表す。R8、R9が複数個存在する場合、同じであっても異なっていても良い。) The polymer according to claim 5, wherein the Ar 4 is an aromatic hydrocarbon group or an aromatic heterocyclic group linked together via a linking group represented by the following formula (6).
Ar27及びAr28は、各々独立に、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar29〜Ar31は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Tは架橋性基を表す。
但し、Ar27及びAr28のいずれもが、直接結合であることはない。) The polymer as described in any one of Claims 1-6 which has a repeating unit shown by following formula (7) separately from the repeating unit represented by the said Formula (1).
Ar 27 and Ar 28 each independently represents a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 29 to Ar 31 each independently represent an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group.
However, neither Ar 27 nor Ar 28 is a direct bond. )
R15は、置換基を有していてもよい1〜24のアルキル基、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar32及びAr33は、各々独立に、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar34〜Ar38は、各々独立に、置換基を有していてもよい芳香族炭化水素基又芳香族複素環基を表し、
Tは架橋性基を表す。
但し、Ar32及びAr33のいずれもが、直接結合であることはない。) The polymer as described in any one of Claims 1-6 which has a repeating unit shown by following formula (8) separately from the repeating unit represented by the said Formula (1).
R 15 represents an alkyl group of 1 to 24 which may have a substituent, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 32 and Ar 33 each independently represent a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
Ar 34 to Ar 38 each independently represents an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group.
However, neither Ar 32 nor Ar 33 is a direct bond. )
Ar39、 Ar40、 Ar42、およびAr43は、各々独立に、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Ar41は、直接結合、置換基を有していてもよい芳香族炭化水素基又は芳香族複素環基を表し、
Tは架橋性基を表す。) The polymer as described in any one of Claims 1-6 which has a repeating unit shown by following formula (9) separately from the repeating unit represented by the said Formula (1).
Ar 39 , Ar 40 , Ar 42 , and Ar 43 each independently represent an optionally substituted aromatic hydrocarbon group or aromatic heterocyclic group,
Ar 41 represents a direct bond, an aromatic hydrocarbon group or an aromatic heterocyclic group which may have a substituent,
T represents a crosslinkable group. )
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