JP2013209300A - Material for organic electroluminescence device, and its use - Google Patents
Material for organic electroluminescence device, and its use Download PDFInfo
- Publication number
- JP2013209300A JP2013209300A JP2012078541A JP2012078541A JP2013209300A JP 2013209300 A JP2013209300 A JP 2013209300A JP 2012078541 A JP2012078541 A JP 2012078541A JP 2012078541 A JP2012078541 A JP 2012078541A JP 2013209300 A JP2013209300 A JP 2013209300A
- Authority
- JP
- Japan
- Prior art keywords
- group
- substituted
- unsubstituted
- hydrocarbon group
- general formula
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 37
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 20
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 137
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims abstract description 74
- 150000001875 compounds Chemical class 0.000 claims abstract description 65
- 125000006615 aromatic heterocyclic group Chemical group 0.000 claims abstract description 64
- 125000000623 heterocyclic group Chemical group 0.000 claims abstract description 62
- 238000002347 injection Methods 0.000 claims abstract description 39
- 239000007924 injection Substances 0.000 claims abstract description 39
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 33
- 125000003277 amino group Chemical group 0.000 claims abstract description 26
- 230000005525 hole transport Effects 0.000 claims abstract description 21
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 20
- 125000005843 halogen group Chemical group 0.000 claims abstract description 19
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 18
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 18
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 107
- 238000000034 method Methods 0.000 claims description 46
- 239000012044 organic layer Substances 0.000 claims description 16
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 125000004434 sulfur atom Chemical group 0.000 claims description 12
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000000576 coating method Methods 0.000 abstract description 9
- 239000011248 coating agent Substances 0.000 abstract description 6
- 239000000243 solution Substances 0.000 abstract description 6
- 125000001424 substituent group Chemical group 0.000 abstract description 5
- 150000004982 aromatic amines Chemical class 0.000 abstract description 2
- 235000006629 Prosopis spicigera Nutrition 0.000 abstract 1
- 240000000037 Prosopis spicigera Species 0.000 abstract 1
- -1 tert-octyloxy group Chemical group 0.000 description 107
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 239000010408 film Substances 0.000 description 27
- 125000004432 carbon atom Chemical group C* 0.000 description 14
- 239000000203 mixture Substances 0.000 description 11
- 239000002904 solvent Substances 0.000 description 11
- 238000004528 spin coating Methods 0.000 description 10
- 125000003118 aryl group Chemical group 0.000 description 8
- 238000003763 carbonization Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011521 glass Substances 0.000 description 7
- 239000000758 substrate Substances 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 6
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 5
- 125000002950 monocyclic group Chemical group 0.000 description 5
- 0 CCC(C)(*)C1C*CC1 Chemical compound CCC(C)(*)C1C*CC1 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000000903 blocking effect Effects 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- NAWXUBYGYWOOIX-SFHVURJKSA-N (2s)-2-[[4-[2-(2,4-diaminoquinazolin-6-yl)ethyl]benzoyl]amino]-4-methylidenepentanedioic acid Chemical compound C1=CC2=NC(N)=NC(N)=C2C=C1CCC1=CC=C(C(=O)N[C@@H](CC(=C)C(O)=O)C(O)=O)C=C1 NAWXUBYGYWOOIX-SFHVURJKSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000004450 alkenylene group Chemical group 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 125000000304 alkynyl group Chemical group 0.000 description 3
- 125000004419 alkynylene group Chemical group 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000002993 cycloalkylene group Chemical group 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000007650 screen-printing Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 125000004665 trialkylsilyl group Chemical group 0.000 description 3
- 125000005106 triarylsilyl group Chemical group 0.000 description 3
- DPZNOMCNRMUKPS-UHFFFAOYSA-N 1,3-Dimethoxybenzene Chemical compound COC1=CC=CC(OC)=C1 DPZNOMCNRMUKPS-UHFFFAOYSA-N 0.000 description 2
- CHLICZRVGGXEOD-UHFFFAOYSA-N 1-Methoxy-4-methylbenzene Chemical compound COC1=CC=C(C)C=C1 CHLICZRVGGXEOD-UHFFFAOYSA-N 0.000 description 2
- 125000002941 2-furyl group Chemical group O1C([*])=C([H])C([H])=C1[H] 0.000 description 2
- 125000003682 3-furyl group Chemical group O1C([H])=C([*])C([H])=C1[H] 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000002723 alicyclic group Chemical group 0.000 description 2
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000005388 borosilicate glass Substances 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- XSIFPSYPOVKYCO-UHFFFAOYSA-N butyl benzoate Chemical compound CCCCOC(=O)C1=CC=CC=C1 XSIFPSYPOVKYCO-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000009500 colour coating Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- HHNHBFLGXIUXCM-GFCCVEGCSA-N cyclohexylbenzene Chemical compound [CH]1CCCC[C@@H]1C1=CC=CC=C1 HHNHBFLGXIUXCM-GFCCVEGCSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 238000010030 laminating Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 2
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- 238000001931 thermography Methods 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 238000001771 vacuum deposition Methods 0.000 description 2
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- OSIGJGFTADMDOB-UHFFFAOYSA-N 1-Methoxy-3-methylbenzene Chemical compound COC1=CC=CC(C)=C1 OSIGJGFTADMDOB-UHFFFAOYSA-N 0.000 description 1
- 125000004973 1-butenyl group Chemical group C(=CCC)* 0.000 description 1
- 125000004972 1-butynyl group Chemical group [H]C([H])([H])C([H])([H])C#C* 0.000 description 1
- BLMBNEVGYRXFNA-UHFFFAOYSA-N 1-methoxy-2,3-dimethylbenzene Chemical compound COC1=CC=CC(C)=C1C BLMBNEVGYRXFNA-UHFFFAOYSA-N 0.000 description 1
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000005978 1-naphthyloxy group Chemical group 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical group CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- 125000006017 1-propenyl group Chemical group 0.000 description 1
- 125000006411 1-propenylene group Chemical group [H]\C(*)=C(\[H])C([H])([H])[H] 0.000 description 1
- 125000000530 1-propynyl group Chemical group [H]C([H])([H])C#C* 0.000 description 1
- 125000001462 1-pyrrolyl group Chemical group [*]N1C([H])=C([H])C([H])=C1[H] 0.000 description 1
- UJCFZCTTZWHRNL-UHFFFAOYSA-N 2,4-Dimethylanisole Chemical compound COC1=CC=C(C)C=C1C UJCFZCTTZWHRNL-UHFFFAOYSA-N 0.000 description 1
- SHZXKQJLRLVYGP-UHFFFAOYSA-N 2-[7-(1,3,2-dioxaborinan-2-yl)-9,9-dihexylfluoren-2-yl]-1,3,2-dioxaborinane Chemical compound C1=C2C(CCCCCC)(CCCCCC)C3=CC(B4OCCCO4)=CC=C3C2=CC=C1B1OCCCO1 SHZXKQJLRLVYGP-UHFFFAOYSA-N 0.000 description 1
- 125000004974 2-butenyl group Chemical group C(C=CC)* 0.000 description 1
- 125000000069 2-butynyl group Chemical group [H]C([H])([H])C#CC([H])([H])* 0.000 description 1
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 1
- 125000001622 2-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C(*)C([H])=C([H])C2=C1[H] 0.000 description 1
- 125000005979 2-naphthyloxy group Chemical group 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 description 1
- 125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000389 2-pyrrolyl group Chemical group [H]N1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000000175 2-thienyl group Chemical group S1C([*])=C([H])C([H])=C1[H] 0.000 description 1
- MCZYEFODKAZWIH-UHFFFAOYSA-N 3-(chloromethyl)-3-methyloxetane Chemical compound ClCC1(C)COC1 MCZYEFODKAZWIH-UHFFFAOYSA-N 0.000 description 1
- 125000004975 3-butenyl group Chemical group C(CC=C)* 0.000 description 1
- 125000000474 3-butynyl group Chemical group [H]C#CC([H])([H])C([H])([H])* 0.000 description 1
- 125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001397 3-pyrrolyl group Chemical group [H]N1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- 125000001541 3-thienyl group Chemical group S1C([H])=C([*])C([H])=C1[H] 0.000 description 1
- GZFGOTFRPZRKDS-UHFFFAOYSA-N 4-bromophenol Chemical compound OC1=CC=C(Br)C=C1 GZFGOTFRPZRKDS-UHFFFAOYSA-N 0.000 description 1
- 125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N Benzoic acid Natural products OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- MRABAEUHTLLEML-UHFFFAOYSA-N Butyl lactate Chemical compound CCCCOC(=O)C(C)O MRABAEUHTLLEML-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 235000002597 Solanum melongena Nutrition 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- IPBVNPXQWQGGJP-UHFFFAOYSA-N acetic acid phenyl ester Natural products CC(=O)OC1=CC=CC=C1 IPBVNPXQWQGGJP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000005354 aluminosilicate glass Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000002078 anthracen-1-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([*])=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 125000000748 anthracen-2-yl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C([H])=C([*])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 150000008378 aryl ethers Chemical class 0.000 description 1
- 125000005104 aryl silyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- UDEWPOVQBGFNGE-UHFFFAOYSA-N benzoic acid n-propyl ester Natural products CCCOC(=O)C1=CC=CC=C1 UDEWPOVQBGFNGE-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004976 cyclobutylene group Chemical group 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000004977 cycloheptylene group Chemical group 0.000 description 1
- 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 1
- 125000004956 cyclohexylene group Chemical group 0.000 description 1
- FHADSMKORVFYOS-UHFFFAOYSA-N cyclooctanol Chemical compound OC1CCCCCCC1 FHADSMKORVFYOS-UHFFFAOYSA-N 0.000 description 1
- IIRFCWANHMSDCG-UHFFFAOYSA-N cyclooctanone Chemical compound O=C1CCCCCCC1 IIRFCWANHMSDCG-UHFFFAOYSA-N 0.000 description 1
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 125000004978 cyclooctylene group Chemical group 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000004979 cyclopentylene group Chemical group 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 125000004980 cyclopropylene group Chemical group 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000007607 die coating method Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 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 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005677 ethinylene group Chemical group [*:2]C#C[*:1] 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 229940116333 ethyl lactate Drugs 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000007646 gravure printing Methods 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000593 indol-1-yl group Chemical group [H]C1=C([H])C([H])=C2N([*])C([H])=C([H])C2=C1[H] 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000555 isopropenyl group Chemical group [H]\C([H])=C(\*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005355 lead glass Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 1
- 239000003550 marker Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- 229940095102 methyl benzoate Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- OLXYLDUSSBULGU-UHFFFAOYSA-N methyl pyridine-4-carboxylate Chemical compound COC(=O)C1=CC=NC=C1 OLXYLDUSSBULGU-UHFFFAOYSA-N 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 125000004312 morpholin-2-yl group Chemical group [H]N1C([H])([H])C([H])([H])OC([H])(*)C1([H])[H] 0.000 description 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 description 1
- 229940017144 n-butyl lactate Drugs 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- WSGCRAOTEDLMFQ-UHFFFAOYSA-N nonan-5-one Chemical compound CCCCC(=O)CCCC WSGCRAOTEDLMFQ-UHFFFAOYSA-N 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 description 1
- 125000005064 octadecenyl group Chemical group C(=CCCCCCCCCCCCCCCCC)* 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000005447 octyloxy 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])O* 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- 125000002958 pentadecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004817 pentamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 1
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 description 1
- 229940049953 phenylacetate Drugs 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical compound OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 125000000587 piperidin-1-yl group Chemical group [H]C1([H])N(*)C([H])([H])C([H])([H])C([H])([H])C1([H])[H] 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 125000002572 propoxy group Chemical group [*]OC([H])([H])C(C([H])([H])[H])([H])[H] 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000005361 soda-lime glass Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 125000001425 triazolyl group Chemical group 0.000 description 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 description 1
- 125000000025 triisopropylsilyl group Chemical group C(C)(C)[Si](C(C)C)(C(C)C)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
Images
Landscapes
- Electroluminescent Light Sources (AREA)
- Epoxy Compounds (AREA)
- Plural Heterocyclic Compounds (AREA)
- Polyethers (AREA)
Abstract
Description
本発明は新規な有機エレクトロルミネッセンス素子用材料に関する。さらに詳しくは、有機エレクトロルミネッセンス素子(以下有機EL素子と略記)に用いた場合、塗布による製膜が可能である正孔輸送層、および正孔注入層用材料として有用なアリールアミンポリマーを含有する有機エレクトロルミネッセンス素子用材料に関する。 The present invention relates to a novel material for an organic electroluminescence device. More specifically, when it is used for an organic electroluminescence device (hereinafter abbreviated as an organic EL device), it contains an arylamine polymer that is useful as a material for a hole transport layer and a hole injection layer that can be formed by coating. The present invention relates to a material for an organic electroluminescence element.
近年、有機EL素子においては、素子の長寿命化が求められている。素子の寿命に影響を及ぼす原因は様々な因子が考えられるが、その一つとして、素子を構成する材料のガラス転移温度(Tg)が、素子の寿命に大きな影響を及ぼすものと考えられている。すなわち、素子の使用環境や駆動時の発熱などにより、素子の温度が構成する材料のTgを上回ると、構成する材料の結晶化が起こり、ダークスポットと呼ばれる非発光領域が発生することが指摘されている。そのため、より高いTgを示す材料が求められてきた(非特許文献1、2)。
In recent years, organic EL elements have been required to have a long lifetime. There are various factors that can affect the lifetime of the device. One of the factors is considered to be that the glass transition temperature (Tg) of the material constituting the device has a significant effect on the lifetime of the device. . That is, it is pointed out that when the temperature of the element exceeds the Tg of the constituent material due to the use environment of the element or the heat generated during driving, the constituent material is crystallized and a non-light emitting region called a dark spot is generated. ing. For this reason, materials having higher Tg have been demanded (Non-Patent
また、有機EL素子の成膜方法も、高真空中での蒸着法の他、湿式成膜法も多く検討されてきた。特に、湿式成膜法は、太面積化が容易であり、将来有望と考えられているが、正孔注入層にPEDOT/PSSを用い、その上に発光層が直接接すると、有機EL素子の寿命が著しく短くなるという問題点があった。また、有機層を塗布で成膜する場合、水系溶媒での塗布と、有機溶媒系での塗布は積層可能であるが同一溶媒系での積層は困難である。よって、PEDOT/PSSと発光層の間に正孔輸送層を塗布法で成膜することは、困難であった。 In addition to the deposition method in a high vacuum, many wet deposition methods have been studied as a method for forming an organic EL element. In particular, the wet film formation method is easy to increase in area and is considered promising in the future. However, when PEDOT / PSS is used for the hole injection layer and the light emitting layer is in direct contact therewith, the organic EL element There was a problem that the lifetime was significantly shortened. In addition, when an organic layer is formed by coating, coating with an aqueous solvent and coating with an organic solvent system can be stacked, but stacking with the same solvent system is difficult. Therefore, it has been difficult to form a hole transport layer between the PEDOT / PSS and the light emitting layer by a coating method.
また、塗布型の正孔輸送材料として、アミン含有ポリマー材料が開発されてきた。しかしながら、発光層と同一溶媒で塗布するとことが困難であるという欠点があった。(特許文献1〜5、非特許文献3)。
Also, amine-containing polymer materials have been developed as coating-type hole transport materials. However, there is a drawback that it is difficult to apply with the same solvent as the light emitting layer. (
本発明の課題は、有機EL素子用材料に有用な化合物を提供すること、特に正孔注入層もしくは正孔輸送層用材料として好適に用いることができる化合物を提供することにある。さらには、この有機エレクトロルミネッセンス素子用材料を用いることにより、高い発光効率、低電圧駆動、色純度、長寿命、耐熱性などの優れた特性を示す有機EL素子を提供することである。 An object of the present invention is to provide a compound useful for an organic EL device material, and particularly to provide a compound that can be suitably used as a material for a hole injection layer or a hole transport layer. Furthermore, it is to provide an organic EL element exhibiting excellent characteristics such as high luminous efficiency, low voltage driving, color purity, long life, heat resistance, and the like by using the material for organic electroluminescence element.
本発明者らは、前記諸問題を解決するために、鋭意研究を重ねた結果、本発明に至った。 As a result of intensive studies to solve the above problems, the present inventors have arrived at the present invention.
すなわち本発明は、下記一般式[1]で表される重合性化合物に関する。 That is, the present invention relates to a polymerizable compound represented by the following general formula [1].
一般式[1]
(一般式[1]中、R1およびR2は、それぞれ独立に、水素原子、シアノ基、ニトロ基、ハロゲン原子、ヒドロキシル基、アルコキシル基、アリ−ルオキシ基、カルボキシル基、置換または未置換のアミノ基、置換または未置換のシリル基、置換または未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、R1およびR2は、隣接した基が互いに結合して環を形成しても良い。
R3およびR4は、それぞれ独立に、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表す。
J1およびJ2は、それぞれ独立に、下記一般式[2]、または、一般式[3]で表される基である。)
(In the general formula [1], R 1 and R 2 are each independently a hydrogen atom, cyano group, nitro group, halogen atom, hydroxyl group, alkoxyl group, aryloxy group, carboxyl group, substituted or unsubstituted group. Amino group, substituted or unsubstituted silyl group, substituted or unsubstituted monovalent aliphatic hydrocarbon group, substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic complex It represents a cyclic group or a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 1 and R 2 may be bonded to each other to form a ring.
R 3 and R 4 each independently represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic complex, A cyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group is represented.
J 1 and J 2 are each independently a group represented by the following general formula [2] or general formula [3]. )
一般式[2]
(一般式[2]中、R5は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、
R6は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、
X1は、直接結合、酸素原子、または、硫黄原子を表す。)
(In the general formula [2], R 5 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group,
R 6 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X 1 represents a direct bond, an oxygen atom, or a sulfur atom. )
一般式[3]
(一般式[3]中、R7は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、
R8は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、
X2は、直接結合、酸素原子、または、硫黄原子を表す。)
(In the general formula [3], R 7 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group,
R 8 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X 2 represents a direct bond, an oxygen atom, or a sulfur atom. )
また、本発明は、上記重合性化合物を重合してなる高分子化合物に関する。 The present invention also relates to a polymer compound obtained by polymerizing the polymerizable compound.
また、本発明は、上記重合性化合物、または、上記高分子化合物を含有する、有機エレクトロルミネッセンス素子用材料に関する。 Moreover, this invention relates to the material for organic electroluminescent elements containing the said polymeric compound or the said high molecular compound.
また、本発明は、一対の電極間に複数層の有機層を形成してなる有機エレクトロルミネッセンス素子において、前記有機層の少なくとも一層が、上記有機エレクトロルミネッセンス素子用材料を含んでなる有機エレクトロルミネッセンス素子に関する。 In addition, the present invention provides an organic electroluminescence device comprising a plurality of organic layers formed between a pair of electrodes, wherein at least one of the organic layers comprises the material for an organic electroluminescence device. About.
また、本発明は、一対の電極間に正孔注入層、正孔輸送層を含む複数層の有機層を形成してなる有機エレクトロルミネッセンス素子において、前記有機層の少なくとも一層が、上記有機エレクトロルミネッセンス素子用材料を含んでなる有機エレクトロルミネッセンス素子に関する。 Further, the present invention provides an organic electroluminescence device comprising a plurality of organic layers including a hole injection layer and a hole transport layer between a pair of electrodes, wherein at least one of the organic layers is the above organic electroluminescence. The present invention relates to an organic electroluminescence element comprising an element material.
また、本発明は、正孔注入層、および、正孔輸送層が湿式成膜法により形成されてなる層である上記有機エレクトロルミネッセンス素子に関する。 Moreover, this invention relates to the said organic electroluminescent element which is a layer in which a positive hole injection layer and a positive hole transport layer are formed by the wet film-forming method.
本発明の有機EL素子用材料を用いた有機EL素子は、低い電圧で駆動し、かつ、長寿命であるため、壁掛けテレビ等のフラットパネルディスプレイや平面発光体として好適に使用することができ、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等への応用が可能である。 Since the organic EL element using the organic EL element material of the present invention is driven at a low voltage and has a long life, it can be suitably used as a flat panel display such as a wall-mounted TV or a flat light emitter, It can be applied to light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display panels, and indicator lights.
以下、詳細にわたって本発明を説明する。 Hereinafter, the present invention will be described in detail.
一般式[1]におけるR1およびR2は、それぞれ独立に、水素原子、シアノ基、ニトロ基、ハロゲン原子、ヒドロキシル基、アルコキシル基、アリ−ルオキシ基、カルボキシル基、置換または未置換のアミノ基、置換または未置換のシリル基、置換または未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、R1およびR2は、隣接した基が互いに結合して環を形成しても良い。 R 1 and R 2 in the general formula [1] are each independently a hydrogen atom, cyano group, nitro group, halogen atom, hydroxyl group, alkoxyl group, aryloxy group, carboxyl group, substituted or unsubstituted amino group Substituted or unsubstituted silyl group, substituted or unsubstituted monovalent aliphatic hydrocarbon group, substituted or unsubstituted monovalent aromatic hydrocarbon group, substituted or unsubstituted monovalent aliphatic heterocyclic group Or a substituted or unsubstituted monovalent aromatic heterocyclic group, and R 1 and R 2 may be bonded to each other to form a ring.
ここで、ハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。 Here, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.
また、アルコキシル基としては、メトキシ基、エトキシ基、プロポキシ基、ブトキシ基、tert−ブトキシ基、オクチルオキシ基、tert−オクチルオキシ基といった炭素数1〜8のアルコキシル基が挙げられる。 Moreover, as an alkoxyl group, C1-C8 alkoxyl groups, such as a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a tert-butoxy group, an octyloxy group, a tert-octyloxy group, are mentioned.
また、アリールオキシ基としては、フェノキシ基、4−tert−ブチルフェノキシ基、1−ナフチルオキシ基、2−ナフチルオキシ基、9−アンスリルオキシ基といった炭素数6〜14のアリ−ルオキシ基が挙げられる。 Examples of the aryloxy group include aryloxy groups having 6 to 14 carbon atoms such as phenoxy group, 4-tert-butylphenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, and 9-anthryloxy group. It is done.
また、置換または未置換のアミノ基としては、未置換のアミノ基、N−メチルアミノ基、N−エチルアミノ基、N,N−ジエチルアミノ基、N,N−ジイソプロピルアミノ基、N,N−ジブチルアミノ基、N−ベンジルアミノ基、N,N−ジベンジルアミノ基、N−フェニルアミノ基、N−フェニル−N−メチルアミノ基、N,N−ジフェニルアミノ基、N,N−ビス(m−トリル)アミノ基、N,N−ビス(p−トリル)アミノ基、N,N−ビス(p−ビフェニリル)アミノ基、ビス[4−(4−メチル)ビフェニリル]アミノ基、N−α−ナフチル−N−フェニルアミノ基、N−β−ナフチル−N−フェニルアミノ基等の置換または未置換のアミノ基が挙げられる。 Examples of the substituted or unsubstituted amino group include unsubstituted amino group, N-methylamino group, N-ethylamino group, N, N-diethylamino group, N, N-diisopropylamino group, N, N-dibutyl. Amino group, N-benzylamino group, N, N-dibenzylamino group, N-phenylamino group, N-phenyl-N-methylamino group, N, N-diphenylamino group, N, N-bis (m- Tolyl) amino group, N, N-bis (p-tolyl) amino group, N, N-bis (p-biphenylyl) amino group, bis [4- (4-methyl) biphenylyl] amino group, N-α-naphthyl Examples thereof include substituted or unsubstituted amino groups such as -N-phenylamino group and N-β-naphthyl-N-phenylamino group.
また、置換または未置換のシリル基としては、未置換のシリル基、置換もしくは未置換のアルキル基、または、置換もしくは未置換のアリール基によって置換されたシリル基であり、モノアルキルシリル基、モノアリールシリル基、ジアルキルシリル基、ジアリールシリル基、トリアルキルシリル基、トリアリールシリル基等といった置換または未置換のシリル基が挙げられる。 The substituted or unsubstituted silyl group is an unsubstituted silyl group, a substituted or unsubstituted alkyl group, or a silyl group substituted by a substituted or unsubstituted aryl group. Examples thereof include substituted or unsubstituted silyl groups such as arylsilyl group, dialkylsilyl group, diarylsilyl group, trialkylsilyl group, and triarylsilyl group.
ここで、モノアルキルシリル基としては、モノメチルシリル基、モノエチルシリル基、モノブチルシリル基、モノイソプロピルシリル基、モノデカンシリル、モノイコサンシリル基、モノトリアコンタンシリル基等のモノアルキルシリル基が挙げられる。 Here, as the monoalkylsilyl group, a monoalkylsilyl group such as a monomethylsilyl group, a monoethylsilyl group, a monobutylsilyl group, a monoisopropylsilyl group, a monodecanesilyl, a monoicosanesilyl group, or a monotriacontanesilyl group Is mentioned.
さらに、モノアリールシリル基としては、モノフェニルシリル基、モノトリルシリル基、モノナフチルシリル基、モノアンスリルシリル基等のモノアリールシリルが挙げられる。 Furthermore, examples of the monoarylsilyl group include monoarylsilyl such as a monophenylsilyl group, a monotolylsilyl group, a mononaphthylsilyl group, and a monoanthrylsilyl group.
さらに、ジアルキルシリル基としては、ジメチルシリル基、ジエチルシリル基、ジメチルエチルシリル基、ジイソプロピルシリル基、ジブチルシリル基、ジオクチルシリル基、ジデカンシリル基等のジアルキルシリル基が挙げられる。 Furthermore, examples of the dialkylsilyl group include dialkylsilyl groups such as dimethylsilyl group, diethylsilyl group, dimethylethylsilyl group, diisopropylsilyl group, dibutylsilyl group, dioctylsilyl group, and didecanesilyl group.
さらに、ジアリールシリル基としては、ジフェニルシリル基、ジトリルシリル基等のジアリールシリルが挙げられる。 Further, examples of the diarylsilyl group include diarylsilyl such as diphenylsilyl group and ditolylsilyl group.
さらに、トリアルキルシリル基としては、トリメチルシリル基、トリエチルシリル基、ジメチルエチルシリル基、トリイソプロピルシリル基、トリブチルシリル基、トリオクチルシリル基等のトリアルキルシリル基が挙げられる。 Furthermore, examples of the trialkylsilyl group include trialkylsilyl groups such as trimethylsilyl group, triethylsilyl group, dimethylethylsilyl group, triisopropylsilyl group, tributylsilyl group, and trioctylsilyl group.
さらに、トリアリールシリル基としては、トリフェニルシリル基、トリトリルシリル基等のトリアリールシリル基が挙げられる。 Furthermore, examples of the triarylsilyl group include triarylsilyl groups such as a triphenylsilyl group and a tolylsilylsilyl group.
また、1価の脂肪族炭化水素基としては、炭素数1〜18の1価の脂肪族炭化水素基を指し、そのようなものとしては、アルキル基、アルケニル基、アルキニル基、シクロアルキル基が挙げられる。 In addition, the monovalent aliphatic hydrocarbon group refers to a monovalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, and examples thereof include an alkyl group, an alkenyl group, an alkynyl group, and a cycloalkyl group. Can be mentioned.
ここで、アルキル基としては、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、イソブチル基、sec−ブチル基、tert−ブチル基、ペンチル基、イソペンチル基、ヘキシル基、ヘプチル基、オクチル基、デシル基、ドデシル基、ペンタデシル基、オクタデシル基といった炭素数1〜18のアルキル基が挙げられる。 Here, as the alkyl group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group , An alkyl group having 1 to 18 carbon atoms such as a decyl group, a dodecyl group, a pentadecyl group, and an octadecyl group.
さらに、アルケニル基としては、ビニル基、1−プロペニル基、2−プロペニル基、イソプロペニル基、1−ブテニル基、2−ブテニル基、3−ブテニル基、1−オクテニル基、1−デセニル基、1−オクタデセニル基といった炭素数2〜18のアルケニル基が挙げられる。 Furthermore, examples of the alkenyl group include a vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-octenyl group, 1-decenyl group, 1 -C2-C18 alkenyl groups, such as an octadecenyl group, are mentioned.
さらに、アルキニル基としては、エチニル基、1−プロピニル基、2−プロピニル基、1−ブチニル基、2−ブチニル基、3−ブチニル基、1−オクチニル基、1−デシニル基、1−オクタデシニル基といった炭素数2〜18のアルキニル基が挙げられる。 Further, as the alkynyl group, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1-octynyl group, 1-decynyl group, 1-octadecynyl group, etc. Examples include alkynyl groups having 2 to 18 carbon atoms.
さらに、シクロアルキル基としては、シクロプロピル基、シクロブチル基、シクロペンチル基、シクロヘキシル基、シクロヘプチル基、シクロオクチル基、シクロオクタデシル基、2−インデノ基といった炭素数3〜18のシクロアルキル基が挙げられる。 Further, examples of the cycloalkyl group include cycloalkyl groups having 3 to 18 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclooctadecyl group, and 2-indeno group. .
また、1価の芳香族炭化水素基としては、1価の単環、縮合環、環集合芳香族炭化水素基が挙げられる。 Moreover, as a monovalent | monohydric aromatic hydrocarbon group, a monovalent | monohydric monocycle, a condensed ring, and a ring assembly aromatic hydrocarbon group are mentioned.
ここで、1価の単環芳香族炭化水素基としては、フェニル基、o−トリル基、m−トリル基、p−トリル基、2,4−キシリル基、p−クメニル基、メシチル基等の炭素数6〜18の1価の単環芳香族炭化水素基が挙げられる。 Here, examples of the monovalent monocyclic aromatic hydrocarbon group include a phenyl group, an o-tolyl group, an m-tolyl group, a p-tolyl group, a 2,4-xylyl group, a p-cumenyl group, and a mesityl group. Examples thereof include monovalent monocyclic aromatic hydrocarbon groups having 6 to 18 carbon atoms.
さらに、1価の縮合環芳香族炭化水素基としては、1−ナフチル基、2−ナフチル基、1−アンスリル基、2−アンスリル基、5−アンスリル基、1−フェナンスリル基、9−フェナンスリル基、1−アセナフチル基、2−アズレニル基、1−ピレニル基、2−トリフェニレル基等の炭素数10〜18の1価の縮合環芳香族炭化水素基が挙げられる。 Furthermore, as the monovalent condensed ring aromatic hydrocarbon group, 1-naphthyl group, 2-naphthyl group, 1-anthryl group, 2-anthryl group, 5-anthryl group, 1-phenanthryl group, 9-phenanthryl group, C1-C18 monovalent | monohydric condensed ring aromatic hydrocarbon groups, such as 1-acenaphthyl group, 2-azurenyl group, 1-pyrenyl group, 2-triphenylyl group, are mentioned.
さらに、1価の環集合芳香族炭化水素基としては、o−ビフェニリル基、m−ビフェニリル基、p−ビフェニリル基等の炭素数12〜18の1価の環集合芳香族炭化水素基が挙げられる。 Furthermore, examples of the monovalent ring-assembled aromatic hydrocarbon group include C1-C18 monovalent ring-assembled aromatic hydrocarbon groups such as o-biphenylyl group, m-biphenylyl group, and p-biphenylyl group. .
また、1価の脂肪族複素環基としては、2−ピラゾリノ基、ピペリジノ基、モルホリノ基、2−モルホリニル基といった炭素数3〜18の1価の脂肪族複素環基が挙げられる。 Examples of the monovalent aliphatic heterocyclic group include monovalent aliphatic heterocyclic groups having 3 to 18 carbon atoms such as a 2-pyrazolino group, a piperidino group, a morpholino group, and a 2-morpholinyl group.
また、1価の芳香族複素環基としては、トリアゾリル基、3−オキサジアゾリル基、2−フラニル基、3−フラニル基、2−フリル基、3−フリル基、2−チエニル基、3−チエニル基、1−ピロ−リル基、2−ピロ−リル基、3−ピロ−リル基、2−ピリジル基、3−ピリジル基、4−ピリジル基、2−ピラジル基、2−オキサゾリル基、3−イソオキサゾリル基、2−チアゾリル基、3−イソチアゾリル基、2−イミダゾリル基、3−ピラゾリル基、2−キノリル基、3−キノリル基、4−キノリル基、5−キノリル基、6−キノリル基、7−キノリル基、8−キノリル基、1−イソキノリル基、2−キノキサリニル基、2−ベンゾフリル基、2−ベンゾチエニル基、N−インドリル基、N−カルバゾリル基、N−アクリジニル基、2−チオフェニル基、3−チオフェニル基、ビピリジル基、フェナントロリル基といった炭素数2〜18の1価の芳香族複素環基が挙げられる。 Examples of the monovalent aromatic heterocyclic group include triazolyl group, 3-oxadiazolyl group, 2-furanyl group, 3-furanyl group, 2-furyl group, 3-furyl group, 2-thienyl group and 3-thienyl group. 1-pyrrolyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrazyl group, 2-oxazolyl group, 3-isoxazolyl Group, 2-thiazolyl group, 3-isothiazolyl group, 2-imidazolyl group, 3-pyrazolyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, 7-quinolyl group Group, 8-quinolyl group, 1-isoquinolyl group, 2-quinoxalinyl group, 2-benzofuryl group, 2-benzothienyl group, N-indolyl group, N-carbazolyl group, N-acridinyl group, 2- Ofeniru group, 3-thiophenyl group, bipyridyl group, and monovalent aromatic heterocyclic group having 2 to 18 carbon atoms such phenanthrolyl group.
一般式[1]におけるR3およびR4は、それぞれ独立に、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表す。 R 3 and R 4 in the general formula [1] are each independently a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted group. A divalent aliphatic heterocyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group is represented.
ここで、2価の脂肪族炭化水素基としては、炭素数1〜18の2価の脂肪族炭化水素基を指し、そのようなものとしては、アルキレン基、アルケニレン基、アルキニレン基、シクロアルキレン基が挙げられる。 Here, the divalent aliphatic hydrocarbon group refers to a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms, such as an alkylene group, an alkenylene group, an alkynylene group, a cycloalkylene group. Is mentioned.
ここで、アルキレン基としては、メチレン基、エチレン基、プロピレン基、イソプロピレン基、ブチレン基、イソブチレン基、sec−ブチレン基、tert−ブチレン基、ペンチレン基、イソペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、デシレン基、ドデシレン基、ペンタデシレン基、オクタデシレン基といった炭素数1〜18のアルキレン基が挙げられる。 Here, as the alkylene group, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, sec-butylene group, tert-butylene group, pentylene group, isopentylene group, hexylene group, heptylene group, octylene. And an alkylene group having 1 to 18 carbon atoms such as a group, a decylene group, a dodecylene group, a pentadecylene group, and an octadecylene group.
さらに、アルケニレン基としては、エチレニレン基、1−プロペニレン基、2−プロペニレン基、イソプロペニレン基、1−ブテニレン基、2−ブテニレン基、3−ブテニレン基、1−オクテニレン基、1−デセニレン基、1−オクタデセニレン基といった炭素数2〜18のアルケニレン基が挙げられる。 Furthermore, as an alkenylene group, an ethylenylene group, 1-propenylene group, 2-propenylene group, isopropenylene group, 1-butenylene group, 2-butenylene group, 3-butenylene group, 1-octenylene group, 1-decenylene group, C2-C18 alkenylene groups, such as 1-octadecenylene group, are mentioned.
さらに、アルキニレン基としては、エチニレン基、1−プロピニレン基、2−プロピニレン基、1−ブチニレン基、2−ブチニレン基、3−ブチニレン基、1−オクチニレン基、1−デシニレン基、1−オクタデシニレン基といった炭素数2〜18のアルキニレン基が挙げられる。 Further, examples of the alkynylene group include an ethynylene group, a 1-propynylene group, a 2-propynylene group, a 1-butynylene group, a 2-butynylene group, a 3-butynylene group, a 1-octynylene group, a 1-decynylene group, and a 1-octadecynylene group. Examples thereof include alkynylene groups having 2 to 18 carbon atoms.
さらに、シクロアルキレン基としては、シクロプロピレン基、シクロブチレン基、シクロペンチレン基、シクロヘキシレン基、シクロヘプチレン基、シクロオクチレン基、シクロオクタデシレン基、2−インデニレン基といった炭素数3〜18のシクロアルキレン基が挙げられる。 Furthermore, as a cycloalkylene group, a C3-C18 such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a cyclooctadecylene group, and a 2-indenylene group. A cycloalkylene group is mentioned.
また、2価の芳香族炭化水素基としては、2価の単環、縮合環、環集合芳香族炭化水素基が挙げられる。 Examples of the divalent aromatic hydrocarbon group include a divalent monocyclic ring, a condensed ring, and a ring assembly aromatic hydrocarbon group.
ここで、2価の単環芳香族炭化水素基としては、フェニレニル基、o−トリレニル基、m−トリレニル基、p−トリレニル基、2,4−キシリレニル基、p−クメニレニル基、メシチレニル基等の炭素数6〜18の2価の単環芳香族炭化水素基が挙げられる。 Here, examples of the divalent monocyclic aromatic hydrocarbon group include a phenylenyl group, an o-tolylenyl group, an m-tolylenyl group, a p-tolylenyl group, a 2,4-xylylenyl group, a p-cumenylenyl group, and a mesityrenyl group. Examples thereof include a bivalent monocyclic aromatic hydrocarbon group having 6 to 18 carbon atoms.
さらに、2価の縮合環芳香族炭化水素基としては、1−ナフチレニル基、2−ナフチレニル基、1−アンスリレニル基、2−アンスリレニル基、5−アンスリレニル基、1−フェナンスレニル基、9−フェナンスレニル基、1−アセナフチレニル基、2−アズレニレニル基、1−ピレニレニル基、2−トリフェニレニル基等の炭素数10〜18の2価の縮合環芳香族炭化水素基が挙げられる。 Furthermore, as the divalent condensed ring aromatic hydrocarbon group, 1-naphthylenyl group, 2-naphthylenyl group, 1-anthrylenyl group, 2-anthrylenyl group, 5-anthrylenyl group, 1-phenanthrenyl group, 9-phenanthrenyl group, Examples thereof include C10-18 divalent condensed ring aromatic hydrocarbon groups such as 1-acenaphthylenyl group, 2-azurenylenyl group, 1-pyrenylenyl group, 2-triphenylenyl group and the like.
さらに、2価の環集合芳香族炭化水素基としては、o−ビフェニレニル基、m−ビフェニレニル基、p−ビフェニレニル基等の炭素数12〜18の2価の環集合芳香族炭化水素基が挙げられる。 Furthermore, examples of the divalent ring-assembled aromatic hydrocarbon group include divalent ring-assembled aromatic hydrocarbon groups having 12 to 18 carbon atoms such as o-biphenylenyl group, m-biphenylenyl group, and p-biphenylenyl group. .
また、2価の脂肪族複素環基としては、2−ピラゾリニレン基、ピペリジニレン基、モルホリニレン基、2−モルホリニレン基といった炭素数3〜18の2価の脂肪族複素環基が挙げられる。 Moreover, as a bivalent aliphatic heterocyclic group, C3-C18 bivalent aliphatic heterocyclic groups, such as 2-pyrazolinylene group, piperidinylene group, morpholinylene group, 2-morpholinylene group, are mentioned.
また、2価の芳香族複素環基としては、トリアゾレニル基、3−オキサジアゾレニル基、2−フラニレニル基、3−フラニレニル基、2−フリレニル基、3−フリレニル基、2−チエニレニル基、3−チエニレニル基、1−ピロ−リレニル基、2−ピロ−リレニル基、3−ピロ−リレニル基、2−ピリジレニル基、3−ピリジレニル基、4−ピリジレニル基、2−ピラジレニル基、2−オキサゾリレニル基、3−イソオキサゾリレニル基、2−チアゾリレニル基、3−イソチアゾリレニル基、2−イミダゾリレニル基、3−ピラゾリレニル基、2−キノリレニル基、3−キノリレニル基、4−キノリレニル基、5−キノリレニル基、6−キノリレニル基、7−キノリレニル基、8−キノリレニル基、1−イソキノリレニル基、2−キノキサリニレニル基、2−ベンゾフリレニル基、2−ベンゾチエニレニル基、N−インドリレニル基、N−カルバゾリレニル基、N−アクリジニレニル基、2−チオフェニレニル基、3−チオフェニレニル基、ビピリジレニル基、フェナントロリレニル基といった炭素数2〜18の2価の芳香族複素環基が挙げられる。 Examples of the divalent aromatic heterocyclic group include a triazorenyl group, 3-oxadiazorenyl group, 2-furanylenyl group, 3-furanylenyl group, 2-furylenyl group, 3-furylenyl group, 2-thienylenyl group, 3 -Thienylenyl group, 1-pyro-rylenyl group, 2-pyrrole-relenyl group, 3-pyrrole-ylenyl group, 2-pyridylenyl group, 3-pyridylenyl group, 4-pyridylenyl group, 2-pyrazylenyl group, 2-oxazolylenyl group, 3-isoxazolylenyl group, 2-thiazolylenyl group, 3-isothiazolylenyl group, 2-imidazolylenyl group, 3-pyrazolylenyl group, 2-quinolylenyl group, 3-quinolylenyl group, 4-quinolylenyl group, 5-quinolylenyl group Group, 6-quinolylenyl group, 7-quinolylenyl group, 8-quinolylenyl group, 1-isoquinolylenyl group, 2-quinoxalyl Renyl group, 2-benzofurenyl group, 2-benzothienylenyl group, N-indolinylenyl group, N-carbazolylenyl group, N-acridinylenyl group, 2-thiophenylenyl group, 3-thiophenylenyl group, bipyridylenyl group, phenanthrylylenyl group And a divalent aromatic heterocyclic group having 2 to 18 carbon atoms.
一般式[2]中、R5は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R6は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、X1は、直接結合、酸素原子、または、硫黄原子を表す。 In general formula [2], R 5 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic complex. Represents a cyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 6 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent Represents an aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and X 1 represents a direct bond, an oxygen atom, or Represents a sulfur atom.
一般式[3]中、R7は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R8は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、X2は、直接結合、酸素原子、または、硫黄原子を表す。 In the general formula [3], R 7 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic complex. Represents a cyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 8 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent Represents an aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, and X 2 represents a direct bond, an oxygen atom, or Represents a sulfur atom.
ここで、一般式[2]および[3]における、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、および、置換もしくは未置換の1価の芳香族複素環基、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基は前述のものが挙げられる。 Here, in the general formulas [2] and [3], a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent An aliphatic heterocyclic group, and a substituted or unsubstituted monovalent aromatic heterocyclic group, a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, Examples of the substituted or unsubstituted divalent aliphatic heterocyclic group or the substituted or unsubstituted divalent aromatic heterocyclic group include those described above.
ここで、1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、2価の脂肪族複素環基、および、2価の芳香族複素環基は置換されていても良い。その場合の置換基としては、前述の1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、2価の脂肪族複素環基、2価の芳香族複素環基シアノ基、ニトロ基、ハロゲン原子、ヒドロキシル基、アルコキシル基、アリ−ルオキシ基、カルボキシル基、シリル基、アミノ基が挙げられる。 Here, monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, divalent aliphatic hydrocarbon group, divalent The aromatic hydrocarbon group, divalent aliphatic heterocyclic group and divalent aromatic heterocyclic group may be substituted. In this case, the substituent is the monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, divalent aliphatic group described above. Aromatic hydrocarbon group, divalent aromatic hydrocarbon group, divalent aliphatic heterocyclic group, divalent aromatic heterocyclic group cyano group, nitro group, halogen atom, hydroxyl group, alkoxyl group, aryloxy group , Carboxyl group, silyl group, and amino group.
本発明で用いられる一般式[1]で表される化合物の代表例を、以下の表1に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the compound represented by the general formula [1] used in the present invention are shown in the following Table 1, but the present invention is not limited to these representative examples.
本発明の重合性化合物は、他の重合性化合物と組み合わせて用いても良い。その例としては、下記一般式[4]〜[6]で表される重合性化合物、下記一般式[12]〜[13]で表される重合性化合物、または、下記一般式[19]で表される重合性化合物などが挙げられるが、組み合わせて用いることのできる重合性化合物はこれに限定されるものではない。 The polymerizable compound of the present invention may be used in combination with other polymerizable compounds. Examples thereof include a polymerizable compound represented by the following general formulas [4] to [6], a polymerizable compound represented by the following general formulas [12] to [13], or the following general formula [19]. Although the polymerizable compound etc. which are represented are mentioned, The polymeric compound which can be used in combination is not limited to this.
一般式[4]
一般式[5]
一般式[6]
(一般式[4]、一般式[5]、および、一般式[6]中、
Aは、下記一般式[7]を、
Bは、下記一般式[8]を、
EおよびFはそれぞれ独立に、水素原子、ハロゲン原子、または、下記一般式[11]を、l、m、および、nは、それぞれ独立に、1以上の整数を表す。)
(In General Formula [4], General Formula [5], and General Formula [6],
A represents the following general formula [7]:
B represents the following general formula [8]:
E and F each independently represent a hydrogen atom, a halogen atom, or the following general formula [11], and l, m, and n each independently represent an integer of 1 or more. )
一般式[7]
(一般式[7]中、R9およびR10は、それぞれ独立に、水素原子、置換または未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基を表す。) (In General Formula [7], R 9 and R 10 are each independently a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, Represents a substituted or unsubstituted monovalent aliphatic heterocyclic group or a substituted or unsubstituted monovalent aromatic heterocyclic group.)
一般式[8]
(一般式[8]中、R11〜R28は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、R11〜R28は、隣接した基が互いに結合して環を形成しても良い。ただし、R11〜R28のうち少なくとも1つは、下記一般式[9]、または一般式[10]で表される基である。) (In the general formula [8], R 11 to R 28 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group represents a group, R 11 to R 28 may combine adjacent groups together may form a ring. However, at least one of R 11 to R 28 is represented by the following general formula [9] or general, It is a group represented by the formula [10].)
一般式[9]
(一般式[9]中、R29は、直接結合、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R30は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R31は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、X3は、直接結合、酸素原子、または、硫黄原子を表す。) (In the general formula [9], R 29 is a direct bond, a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent group. Represents an aliphatic heterocyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 30 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent group. Represents an aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 31 represents a hydrogen atom, substituted or unsubstituted A monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic group a heterocyclic group, X 3 is a direct bond, an oxygen atom, or a sulfur atom It is.)
一般式[10]
(一般式[10]中、R32は、直接結合、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R33は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R34は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、X4は、直接結合、酸素原子、または、硫黄原子を表す。) (In the general formula [10], R 32 represents a direct bond, a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent group. Represents an aliphatic heterocyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 33 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent Represents an aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 34 represents a hydrogen atom, substituted or unsubstituted A monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic group a heterocyclic group, X 4 is a direct bond, an oxygen atom or a sulfur atom Represent.)
一般式[11]
(一般式[11]中、R35〜R39は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、R27〜R31は、隣接した基が互いに結合して環を形成しても良い。) (In the general formula [11], R 35 to R 39 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group R 27 to R 31 may represent a group, and adjacent groups may be bonded to each other to form a ring.
ここで、一般式[7]〜[11]における、ハロゲン原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基は前述のものが挙げられる。 Here, in the general formulas [7] to [11], a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group, substituted or unsubstituted divalent aliphatic carbonization The hydrogen group, substituted or unsubstituted divalent aromatic hydrocarbon group, substituted or unsubstituted divalent aliphatic heterocyclic group, or substituted or unsubstituted divalent aromatic heterocyclic group are as described above. Is mentioned.
さらに、1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、2価の脂肪族複素環基、および、2価の芳香族複素環基は置換されていても良い。その場合の置換基としては、前述の1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、ハロゲン原子、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基が挙げられる。 Furthermore, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a divalent aliphatic hydrocarbon group, a divalent aliphatic group, The aromatic hydrocarbon group, divalent aliphatic heterocyclic group, and divalent aromatic heterocyclic group may be substituted. In this case, examples of the substituent include the aforementioned monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, halogen atom, cyano Group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group.
また、一般式[4]、[5]、および、[6]における、l、m、および、nは、それぞれ独立に、1以上の整数を表す。ここで、l、m、および、nは好ましくは1〜1000であり、特に好ましくは1〜100である。この理由として、分子量が大きいと、汎用性有機溶媒に溶解しづらくなる懸念があるためである。 In general formulas [4], [5], and [6], l, m, and n each independently represent an integer of 1 or more. Here, l, m, and n are preferably 1-1000, particularly preferably 1-100. This is because if the molecular weight is large, there is a concern that it is difficult to dissolve in a general-purpose organic solvent.
本発明で用いられる、一般式[4]で表される重合性化合物の代表例を、以下の表2に示すが、本発明は、この代表例に限定されるものではない。 Typical examples of the polymerizable compound represented by the general formula [4] used in the present invention are shown in Table 2 below, but the present invention is not limited to these representative examples.
本発明で用いられる一般式[5]で表される化合物の代表例を、以下の表3に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the compound represented by the general formula [5] used in the present invention are shown in Table 3 below, but the present invention is not limited to these representative examples.
本発明で用いられる一般式[6]で表される化合物の代表例を、以下の表4に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the compound represented by the general formula [6] used in the present invention are shown in Table 4 below, but the present invention is not limited to these representative examples.
一般式[12]
Formula [12]
一般式[13]
(一般式[12]及び一般式[13]中、
Cは、下記一般式[14]を、
Dは、下記一般式[15]を、
Gは、下記一般式[16]、または一般式[17]を、
Hは、水素原子、下記一般式[18]、もしくは、ハロゲン原子を表し、
y及びzは、それぞれ独立に、1以上の整数を表す。)
(In General Formula [12] and General Formula [13],
C represents the following general formula [14]:
D represents the following general formula [15]:
G represents the following general formula [16] or general formula [17],
H represents a hydrogen atom, the following general formula [18], or a halogen atom,
y and z each independently represents an integer of 1 or more. )
一般式[14]
(一般式[14]中、R40およびR41は、それぞれ独立に、水素原子、置換または未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基を表す。) (In the general formula [14], R 40 and R 41 each independently represent a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, Represents a substituted or unsubstituted monovalent aliphatic heterocyclic group or a substituted or unsubstituted monovalent aromatic heterocyclic group.)
一般式[15]
(一般式[15]中、R42〜R59は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、R42〜R59は、隣接した基が互いに結合して環を形成しても良い。) (In the general formula [15], R 42 to R 59 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group And R 42 to R 59 may be bonded to each other to form a ring.
一般式[16]
(一般式[16]中、R60は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R61は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、X5は、直接結合、酸素原子、または、硫黄原子を表す。) (In the general formula [16], R 60 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 61 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent group. An aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, X 5 represents a direct bond, an oxygen atom, or Represents a sulfur atom.)
一般式[17]
(一般式[17]中、R62は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、R63は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、X6は、直接結合、酸素原子、または、硫黄原子を表す。) (In the general formula [17], R 62 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group, and R 63 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent group. An aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or a substituted or unsubstituted monovalent aromatic heterocyclic group, X 6 represents a direct bond, an oxygen atom, or Represents a sulfur atom.)
一般式[18]
(一般式[18]中、R64〜R68は、それぞれ独立に、水素原子、ハロゲン原子、置換または未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、R64〜R68は、隣接した基が互いに結合して環を形成しても良い。) (In the general formula [18], R 64 to R 68 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group And R 64 to R 68 may be adjacent to each other to form a ring.
ここで、一般式[14]〜[18]における、ハロゲン原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基は前述のものが挙げられる。 Here, in the general formulas [14] to [18], a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group, substituted or unsubstituted divalent aliphatic carbonization The hydrogen group, substituted or unsubstituted divalent aromatic hydrocarbon group, substituted or unsubstituted divalent aliphatic heterocyclic group, or substituted or unsubstituted divalent aromatic heterocyclic group are as described above. Is mentioned.
さらに、1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、2価の脂肪族複素環基、および、2価の芳香族複素環基は置換されていても良い。その場合の置換基としては、前述の1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、ハロゲン原子、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基が挙げられる。 Furthermore, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a divalent aliphatic hydrocarbon group, a divalent aliphatic group, The aromatic hydrocarbon group, divalent aliphatic heterocyclic group, and divalent aromatic heterocyclic group may be substituted. In this case, examples of the substituent include the aforementioned monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, halogen atom, cyano Group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group.
また、一般式[12]、および、[13]における、y、および、zは、それぞれ独立に、1以上の整数を表す。ここで、y、および、zは好ましくは1〜1000であり、特に好ましくは1〜100である。この理由として、分子量が大きいと、汎用性有機溶媒に溶解しづらくなる懸念があるためである。 In general formulas [12] and [13], y and z each independently represent an integer of 1 or more. Here, y and z are preferably 1-1000, particularly preferably 1-100. This is because if the molecular weight is large, there is a concern that it is difficult to dissolve in a general-purpose organic solvent.
本発明で用いられる、一般式[12]で表される重合性化合物の代表例を、以下の表5に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the polymerizable compound represented by the general formula [12] used in the present invention are shown in Table 5 below, but the present invention is not limited to these representative examples.
本発明で用いられる一般式[13]で表される化合物の代表例を、以下の表6に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the compound represented by the general formula [13] used in the present invention are shown in Table 6 below, but the present invention is not limited to these representative examples.
一般式[19]
(一般式[19]中、R69〜R86は、それぞれ独立に、水素原子、ハロゲン原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、または、置換アミノ基を表し、R69〜R86は、隣接した基が互いに結合して環を形成しても良い。
J3およびJ4は、それぞれ独立に、下記一般式[20]、または、一般式[21]で表される基である。)
(In the general formula [19], R 69 to R 86 are each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic carbonization. Hydrogen group, substituted or unsubstituted monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, cyano group, substituted silyl group, alkoxyl group, aryloxy group, or substituted amino group R 69 to R 86 may represent a group, and adjacent groups may be bonded to each other to form a ring.
J 3 and J 4 are each independently a group represented by the following general formula [20] or general formula [21]. )
一般式[20]
(一般式[20]中、R87は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、
R88は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、
X7は、直接結合、酸素原子、または、硫黄原子を表す。)
(In the general formula [20], R 87 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group,
R 88 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X 7 represents a direct bond, an oxygen atom, or a sulfur atom. )
一般式[21]
(一般式[21]中、R89は、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表し、
R90は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、
X8は、直接結合、酸素原子、または、硫黄原子を表す。)
(In the general formula [21], R 89 represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic group. Represents a heterocyclic group, or a substituted or unsubstituted divalent aromatic heterocyclic group,
R 90 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X 8 represents a direct bond, an oxygen atom, or a sulfur atom. )
ここで、一般式[19]〜[21]における、ハロゲン原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、置換もしくは未置換の1価の芳香族複素環基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基は前述のものが挙げられる。 Here, in the general formulas [19] to [21], a halogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted Monovalent aliphatic heterocyclic group, substituted or unsubstituted monovalent aromatic heterocyclic group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group, substituted or unsubstituted divalent aliphatic carbonization The hydrogen group, substituted or unsubstituted divalent aromatic hydrocarbon group, substituted or unsubstituted divalent aliphatic heterocyclic group, or substituted or unsubstituted divalent aromatic heterocyclic group are as described above. Is mentioned.
さらに、1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、2価の脂肪族炭化水素基、2価の芳香族炭化水素基、2価の脂肪族複素環基、および、2価の芳香族複素環基は置換されていても良い。その場合の置換基としては、前述の1価の脂肪族炭化水素基、1価の芳香族炭化水素基、1価の脂肪族複素環基、1価の芳香族複素環基、ハロゲン原子、シアノ基、置換シリル基、アルコキシル基、アリ−ルオキシ基、置換アミノ基が挙げられる。 Furthermore, a monovalent aliphatic hydrocarbon group, a monovalent aromatic hydrocarbon group, a monovalent aliphatic heterocyclic group, a monovalent aromatic heterocyclic group, a divalent aliphatic hydrocarbon group, a divalent aliphatic group, The aromatic hydrocarbon group, divalent aliphatic heterocyclic group, and divalent aromatic heterocyclic group may be substituted. In this case, examples of the substituent include the aforementioned monovalent aliphatic hydrocarbon group, monovalent aromatic hydrocarbon group, monovalent aliphatic heterocyclic group, monovalent aromatic heterocyclic group, halogen atom, cyano Group, substituted silyl group, alkoxyl group, aryloxy group, substituted amino group.
本発明で用いられる、一般式[19]で表される重合性化合物の代表例を、以下の表7に示すが、本発明は、この代表例に限定されるものではない。 Representative examples of the polymerizable compound represented by the general formula [19] used in the present invention are shown in Table 7 below, but the present invention is not limited to these representative examples.
本発明における高分子化合物は、本発明の重合性化合物を単独、または、他の重合性化合物と混合した後に、熱、光、開始剤等により重合することで得ることができる。 The polymer compound in the present invention can be obtained by polymerizing the polymerizable compound of the present invention alone or with another polymerizable compound and then polymerizing with heat, light, an initiator or the like.
本発明における重合性化合物および高分子化合物は、有機エレクトロルミネッセンス素子用材料として用いることができる。 The polymerizable compound and the polymer compound in the present invention can be used as a material for an organic electroluminescence element.
本発明における有機エレクトロルミネッセンス素子用材料を用いて有機EL素子を作成する場合には、湿式成膜法を用いることが好ましい。 When producing an organic EL element using the organic electroluminescence element material in the present invention, it is preferable to use a wet film-forming method.
ここで、本発明における、湿式成膜法とは、塗布法、インクジェット法、ディップコート法、ダイコート法、スプレーコート法、スピンコート法、ロールコーター法、湿漬塗布法、スクリーン印刷法、フレキソ印刷、スクリーン印刷法、LB法等などにより、組成物を塗布して成膜することである。 Here, in the present invention, the wet film forming method is a coating method, an inkjet method, a dip coating method, a die coating method, a spray coating method, a spin coating method, a roll coater method, a dipping coating method, a screen printing method, a flexographic printing method. In other words, the composition is applied to form a film by a screen printing method, an LB method, or the like.
本発明における有機エレクトロルミネッセンス素子用材料を湿式成膜法で用いるためには、本発明の重合性化合物と溶剤とを含有する有機EL素子用インキ組成物とすることが好ましい。 In order to use the organic electroluminescent device material of the present invention in a wet film-forming method, it is preferable to use an organic EL device ink composition containing the polymerizable compound of the present invention and a solvent.
このとき、有機EL素子用インキ組成物は、湿式成膜法で成膜後、加熱により重合性化合物を重合させることで、有機EL素子における層を形成することができる。 At this time, the ink composition for organic EL elements can form a layer in the organic EL element by polymerizing a polymerizable compound by heating after film formation by a wet film formation method.
有機EL素子用インキ組成物に含まれる溶剤としては種々の溶剤が適用可能であり、特に限定されない。例えば、トルエン、キシレン、メシチレン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素;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;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;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;シクロヘキサノン、シクロオクタノン等の脂環を有するケトン;メチルエチルケトン、ジブチルケトン等の脂肪族ケトン;メチルエチルケトン、シクロヘキサノール、シクロオクタノール等の脂環を有するアルコール;ブタノール、ヘキサノール等の脂肪族アルコール;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;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等が挙げられる。 Various solvents are applicable as the solvent contained in the ink composition for organic EL elements, and are not particularly limited. For example, aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, and tetralin; halogenated aromatic hydrocarbons such as chlorobenzene, dichlorobenzene, and trichlorobenzene; 1,2-dimethoxybenzene, 1,3-dimethoxybenzene, anisole , Phenetole, 2-methoxytoluene, 3-methoxytoluene, 4-methoxytoluene, 2,3-dimethylanisole, 2,4-dimethylanisole and other aromatic ethers; phenyl acetate, phenyl propionate, methyl benzoate, benzoic acid Aromatic esters such as ethyl, propyl benzoate and n-butyl benzoate; ketones having an alicyclic ring such as cyclohexanone and cyclooctanone; aliphatic ketones such as methyl ethyl ketone and dibutyl ketone; methyl ethyl ketone and cyclohexano Alcohol having an alicyclic ring such as ruthenium or cyclooctanol; Aliphatic alcohol such as butanol or hexanol; Aliphatic ether such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether or propylene glycol-1-monomethyl ether acetate (PGMEA); Ethyl acetate And aliphatic esters such as n-butyl acetate, ethyl lactate and n-butyl lactate.
これらのうち、水の溶解度が低い点、容易には変質しない点で、トルエン、キシレン、メシチレン、シクロヘキシルベンゼン、テトラリン等の芳香族炭化水素が好ましい。 Of these, aromatic hydrocarbons such as toluene, xylene, mesitylene, cyclohexylbenzene, tetralin and the like are preferable in that they have low water solubility and are not easily altered.
また、これらの溶剤は単独で使用しても複数混合して用いてもよい。尚、使用可能な溶剤はこれらに限定されるものではない。 These solvents may be used alone or in combination. In addition, the solvent which can be used is not limited to these.
有機電界発光素子には、陰極等の水分により著しく劣化する材料が多く使用されているため、組成物中の水分の存在は、乾燥後の膜中に水分が残留し、素子の特性を低下させる可能性が考えられ好ましくない。 Since organic electroluminescent devices use many materials such as cathodes that deteriorate significantly due to moisture, the presence of moisture in the composition causes moisture to remain in the dried film, degrading the device characteristics. The possibility is considered and it is not preferable.
また、湿式成膜時における組成物からの溶剤蒸発による、成膜安定性の低下を低減するためには、有機EL素子用組成物の溶剤として、沸点が100℃以上、好ましくは沸点が150℃以上、より好ましくは沸点が200℃以上の溶剤を用いることが効果的である。 Further, in order to reduce a decrease in film formation stability due to solvent evaporation from the composition during wet film formation, the boiling point is 100 ° C. or higher, preferably 150 ° C. as the solvent of the composition for organic EL elements. As described above, it is more effective to use a solvent having a boiling point of 200 ° C. or higher.
本発明の有機EL素子用インキ組成物は、本発明の有機EL素子用材料の含有量が0.5wt%以上であることが好ましい。通常、有機EL素子の発光層膜厚は10〜100nmであるが、一般的には50nm以上の場合が多い。50nmよりも薄い膜厚になると発光性能の低下や大幅な色調のずれ等の不具合を生じてしまう。50nm以上の膜厚を容易に形成するには0.5wt%以上の溶液濃度であることが好ましい。0.5wt%よりも濃度が低い場合は厚膜形成が困難となる。 In the organic EL element ink composition of the present invention, the content of the organic EL element material of the present invention is preferably 0.5 wt% or more. Usually, the thickness of the light-emitting layer of the organic EL element is 10 to 100 nm, but generally it is often 50 nm or more. When the film thickness is less than 50 nm, problems such as a decrease in light emission performance and a large color tone deviation occur. In order to easily form a film thickness of 50 nm or more, the solution concentration is preferably 0.5 wt% or more. When the concentration is lower than 0.5 wt%, it is difficult to form a thick film.
本発明の有機EL素子用インキ組成物には、上述した有機EL素子用材料と溶剤の他に、必要に応じて公知の添加剤を添加してもよい。 In addition to the organic EL element material and solvent described above, a known additive may be added to the ink composition for an organic EL element of the present invention as necessary.
ここで、本発明の化合物からなる有機エレクトロルミネッセンス素子用材料を用いて作成することができる有機EL素子について詳細に説明する。 Here, the organic EL element which can be produced using the organic electroluminescent element material comprising the compound of the present invention will be described in detail.
有機EL素子は、陽極と陰極間に一層または多層の有機層を形成した素子から構成されるが、ここで、一層型有機EL素子とは、陽極と陰極との間に発光層のみからなる素子を指す。一方、多層型有機EL素子とは、発光層の他に、発光層への正孔や電子の注入を容易にしたり、発光層内での正孔と電子との再結合を円滑に行わせたりすることを目的として、正孔注入層、正孔輸送層、正孔阻止層、電子注入層などを積層させたものを指す。また、発光層と陽極との間で発光層に隣接して存在し、発光層と陽極、又は発光層と、正孔注入層若しくは正孔輸送層とを隔離する役割をもつ層であるインターレイヤー層を挿入しても良い。したがって、多層型有機EL素子の代表的な素子構成としては、(1)陽極/正孔注入層/発光層/陰極、(2)陽極/正孔注入層/正孔輸送層/発光層/陰極、(3)陽極/正孔注入層/発光層/電子注入層/陰極、(4)陽極/正孔注入層/正孔輸送層/発光層/電子注入層/陰極、(5)陽極/正孔注入層/発光層/正孔阻止層/電子注入層/陰極、(6)陽極/正孔注入層/正孔輸送層/発光層/正孔阻止層/電子注入層/陰極、(7)陽極/発光層/正孔阻止層/電子注入層/陰極、(8)陽極/発光層/電子注入層/陰極(9)陽極/正孔注入層/正孔輸送層/インターレイヤー層/発光層/陰極、(10)陽極/正孔注入層/インターレイヤー層/発光層/電子注入層/陰極、(11)陽極/正孔注入層/正孔輸送層/インターレイヤー層/発光層/電子注入層/陰極、等の多層構成で積層した素子構成が考えられる。 The organic EL element is composed of an element in which a single layer or a multilayer organic layer is formed between an anode and a cathode. Here, the single layer type organic EL element is an element composed of only a light emitting layer between an anode and a cathode. Point to. On the other hand, the multilayer organic EL element facilitates injection of holes and electrons into the light emitting layer in addition to the light emitting layer, and facilitates recombination of holes and electrons in the light emitting layer. For the purpose of this, it refers to a layer in which a hole injection layer, a hole transport layer, a hole blocking layer, an electron injection layer, and the like are laminated. Further, an interlayer that is adjacent to the light emitting layer between the light emitting layer and the anode and has a role of separating the light emitting layer and the anode or the light emitting layer from the hole injection layer or the hole transport layer. Layers may be inserted. Therefore, typical element configurations of the multilayer organic EL element include (1) anode / hole injection layer / light emitting layer / cathode, and (2) anode / hole injection layer / hole transport layer / light emitting layer / cathode. (3) Anode / hole injection layer / light emitting layer / electron injection layer / cathode, (4) Anode / hole injection layer / hole transport layer / light emitting layer / electron injection layer / cathode, (5) Anode / positive Hole injection layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (6) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron injection layer / cathode, (7) Anode / light emitting layer / hole blocking layer / electron injection layer / cathode, (8) anode / light emitting layer / electron injection layer / cathode (9) anode / hole injection layer / hole transport layer / interlayer layer / light emitting layer / Cathode, (10) anode / hole injection layer / interlayer layer / light emitting layer / electron injection layer / cathode, (11) anode / hole injection layer / hole transport layer / inter layer Layer / light emitting layer / electron injection layer / cathode, an element formed by laminating a multilayer structure etc. can be considered.
また、上述した各有機層は、それぞれ二層以上の層構成により形成されても良く、いくつかの層が繰り返し積層されていても良い。そのような例として、近年、光取り出し効率の向上を目的に、上述の多層型有機EL素子の一部の層を多層化する「マルチ・フォトン・エミッション」と呼ばれる素子構成が提案されている。これは例えば、ガラス基板/陽極/正孔輸送層/電子輸送性発光層/電子注入層/電荷発生層/発光ユニット/陰極から構成される有機EL素子に於いて、電荷発生層と発光ユニットの部分を複数層積層するといった方法が挙げられる。 Moreover, each organic layer mentioned above may be formed by the layer structure of two or more layers, respectively, and several layers may be laminated | stacked repeatedly. As such an example, an element configuration called “multi-photon emission” in which a part of the above-described multilayer organic EL element is multilayered has been proposed in recent years for the purpose of improving light extraction efficiency. For example, in an organic EL device composed of a glass substrate / anode / hole transport layer / electron transporting light emitting layer / electron injection layer / charge generating layer / light emitting unit / cathode, the charge generating layer and the light emitting unit There is a method of laminating a plurality of portions.
本発明の有機EL素子を作製する方法については、上記の材料および方法により陽極、発光層、必要に応じて正孔注入層、および必要に応じて電子注入層を形成し、最後に陰極を形成すればよい。また、陰極から陽極へ、前記と逆の順序で有機EL素子を作製することもできる。 Regarding the method for producing the organic EL device of the present invention, an anode, a light emitting layer, a hole injection layer as necessary, and an electron injection layer as necessary are formed by the above materials and methods, and finally a cathode is formed. do it. Moreover, an organic EL element can also be produced from the cathode to the anode in the reverse order.
この有機EL素子は、透光性の基板上に作製する。この透光性基板は有機EL素子を支持する基板であり、その透光性については、400〜700nmの可視領域の光の透過率が50%以上、好ましくは90%以上であるものが望ましく、さらに平滑な基板を用いるのが好ましい。 This organic EL element is manufactured on a translucent substrate. This translucent substrate is a substrate that supports the organic EL element, and for the translucency, it is desirable that the transmittance of light in the visible region of 400 to 700 nm is 50% or more, preferably 90% or more, Further, it is preferable to use a smooth substrate.
これら基板は、機械的、熱的強度を有し、透明であれば特に限定されるものではないが、例えば、ガラス板、合成樹脂板などが好適に用いられる。ガラス板としては、特にソーダ石灰ガラス、バリウム・ストロンチウム含有ガラス、鉛ガラス、アルミノケイ酸ガラス、ホウケイ酸ガラス、バリウムホウケイ酸ガラス、石英などで成形された板が挙げられる。また、合成樹脂板としては、ポリカーボネート樹脂、アクリル樹脂、ポリエチレンテレフタレート樹脂、ポリエーテルサルファイド樹脂、ポリサルフォン樹脂などの板が挙げられる。 These substrates have mechanical and thermal strengths and are not particularly limited as long as they are transparent. For example, glass plates, synthetic resin plates and the like are preferably used. Examples of the glass plate include soda-lime glass, barium / strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass, and quartz. Examples of the synthetic resin plate include plates such as polycarbonate resin, acrylic resin, polyethylene terephthalate resin, polyether sulfide resin, and polysulfone resin.
本発明の有機EL素子の各層の形成方法としては、真空蒸着、電子線ビーム照射、スパッタリング、プラズマ、イオンプレーティング等の乾式成膜法、もしくはスピンコーティング、ディッピング、フローコーティング等の湿式成膜法のいずれかの方法を適用することができる。また、特表2002−534782や、S.T.Lee, et al., Proceedings of SID’02, p.784(2002)に記載されているLITI(Laser Induced Thermal Imaging、レーザー熱転写)法や、印刷(オフセット印刷、フレキソ印刷、グラビア印刷、スクリーン印刷)、インクジェット等の方法を適用することもできる。 As a method for forming each layer of the organic EL element of the present invention, a dry film forming method such as vacuum deposition, electron beam irradiation, sputtering, plasma, ion plating, or a wet film forming method such as spin coating, dipping, or flow coating is used. Either method can be applied. In addition, Special Table 2002-53482, S.I. T.A. Lee, et al. , Proceedings of SID'02, p. LITI (Laser Induced Thermal Imaging) method described in 784 (2002), printing (offset printing, flexographic printing, gravure printing, screen printing), inkjet, and the like can also be applied.
有機層は、特に分子堆積膜であることが好ましい。ここで分子堆積膜とは、気相状態の材料化合物から沈着され形成された薄膜や、溶液状態または液相状態の材料化合物から固体化され形成された膜のことであり、通常この分子堆積膜は、LB法により形成された薄膜(分子累積膜)とは凝集構造、高次構造の相違や、それに起因する機能的な相違により区分することができる。また特開昭57−51781号公報に開示されているように、樹脂等の結着剤と材料化合物とを溶剤に溶かして溶液とした後、これをスピンコート法等により薄膜化することによっても、有機層を形成することができる。各層の膜厚は特に限定されるものではないが、膜厚が厚すぎると一定の光出力を得るために大きな印加電圧が必要となり効率が悪くなり、逆に膜厚が薄すぎるとピンホール等が発生し、電界を印加しても充分な発光輝度が得にくくなる。したがって、各層の膜厚は、1nmから1μmの範囲が適しているが、10nmから0.2μmの範囲がより好ましい。 The organic layer is particularly preferably a molecular deposited film. Here, the molecular deposited film is a thin film formed by deposition from a material compound in a gas phase state or a film formed by solidifying from a material compound in a solution state or a liquid phase state. Can be classified from a thin film (accumulated film) formed by the LB method according to a difference in an agglomerated structure and a higher-order structure and a functional difference resulting therefrom. Further, as disclosed in JP-A-57-51781, a binder such as a resin and a material compound are dissolved in a solvent to form a solution, which is then thinned by a spin coat method or the like. An organic layer can be formed. The film thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, pinholes, etc. And it becomes difficult to obtain sufficient light emission luminance even when an electric field is applied. Accordingly, the thickness of each layer is suitably in the range of 1 nm to 1 μm, but more preferably in the range of 10 nm to 0.2 μm.
また、有機EL素子の温度、湿度、雰囲気等に対する安定性向上のために、素子の表面に保護層を設けたり、樹脂等により素子全体を被覆や封止を施したりしても良い。特に素子全体を被覆や封止する際には、光によって硬化する光硬化性樹脂が好適に使用される。 Further, in order to improve the stability of the organic EL element with respect to temperature, humidity, atmosphere and the like, a protective layer may be provided on the surface of the element, or the entire element may be covered or sealed with a resin or the like. In particular, when the entire element is covered or sealed, a photocurable resin that is cured by light is preferably used.
本発明の有機EL素子に印加する電流は通常、直流であるが、パルス電流や交流を用いてもよい。電流値、電圧値は、素子破壊しない範囲内であれば特に制限はないが、素子の消費電力や寿命を考慮すると、なるべく小さい電気エネルギーで効率良く発光させることが望ましい。 The current applied to the organic EL element of the present invention is usually a direct current, but a pulse current or an alternating current may be used. The current value and the voltage value are not particularly limited as long as the element is within a range not destroying the element. However, considering the power consumption and life of the element, it is desirable to efficiently emit light with as little electrical energy as possible.
本発明の有機EL素子の駆動方法は、パッシブマトリクス法のみならず、アクティブマトリックス法での駆動も可能である。また、本発明の有機EL素子から光を取り出す方法としては、陽極側から光を取り出すボトム・エミッションという方法のみならず、陰極側から光を取り出すトップ・エミッションという方法にも適用可能である。これらの方法や技術は、城戸淳二著、「有機ELのすべて」、日本実業出版社(2003年発行)に記載されている。 The organic EL device driving method of the present invention can be driven not only by the passive matrix method but also by the active matrix method. Further, the method for extracting light from the organic EL device of the present invention is applicable not only to the method of bottom emission for extracting light from the anode side but also to the method of top emission for extracting light from the cathode side. These methods and techniques are described in Shinji Kido, “All about organic EL”, published by Nihon Jitsugyo Shuppansha (published in 2003).
本発明の有機EL素子のフルカラー化方式の主な方式としては、3色塗り分け方式、色変換方式、カラーフィルター方式が挙げられる。3色塗り分け方式では、シャドウマスクを使った蒸着法や、インクジェット法や印刷法が挙げられる。また、特表2002−534782や、S.T.Lee, et al., Proceedings of SID’02, p.784(2002)に記載されているレーザー熱転写法(Laser Induced Thermal Imaging、LITI法ともいわれる)も用いることができる。色変換方式では、青色発光の発光層を使って、蛍光色素を分散した色変換(CCM)層を通して、青色より長波長の緑色と赤色に変換する方法である。カラーフィルター方式では、白色発光の有機EL素子を使って、液晶用カラーフィルターを通して3原色の光を取り出す方法であるが、これら3原色に加えて、一部白色光をそのまま取り出して発光に利用することで、素子全体の発光効率をあげることもできる。 Examples of the main method of full colorization of the organic EL device of the present invention include a three-color coating method, a color conversion method, and a color filter method. In the three-color coating method, an evaporation method using a shadow mask, an ink jet method, and a printing method can be used. In addition, Special Table 2002-53482, S.I. T.A. Lee, et al. , Proceedings of SID'02, p. 784 (2002) can also be used. The laser thermal transfer method (also referred to as Laser Induced Thermal Imaging, LITI method) can also be used. In the color conversion method, a blue light emitting layer is used to convert green and red having a longer wavelength than blue through a color conversion (CCM) layer in which fluorescent dyes are dispersed. The color filter method uses a white light emitting organic EL element to extract light of three primary colors through a color filter for liquid crystal. In addition to these three primary colors, a part of white light is directly extracted and used for light emission. Thus, the luminous efficiency of the entire device can be increased.
さらに、本発明の有機EL素子は、マイクロキャビティ構造を採用しても構わない。これは、有機EL素子は、発光層が陽極と陰極との間に挟持された構造であり、発光した光は陽極と陰極との間で多重干渉を生じるが、陽極及び陰極の反射率、透過率などの光学的な特性と、これらに挟持された有機層の膜厚とを適当に選ぶことにより、多重干渉効果を積極的に利用し、素子より取り出される発光波長を制御するという技術である。これにより、発光色度を改善することも可能となる。この多重干渉効果のメカニズムについては、J.Yamada等によるAM−LCD Digest of Technical Papers,OD−2,p.77〜80(2002)に記載されている。 Furthermore, the organic EL element of the present invention may adopt a microcavity structure. This is because the organic EL element has a structure in which the light emitting layer is sandwiched between the anode and the cathode, and the emitted light causes multiple interference between the anode and the cathode, but the reflectance and transmission of the anode and the cathode. This is a technology that actively uses the multiple interference effect and controls the emission wavelength extracted from the device by appropriately selecting the optical characteristics such as the rate and the film thickness of the organic layer sandwiched between them. . Thereby, it is also possible to improve the emission chromaticity. For the mechanism of this multiple interference effect, see J.A. Yamada et al., AM-LCD Digest of Technical Papers, OD-2, p. 77-80 (2002).
以上述べたように、本発明の有機エレクトロルミネッセンス素子用材料を用いた有機EL素子は、低い駆動電圧で長時間の青色発光を得ることが可能である。故に、本有機EL素子は、壁掛けテレビ等のフラットパネルディスプレイや各種の平面発光体として、さらには、複写機やプリンター等の光源、液晶ディスプレイや計器類等の光源、表示板、標識灯等への応用が考えられる。 As described above, the organic EL element using the organic electroluminescence element material of the present invention can obtain long-term blue light emission at a low driving voltage. Therefore, this organic EL device can be used as a flat panel display such as a wall-mounted television and various flat light emitters, as well as a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, a marker lamp, etc. Can be applied.
以下、本発明を実施例で説明するが、本発明はこれら実施例になんら限定されるものではない。なお、以下の製造例、実施例、比較例の説明中、部は重量部、% は重量% を表す。また、以下の製造例においては、赤外線吸収スペクトル(IR)は、パーキンエルマー社製Spectrum One Ver.A フーリエ変換赤外線分光分析装置を用いて測定した。また、NMRスペクトルは、日本電子社製GSX270 FT−NMR分析装置を用いて測定した。さらに、TOF−MSスペクトルは、ブルカー・ダルトニクス社製autoflex IIを用いて測定した。 EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples at all. In the following description of production examples, examples and comparative examples, parts represent parts by weight and% represents% by weight. Further, in the following production examples, infrared absorption spectrum (IR) is measured by Perkin Elmer Spectrum One Ver. A It measured using the Fourier-transform infrared spectroscopy analyzer. Further, the NMR spectrum was measured using a GSX270 FT-NMR analyzer manufactured by JEOL. Furthermore, the TOF-MS spectrum was measured using an autoflex II manufactured by Bruker Daltonics.
実施例1
化合物(1)の合成方法
反応式(1−1)〜(1−2)を用いて化合物(1)を合成した。
Example 1
Method for Synthesizing Compound (1) Compound (1) was synthesized using reaction formulas (1-1) to (1-2).
反応式(1−1)
窒素雰囲気下、500mLナスフラスコに4−ブロモフェノール13.8g(80mmol)、細かく砕いたNaOH粉末16g(400mmol)を入れ、DMSO100mL加え室温で24時間攪拌した。その後、3−(クロロメチル)−3−メチルオキセタン12.1g(100mmol)をゆっくりと滴下し、滴下終了後室温で120時間攪拌した。その後、反応液に水300mLを加え室温で1時間攪拌した。析出した白色固体を濾別し水でふりかけ洗浄した。得られた白色固体を40℃真空乾燥することにより、中間体(I)を白色固体として収量19.2g(収率93%)で得た。 Under a nitrogen atmosphere, 13.8 g (80 mmol) of 4-bromophenol and 16 g (400 mmol) of finely crushed NaOH powder were placed in a 500 mL eggplant flask, and 100 mL of DMSO was added and stirred at room temperature for 24 hours. Thereafter, 12.1 g (100 mmol) of 3- (chloromethyl) -3-methyloxetane was slowly added dropwise, and the mixture was stirred at room temperature for 120 hours after completion of the addition. Thereafter, 300 mL of water was added to the reaction solution and stirred at room temperature for 1 hour. The precipitated white solid was separated by filtration and washed with water. The obtained white solid was vacuum-dried at 40 ° C. to obtain 19.2 g (yield 93%) of intermediate (I) as a white solid.
反応式(1−2)
窒素雰囲気下、200mL4つ口フラスコに中間体(I)3.21g(12.5mmo
l)、9,9−ジヘキシルフルオレン−2,7−ジボロニックアシッドビス(1,3−プロパンジオール)エステル)2.51g(5mmol)、テトラキス(トリフェニルホスフィン)パラジウム0.14g(0.125mmol)を入れ、炭酸カリウム(2M水溶液)25g、テトラヒドロフラン50mLを加え8時間加熱還流した。その後、反応液をトルエンと水で抽出し、有機層を減圧濃縮した。その後有機層をトルエン:酢酸エチル=9:1のカラムクロマトグラフィーで分離精製することにより、化合物(1)を収量2.7g(収率79%)得た。
Under a nitrogen atmosphere, 3.21 g (12.5 mmol) of intermediate (I) was added to a 200 mL four-necked flask.
l), 9,9-dihexylfluorene-2,7-diboronic acid bis (1,3-propanediol) ester) 2.51 g (5 mmol), tetrakis (triphenylphosphine) palladium 0.14 g (0.125 mmol) ), 25 g of potassium carbonate (2M aqueous solution) and 50 mL of tetrahydrofuran were added, and the mixture was heated to reflux for 8 hours. Thereafter, the reaction solution was extracted with toluene and water, and the organic layer was concentrated under reduced pressure. Thereafter, the organic layer was separated and purified by column chromatography with toluene: ethyl acetate = 9: 1 to obtain 2.7 g (yield 79%) of compound (1).
実施例1の化合物のIRスペクトルを図1に、1H−NMRスペクトルを図2に、TOF−MSスペクトルを図3にそれぞれ示す。またTOF−MSによる分子量測定結果を表8に示す。 FIG. 1 shows the IR spectrum of the compound of Example 1, FIG. 2 shows the 1 H-NMR spectrum, and FIG. 3 shows the TOF-MS spectrum. Table 8 shows the results of molecular weight measurement by TOF-MS.
実施例2〜40 Examples 2-40
実施例1で用いた原料のかわりに、それぞれの実施例に対応する原料を用いる以外は実施例1と同様に表1に示す化合物(2)〜化合物(40)を合成した。TOF−MSによる分子量測定結果を表8に示す。 Instead of the raw materials used in Example 1, the compounds (2) to (40) shown in Table 1 were synthesized in the same manner as in Example 1 except that the raw materials corresponding to the respective examples were used. Table 8 shows the results of molecular weight measurement by TOF-MS.
有機EL素子の実施例
以下、本発明の化合物を有機EL素子用材料として用いた有機EL素子について下記実施例により説明するが、本発明は下記実施例に限定されるものではない。実施例においては、特に断りのない限り、混合比は全て重量比を示す。蒸着(真空蒸着)は10-6Torrの真空中にて、基板の加熱や冷却といった温度制御はしない条件下で行った。また、素子の発光特性は、発光素子面積2mm×2mmの有機EL素子を用いて特性を測定した。
Examples of Organic EL Device Hereinafter, organic EL devices using the compound of the present invention as a material for organic EL devices will be described with reference to the following examples, but the present invention is not limited to the following examples. In the examples, all mixing ratios are weight ratios unless otherwise specified. Vapor deposition (vacuum deposition) was performed in a vacuum of 10 −6 Torr under conditions where temperature control such as heating and cooling of the substrate was not performed. The light emission characteristics of the element were measured using an organic EL element having a light emitting element area of 2 mm × 2 mm.
実施例41
洗浄したITO電極付きガラス板上に、PEDOT/PSS(ポリ(3,4−エチレンジオキシ)−2,5−チオフェン/ポリスチレンスルホン酸、Bayer社製BAYTRON P VP CH8000)をスピンコート法にて製膜し、200℃乾燥により、膜厚60nmの正孔注入層を得た。次いで、本発明の表1中の化合物(1)と表2中の化合物(41)とを50:50の割合で混合し、0.5wt%の濃度でトルエンに溶解させ、スピンコーティング法により20nmの膜厚の正孔輸送層を製膜し200℃にて重合させた。ついで、以下に示す化合物(A)を、1.0wt%の濃度でトルエンに溶解させ、スピンコーティング法により40nmの膜厚の発光層を製膜し、100℃にて乾燥させた。さらにその上に、以下に示す化合物(B)を、真空蒸着して膜厚20nmの電子注入層を作成し、その上に、まずフッ化リチウムを1nm、次いでアルミニウム(Al)を150nm蒸着して電極を形成し、有機EL素子を得た。この素子について通電試験を行ったところ、最大発光輝度550cd/m2の青色発光が得られた。この素子を6Vに駆動させた際の色度は、CIE(x,y)=(0.15,0.11)の青色発光であった。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表9に示す。
Example 41
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured on a cleaned glass plate with an ITO electrode by a spin coating method Then, a hole injection layer having a film thickness of 60 nm was obtained by drying at 200 ° C. Next, the compound (1) in Table 1 of the present invention and the compound (41) in Table 2 were mixed at a ratio of 50:50, dissolved in toluene at a concentration of 0.5 wt%, and 20 nm by spin coating. A hole transport layer having a thickness of 5 mm was formed and polymerized at 200 ° C. Next, the compound (A) shown below was dissolved in toluene at a concentration of 1.0 wt%, a light emitting layer having a thickness of 40 nm was formed by spin coating, and dried at 100 ° C. Further, a compound (B) shown below is vacuum-deposited thereon to form an electron injection layer having a film thickness of 20 nm, and then 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are vapor-deposited thereon. An electrode was formed to obtain an organic EL element. When this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 550 cd / m 2 was obtained. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.11). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 9.
実施例42〜80
実施例41のかわりに、表1〜表7に示す、それぞれの実施例に対応する化合物を用いる以外は実施例41と同様に素子を作成した。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表9に示す。
Examples 42-80
A device was produced in the same manner as in Example 41 except that compounds corresponding to the respective examples shown in Tables 1 to 7 were used instead of Example 41. The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 9.
比較例1
実施例41において、正孔輸送層を製膜しない以外は、実施例41と同様に素子を作成した。この素子を6Vに駆動させた際の色度は、CIE(x,y)=(0.15,0.15)の青色発光であった。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度と半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表9に示す。
Comparative Example 1
In Example 41, an element was prepared in the same manner as in Example 41 except that the hole transport layer was not formed. The chromaticity when this element was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.15). The device was measured for luminance and half-life when the device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 9.
表9
表9から明らかなように、本発明の化合物はいずれも、比較例1で作成した素子よりも、長寿命で且つ、高い輝度が得られた。 As is clear from Table 9, all of the compounds of the present invention had a longer lifetime and higher luminance than the device prepared in Comparative Example 1.
実施例81
洗浄したITO電極付きガラス板上に、PEDOT/PSS(ポリ(3,4−エチレンジオキシ)−2,5−チオフェン/ポリスチレンスルホン酸、Bayer社製BAYTRON P VP CH8000)をスピンコート法にて製膜し、200℃乾燥により、膜厚60nmの正孔注入層を得た。次いで、本発明の表1中の化合物(1)と表4中の化合物(101)とを50:50の割合で混合し、0.5wt%の濃度でトルエンに溶解させ、スピンコーティング法により20nmの膜厚の正孔輸送層を製膜し200℃にて重合させた。ついで、以下に示す化合物(C)と化合物(D)を98:2の割合で混合し、1.0wt%の濃度でトルエンに溶解させ、スピンコーティング法により40nmの膜厚の発光層を製膜し100℃にて乾燥させた。さらにその上に、以下に示す化合物(B)を、真空蒸着して膜厚20nmの電子注入層を作成し、その上に、まずフッ化リチウムを1nm、次いでアルミニウム(Al)を150nm蒸着して電極を形成し、有機EL素子を得た。この素子について通電試験を行ったところ、最大発光輝度700cd/m2の青色発光が得られた。この素子を6Vに駆動させた際の色度は、CIE(x,y)=(0.15,0.12)の青色発光であった。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表10に示す。
Example 81
PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid, BAYTRON P VP CH8000 manufactured by Bayer) manufactured on a cleaned glass plate with an ITO electrode by a spin coating method Then, a hole injection layer having a film thickness of 60 nm was obtained by drying at 200 ° C. Next, the compound (1) in Table 1 of the present invention and the compound (101) in Table 4 were mixed at a ratio of 50:50, dissolved in toluene at a concentration of 0.5 wt%, and 20 nm by spin coating. A hole transport layer having a thickness of 5 mm was formed and polymerized at 200 ° C. Next, the compound (C) and the compound (D) shown below are mixed in a ratio of 98: 2, dissolved in toluene at a concentration of 1.0 wt%, and a light-emitting layer having a thickness of 40 nm is formed by spin coating. And dried at 100 ° C. Further, a compound (B) shown below is vacuum-deposited thereon to form an electron injection layer having a film thickness of 20 nm, and then 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are vapor-deposited thereon. An electrode was formed to obtain an organic EL element. When this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 700 cd / m 2 was obtained. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.12). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 10.
実施例82〜120
実施例41のかわりに、表1〜表7に示す、それぞれの実施例に対応する化合物を用いる以外は実施例81と同様に素子を作成した。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表10に示す。
Examples 82-120
A device was prepared in the same manner as in Example 81 except that compounds corresponding to the respective examples shown in Tables 1 to 7 were used instead of Example 41. The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 10.
比較例2
実施例81において、正孔輸送層を製膜しない以外は、実施例81と同様に素子を作成した。この素子を6Vに駆動させた際の色度は、CIE(x,y)=(0.15,0.14)の青色発光であった。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度と半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表10に示す。
Comparative Example 2
In Example 81, an element was prepared in the same manner as in Example 81 except that the hole transport layer was not formed. The chromaticity when this element was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.14). The device was measured for luminance and half-life when the device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 10.
表10
表10から明らかなように、本発明の化合物はいずれも、比較例2で作成した素子よりも、長寿命で且つ、高い輝度が得られた。 As is clear from Table 10, all of the compounds of the present invention had a longer lifetime and higher luminance than the device prepared in Comparative Example 2.
実施例121
洗浄したITO電極付きガラス板上に、本発明の表1中の化合物(1)と表6中の化合物(171)と以下に示す化合物(E)とを45:45:10の割合で混合し、0.5wt%の濃度でトルエンに溶解させ、スピンコーティング法により20nmの膜厚の正孔注入層を製膜し200℃にて重合させた。ついで、以下に示した化合物(F)と化合物(G)を、98:2の割合で混合し、1.0wt%の濃度でトルエンに溶解させ、スピンコーティング法により40nmの膜厚の発光層を製膜し100℃にて乾燥させた。さらにその上に、以下に示す化合物(B)を、真空蒸着して膜厚20nmの電子注入層を作成し、その上に、まずフッ化リチウムを1nm、次いでアルミニウム(Al)を150nm蒸着して電極を形成し、有機EL素子を得た。この素子について通電試験を行ったところ、最大発光輝度750cd/m2の青色発光が得られた。この素子を6Vに駆動させた際の色度は、CIE(x,y)=(0.14,0.11)の青色発光であった。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表7に示す。
Example 121
On the cleaned glass plate with ITO electrode, the compound (1) in Table 1 of the present invention, the compound (171) in Table 6 and the compound (E) shown below were mixed at a ratio of 45:45:10. , Dissolved in toluene at a concentration of 0.5 wt%, a 20 nm thick hole injection layer was formed by spin coating and polymerized at 200 ° C. Next, the compound (F) and the compound (G) shown below are mixed at a ratio of 98: 2, dissolved in toluene at a concentration of 1.0 wt%, and a light-emitting layer having a thickness of 40 nm is formed by spin coating. A film was formed and dried at 100 ° C. Further, a compound (B) shown below is vacuum-deposited thereon to form an electron injection layer having a film thickness of 20 nm, and then 1 nm of lithium fluoride and then 150 nm of aluminum (Al) are vapor-deposited thereon. An electrode was formed to obtain an organic EL element. When this device was subjected to an energization test, blue light emission with a maximum light emission luminance of 750 cd / m 2 was obtained. The chromaticity when this device was driven to 6 V was blue light emission of CIE (x, y) = (0.14, 0.11). The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 7.
実施例122〜160
実施例121のかわりに、表1〜表7に示す、それぞれの実施例に対応する化合物を用いる以外は実施例121と同様に素子を作成した。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表11に示す。
Examples 122-160
A device was prepared in the same manner as in Example 121 except that the compounds corresponding to each Example shown in Tables 1 to 7 were used instead of Example 121. The luminance half life when this device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ) was measured. Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 11.
比較例3
実施例121において、正孔注入層にPEDOT/PSSを製膜する以外は、実施例121と同様に素子を作成した。この素子を6Vに駆動させた際の色度は、CIE(x,y)=(0.15,0.14)の青色発光であった。この素子を発光輝度500(cd/m2)で室温にて定電流駆動したときの輝度と半減寿命を測定した。また、電流密度12.5mA/cm2で駆動させた時の初期輝度、および60℃の環境で100時間連続駆動させた後の輝度を測定した。結果を表11に示す。
Comparative Example 3
In Example 121, an element was prepared in the same manner as in Example 121 except that PEDOT / PSS was formed on the hole injection layer. The chromaticity when this element was driven to 6 V was blue light emission of CIE (x, y) = (0.15, 0.14). The device was measured for luminance and half-life when the device was driven at a constant current at room temperature with an emission luminance of 500 (cd / m 2 ). Further, the initial luminance when driven at a current density of 12.5 mA / cm 2 and the luminance after continuous driving for 100 hours in an environment of 60 ° C. were measured. The results are shown in Table 11.
表11
表11から明らかなように、本発明の化合物はいずれも、比較例3で作成した素子よりも、長寿命で且つ、高い輝度が得られた。 As is apparent from Table 11, all the compounds of the present invention had a longer lifetime and higher luminance than the device prepared in Comparative Example 3.
以上のように、本発明で示された有機エレクトロルミネッセンス素子用材料を用いることにより、高い性能のEL素子が作成できる。比較化合物に対して格段に高い性能が発揮されることは明らかであり、有機EL素子の高い発光効率、低駆動電圧化、長寿命化、高色純度な青色発光が達成できる。 As described above, a high-performance EL element can be created by using the organic electroluminescence element material shown in the present invention. It is clear that remarkably high performance is exhibited with respect to the comparative compound, and high emission efficiency, low drive voltage, long life, and high color purity blue light emission of the organic EL element can be achieved.
Claims (6)
一般式[1]
R3およびR4は、それぞれ独立に、置換もしくは未置換の2価の脂肪族炭化水素基、置換もしくは未置換の2価の芳香族炭化水素基、置換もしくは未置換の2価の脂肪族複素環基、または、置換もしくは未置換の2価の芳香族複素環基を表す。
J1およびJ2は、それぞれ独立に、下記一般式[2]、または、一般式[3]で表される基である。)
一般式[2]
R6は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、
X1は、直接結合、酸素原子、または、硫黄原子を表す。)
一般式[3]
R8は、水素原子、置換もしくは未置換の1価の脂肪族炭化水素基、置換もしくは未置換の1価の芳香族炭化水素基、置換もしくは未置換の1価の脂肪族複素環基、または、置換もしくは未置換の1価の芳香族複素環基を表し、
X2は、直接結合、酸素原子、または、硫黄原子を表す。) A polymerizable compound represented by the following general formula [1].
General formula [1]
R 3 and R 4 each independently represents a substituted or unsubstituted divalent aliphatic hydrocarbon group, a substituted or unsubstituted divalent aromatic hydrocarbon group, a substituted or unsubstituted divalent aliphatic complex, A cyclic group or a substituted or unsubstituted divalent aromatic heterocyclic group is represented.
J 1 and J 2 are each independently a group represented by the following general formula [2] or general formula [3]. )
General formula [2]
R 6 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X 1 represents a direct bond, an oxygen atom, or a sulfur atom. )
General formula [3]
R 8 represents a hydrogen atom, a substituted or unsubstituted monovalent aliphatic hydrocarbon group, a substituted or unsubstituted monovalent aromatic hydrocarbon group, a substituted or unsubstituted monovalent aliphatic heterocyclic group, or Represents a substituted or unsubstituted monovalent aromatic heterocyclic group,
X 2 represents a direct bond, an oxygen atom, or a sulfur atom. )
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012078541A JP2013209300A (en) | 2012-03-30 | 2012-03-30 | Material for organic electroluminescence device, and its use |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012078541A JP2013209300A (en) | 2012-03-30 | 2012-03-30 | Material for organic electroluminescence device, and its use |
Publications (1)
Publication Number | Publication Date |
---|---|
JP2013209300A true JP2013209300A (en) | 2013-10-10 |
Family
ID=49527524
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2012078541A Withdrawn JP2013209300A (en) | 2012-03-30 | 2012-03-30 | Material for organic electroluminescence device, and its use |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP2013209300A (en) |
Cited By (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2015110527A (en) * | 2013-12-06 | 2015-06-18 | 信越化学工業株式会社 | Organosilicon compound having oxetane ring and production method thereof |
WO2016030331A1 (en) * | 2014-08-25 | 2016-03-03 | Osram Oled Gmbh | Organic light-emitting component and method for producing an organic light-emitting component |
FR3032970A1 (en) * | 2015-02-23 | 2016-08-26 | Centre Nat De La Rech Scient (Cnrs) | MOLECULAR EMISSIVE MATERIALS PHOTOPOLYMERIZABLE |
JP2016533394A (en) * | 2013-09-30 | 2016-10-27 | エルジー・ケム・リミテッド | Polymerizable liquid crystal compound, liquid crystal composition containing the same, and optical film |
TWI570218B (en) * | 2015-07-03 | 2017-02-11 | 友達光電股份有限公司 | Organic emitting device |
JP2017059699A (en) * | 2015-09-17 | 2017-03-23 | 日立化成株式会社 | Organic electronics material and use of the same |
JPWO2015145871A1 (en) * | 2014-03-25 | 2017-04-13 | 住友化学株式会社 | Polymer compound and light emitting device using the same |
WO2017119483A1 (en) * | 2016-01-08 | 2017-07-13 | 日立化成株式会社 | Organic electronic material, organic electronic element, and organic electroluminescent element |
WO2018021133A1 (en) * | 2016-07-25 | 2018-02-01 | 日立化成株式会社 | Organic electronic material and use of same |
JP2018039984A (en) * | 2012-04-17 | 2018-03-15 | メルク パテント ゲーエムベーハー | Polymers containing substituted triaryl amine unit and electroluminescence element containing these polymers |
JP2018104338A (en) * | 2016-12-26 | 2018-07-05 | 川崎化成工業株式会社 | Anthracene compound having {(3-methyloxetane-3-yl)methyloxy} group, method for producing the same and use therefor |
US10308735B2 (en) | 2014-12-18 | 2019-06-04 | Samsung Electronics Co., Ltd. | Material for organic light-emitting device and organic light-emitting device including the same |
CN109996828A (en) * | 2016-12-22 | 2019-07-09 | 默克专利有限公司 | Material for electronic device |
CN111247656A (en) * | 2017-10-27 | 2020-06-05 | 日立化成株式会社 | Charge-transporting polymer and organic electronic device |
CN113130836A (en) * | 2019-12-31 | 2021-07-16 | 海信视像科技股份有限公司 | Method for manufacturing organic light-emitting display device |
EP3889130A1 (en) | 2020-03-30 | 2021-10-06 | Ricoh Company, Ltd. | Electrochromic element |
EP3961738A4 (en) * | 2019-04-26 | 2022-05-11 | Showa Denko Materials Co., Ltd. | Organic electronics material and method for preparing charge-carrying polymer |
CN115611792A (en) * | 2022-10-24 | 2023-01-17 | 电子科技大学 | Organic diradical monomolecular device stable at room temperature and preparation method thereof |
TWI842682B (en) | 2017-10-27 | 2024-05-21 | 日商力森諾科股份有限公司 | Charge transporting polymer, charge transporting material, ink composition, organic layer, organic electronic element, organic electroluminescent element, display element, lighting device and display device |
-
2012
- 2012-03-30 JP JP2012078541A patent/JP2013209300A/en not_active Withdrawn
Cited By (31)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2018039984A (en) * | 2012-04-17 | 2018-03-15 | メルク パテント ゲーエムベーハー | Polymers containing substituted triaryl amine unit and electroluminescence element containing these polymers |
JP2016533394A (en) * | 2013-09-30 | 2016-10-27 | エルジー・ケム・リミテッド | Polymerizable liquid crystal compound, liquid crystal composition containing the same, and optical film |
JP2015110527A (en) * | 2013-12-06 | 2015-06-18 | 信越化学工業株式会社 | Organosilicon compound having oxetane ring and production method thereof |
JPWO2015145871A1 (en) * | 2014-03-25 | 2017-04-13 | 住友化学株式会社 | Polymer compound and light emitting device using the same |
EP3124518A4 (en) * | 2014-03-25 | 2017-11-01 | Sumitomo Chemical Company Limited | Polymer compound, and light-emitting element using same |
WO2016030331A1 (en) * | 2014-08-25 | 2016-03-03 | Osram Oled Gmbh | Organic light-emitting component and method for producing an organic light-emitting component |
US10308735B2 (en) | 2014-12-18 | 2019-06-04 | Samsung Electronics Co., Ltd. | Material for organic light-emitting device and organic light-emitting device including the same |
FR3032970A1 (en) * | 2015-02-23 | 2016-08-26 | Centre Nat De La Rech Scient (Cnrs) | MOLECULAR EMISSIVE MATERIALS PHOTOPOLYMERIZABLE |
TWI570218B (en) * | 2015-07-03 | 2017-02-11 | 友達光電股份有限公司 | Organic emitting device |
JP2017059699A (en) * | 2015-09-17 | 2017-03-23 | 日立化成株式会社 | Organic electronics material and use of the same |
TWI848266B (en) | 2016-01-08 | 2024-07-11 | 日商力森諾科股份有限公司 | Organic electronic materials, organic electronic components and organic electroluminescent components |
JPWO2017119483A1 (en) * | 2016-01-08 | 2018-10-25 | 日立化成株式会社 | Organic electronics material, organic electronics element, and organic electroluminescence element |
WO2017119483A1 (en) * | 2016-01-08 | 2017-07-13 | 日立化成株式会社 | Organic electronic material, organic electronic element, and organic electroluminescent element |
TWI764881B (en) * | 2016-01-08 | 2022-05-21 | 日商昭和電工材料股份有限公司 | Organic electronic materials, organic electronic components and organic electroluminescent components |
EP3401973A4 (en) * | 2016-01-08 | 2019-07-31 | Hitachi Chemical Co., Ltd. | Organic electronic material, organic electronic element, and organic electroluminescent element |
KR102524730B1 (en) | 2016-01-08 | 2023-04-24 | 가부시끼가이샤 레조낙 | Organic electronic material, organic electronic element, and organic electroluminescent element |
JP2020115554A (en) * | 2016-01-08 | 2020-07-30 | 日立化成株式会社 | Organic electronic material, organic electronic element, and organic electroluminescent element |
KR20200109399A (en) * | 2016-01-08 | 2020-09-22 | 히타치가세이가부시끼가이샤 | Organic electronic material, organic electronic element, and organic electroluminescent element |
US10840452B2 (en) | 2016-01-08 | 2020-11-17 | Hitachi Chemical Company, Ltd. | Organic electronic material including charge transport polymer or oligomer having structural unit containing aromatic amine structure substituted with fluorine atom, organic electronic element, and organic electroluminescent element |
WO2018021133A1 (en) * | 2016-07-25 | 2018-02-01 | 日立化成株式会社 | Organic electronic material and use of same |
CN109996828A (en) * | 2016-12-22 | 2019-07-09 | 默克专利有限公司 | Material for electronic device |
US11261291B2 (en) | 2016-12-22 | 2022-03-01 | Merck Patent Gmbh | Materials for electronic devices |
JP2018104338A (en) * | 2016-12-26 | 2018-07-05 | 川崎化成工業株式会社 | Anthracene compound having {(3-methyloxetane-3-yl)methyloxy} group, method for producing the same and use therefor |
CN111247656B (en) * | 2017-10-27 | 2023-03-24 | 日立化成株式会社 | Charge-transporting polymer and organic electronic device |
CN111247656A (en) * | 2017-10-27 | 2020-06-05 | 日立化成株式会社 | Charge-transporting polymer and organic electronic device |
TWI842682B (en) | 2017-10-27 | 2024-05-21 | 日商力森諾科股份有限公司 | Charge transporting polymer, charge transporting material, ink composition, organic layer, organic electronic element, organic electroluminescent element, display element, lighting device and display device |
EP3961738A4 (en) * | 2019-04-26 | 2022-05-11 | Showa Denko Materials Co., Ltd. | Organic electronics material and method for preparing charge-carrying polymer |
CN113130836A (en) * | 2019-12-31 | 2021-07-16 | 海信视像科技股份有限公司 | Method for manufacturing organic light-emitting display device |
EP3889130A1 (en) | 2020-03-30 | 2021-10-06 | Ricoh Company, Ltd. | Electrochromic element |
CN115611792A (en) * | 2022-10-24 | 2023-01-17 | 电子科技大学 | Organic diradical monomolecular device stable at room temperature and preparation method thereof |
CN115611792B (en) * | 2022-10-24 | 2024-03-22 | 电子科技大学 | Organic double-free radical single-molecule device stable at room temperature and preparation method thereof |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5821602B2 (en) | Material for organic electroluminescence device and use thereof | |
JP2013209300A (en) | Material for organic electroluminescence device, and its use | |
JP5874242B2 (en) | Material for organic electroluminescence device and use thereof | |
JP2013155294A (en) | Material for organic electroluminescence element and use of the same | |
JP2013036023A (en) | Material for organic electroluminescent element and application of the same | |
JP5416906B2 (en) | Fluorescent compound, luminescent ink composition, and organic EL device | |
JP5691192B2 (en) | Material for organic electroluminescence device and use thereof | |
JP5110198B1 (en) | Material for organic electroluminescence device and use thereof | |
JP5673043B2 (en) | Organic electroluminescence device | |
JP4990685B2 (en) | Fluorescent material, luminescent ink composition, and organic EL device | |
JP5152210B2 (en) | Material for organic electroluminescence device and use thereof | |
CN113429395B (en) | Imidazole derivative, organic electroluminescent material, light-emitting element, and consumer product | |
JP6056367B2 (en) | Material for organic electroluminescence device and use thereof | |
KR101382373B1 (en) | Cyclopentafluorene compound and organic light emitting device including the same | |
JP2012190863A (en) | Material for organic electroluminescent element and use thereof | |
WO2008153338A2 (en) | Organic metal complexes derivative and organic light emitting devices using the same | |
CN112940048A (en) | Metal complex, organic electroluminescent material, organic electroluminescent element, and electroluminescent device | |
JP2012188637A (en) | Material for organic electroluminescence element and application thereof | |
JP2012028711A (en) | Material for organic electroluminescent element and use of the same | |
JP5565201B2 (en) | Spiro compound and material for organic electroluminescence device | |
TW201509883A (en) | Hole transporting varnish for metal positive electrodes and composite metal positive electrode | |
JP2013179198A (en) | Material for organic electroluminescent element and application thereof | |
JP5617432B2 (en) | Organic electroluminescence device | |
JP2011132419A (en) | Material for organic electroluminescent element and application thereof | |
JP2014078701A (en) | Material for organic thin film solar cell element and application thereof |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20141106 |
|
A761 | Written withdrawal of application |
Free format text: JAPANESE INTERMEDIATE CODE: A761 Effective date: 20150206 |