WO2022244689A1 - Pyrimidine compound, material for organic electroluminescent element, and organic electroluminescent element - Google Patents
Pyrimidine compound, material for organic electroluminescent element, and organic electroluminescent element Download PDFInfo
- Publication number
- WO2022244689A1 WO2022244689A1 PCT/JP2022/020179 JP2022020179W WO2022244689A1 WO 2022244689 A1 WO2022244689 A1 WO 2022244689A1 JP 2022020179 W JP2022020179 W JP 2022020179W WO 2022244689 A1 WO2022244689 A1 WO 2022244689A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- layer
- pyrimidine compound
- electron
- organic electroluminescent
- Prior art date
Links
- -1 Pyrimidine compound Chemical class 0.000 title claims abstract description 59
- 239000000463 material Substances 0.000 title abstract description 40
- 238000005401 electroluminescence Methods 0.000 claims description 36
- 125000004432 carbon atom Chemical group C* 0.000 claims description 22
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 17
- 125000001624 naphthyl group Chemical group 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 15
- 125000004076 pyridyl group Chemical group 0.000 claims description 11
- 125000000217 alkyl group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 5
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 5
- 125000005551 pyridylene group Chemical group 0.000 claims description 5
- 125000004957 naphthylene group Chemical group 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000010410 layer Substances 0.000 description 157
- 238000002347 injection Methods 0.000 description 36
- 239000007924 injection Substances 0.000 description 36
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- 230000005525 hole transport Effects 0.000 description 18
- 239000010408 film Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 15
- 150000001875 compounds Chemical class 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000000034 method Methods 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 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 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000002356 single layer Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 5
- USQYYBOQKDWTEC-UHFFFAOYSA-N C(C=C1)=CC=C1C(C=C1)=CC=C1C1=NC(C2=CC(C3=CC=CN=C3C3=CC=CC=C3)=CC(C3=CC=CC=C3)=C2)=NC(C(C=C2)=CC=C2C2=CC=CC=C2)=C1 Chemical compound C(C=C1)=CC=C1C(C=C1)=CC=C1C1=NC(C2=CC(C3=CC=CN=C3C3=CC=CC=C3)=CC(C3=CC=CC=C3)=C2)=NC(C(C=C2)=CC=C2C2=CC=CC=C2)=C1 USQYYBOQKDWTEC-UHFFFAOYSA-N 0.000 description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 5
- 238000000151 deposition Methods 0.000 description 5
- 230000008021 deposition Effects 0.000 description 5
- 239000011777 magnesium Substances 0.000 description 5
- 229910052749 magnesium Inorganic materials 0.000 description 5
- 229910000160 potassium phosphate Inorganic materials 0.000 description 5
- 150000003230 pyrimidines Chemical class 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 4
- 125000000714 pyrimidinyl group Chemical group 0.000 description 4
- 238000001771 vacuum deposition Methods 0.000 description 4
- UGOMMVLRQDMAQQ-UHFFFAOYSA-N xphos Chemical group CC(C)C1=CC(C(C)C)=CC(C(C)C)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 UGOMMVLRQDMAQQ-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 229910052769 Ytterbium Inorganic materials 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- 238000007740 vapor deposition Methods 0.000 description 3
- QMKLHPJUOGNMPU-UHFFFAOYSA-N 2-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyridine Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=CN=C1C1=CC=CC=C1 QMKLHPJUOGNMPU-UHFFFAOYSA-N 0.000 description 2
- XMOXBKZALHQJFT-UHFFFAOYSA-N CC1=CN=C(C2=CC=CC=C2)C(C2=CC(C3=CC=CC=C3)=CC(C3=NC(C(C=C4)=CC=C4C4=CC=CC=C4)=CC(C(C=C4)=CC=C4C4=CC=CC=C4)=N3)=C2)=C1 Chemical compound CC1=CN=C(C2=CC=CC=C2)C(C2=CC(C3=CC=CC=C3)=CC(C3=NC(C(C=C4)=CC=C4C4=CC=CC=C4)=CC(C(C=C4)=CC=C4C4=CC=CC=C4)=N3)=C2)=C1 XMOXBKZALHQJFT-UHFFFAOYSA-N 0.000 description 2
- VLWPLCZTUADTGT-UHFFFAOYSA-N ClC1=CC(C2=CC=CC=C2)=CC(C2(C(C=C3)=CC=C3C3=CC=CC=C3)NC(C(C=C3)=CC=C3C3=CC=CC=C3)=NC=C2)=C1 Chemical compound ClC1=CC(C2=CC=CC=C2)=CC(C2(C(C=C3)=CC=C3C3=CC=CC=C3)NC(C(C=C3)=CC=C3C3=CC=CC=C3)=NC=C2)=C1 VLWPLCZTUADTGT-UHFFFAOYSA-N 0.000 description 2
- GSJUWSFLFHUTRT-UHFFFAOYSA-N ClC1=CC(C2=CC=CC=C2)=CC(C2=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=CC(C(C=C3)=CC=C3C3=CC=CC=C3)=N2)=C1 Chemical compound ClC1=CC(C2=CC=CC=C2)=CC(C2=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=CC(C(C=C3)=CC=C3C3=CC=CC=C3)=N2)=C1 GSJUWSFLFHUTRT-UHFFFAOYSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- GOZPTOHMTKTIQP-UHFFFAOYSA-N OC1=CC=CC2=CC=C3C=CC(=NC3=C21)C(=O)O Chemical compound OC1=CC=CC2=CC=C3C=CC(=NC3=C21)C(=O)O GOZPTOHMTKTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 2
- 125000005561 phenanthryl group Chemical group 0.000 description 2
- 235000011009 potassium phosphates Nutrition 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 230000002269 spontaneous effect Effects 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 2
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 1
- WOVPECVORHUBQG-UHFFFAOYSA-N 2-chloro-4,6-bis(4-phenylphenyl)pyrimidine Chemical compound N=1C(Cl)=NC(C=2C=CC(=CC=2)C=2C=CC=CC=2)=CC=1C(C=C1)=CC=C1C1=CC=CC=C1 WOVPECVORHUBQG-UHFFFAOYSA-N 0.000 description 1
- ZGNCKIDXVHSMJL-UHFFFAOYSA-N 2-methylquinoline-8-carboxylic acid Chemical compound C1=CC=C(C(O)=O)C2=NC(C)=CC=C21 ZGNCKIDXVHSMJL-UHFFFAOYSA-N 0.000 description 1
- JIHDJVLBNUGKHB-UHFFFAOYSA-N 3-chloro-5-methyl-2-phenylpyridine Chemical compound ClC1=CC(C)=CN=C1C1=CC=CC=C1 JIHDJVLBNUGKHB-UHFFFAOYSA-N 0.000 description 1
- DDTHMESPCBONDT-UHFFFAOYSA-N 4-(4-oxocyclohexa-2,5-dien-1-ylidene)cyclohexa-2,5-dien-1-one Chemical compound C1=CC(=O)C=CC1=C1C=CC(=O)C=C1 DDTHMESPCBONDT-UHFFFAOYSA-N 0.000 description 1
- ZYASLTYCYTYKFC-UHFFFAOYSA-N 9-methylidenefluorene Chemical compound C1=CC=C2C(=C)C3=CC=CC=C3C2=C1 ZYASLTYCYTYKFC-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- AIRCTMFFNKZQPN-UHFFFAOYSA-N AlO Inorganic materials [Al]=O AIRCTMFFNKZQPN-UHFFFAOYSA-N 0.000 description 1
- 229910017109 AlON Inorganic materials 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- PYGIWPWYFIMLOO-UHFFFAOYSA-N C(C=C1)=CC=C1C(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2C2=CC=CC=C2)=NC(C2=CC(C3=CC=CN=C3C3=CC=CC=C3)=CC(C3=CC=CN=C3C3=CC=CC=C3)=C2)=N1 Chemical compound C(C=C1)=CC=C1C(C=C1)=CC=C1C1=CC(C(C=C2)=CC=C2C2=CC=CC=C2)=NC(C2=CC(C3=CC=CN=C3C3=CC=CC=C3)=CC(C3=CC=CN=C3C3=CC=CC=C3)=C2)=N1 PYGIWPWYFIMLOO-UHFFFAOYSA-N 0.000 description 1
- NNAWHKLGNVKWHS-UHFFFAOYSA-N CC1(C)OB(C(CC(C2=CC=CC=C2)=C2)(C=C2Cl)C2=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=CC(C(C=C3)=CC=C3C3=CC=CC=C3)=N2)OC1(C)C Chemical compound CC1(C)OB(C(CC(C2=CC=CC=C2)=C2)(C=C2Cl)C2=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=CC(C(C=C3)=CC=C3C3=CC=CC=C3)=N2)OC1(C)C NNAWHKLGNVKWHS-UHFFFAOYSA-N 0.000 description 1
- 101100016516 Caenorhabditis elegans hbl-1 gene Proteins 0.000 description 1
- JMIVLNVAZDHVHR-UHFFFAOYSA-N ClC1=CC(C2=NC(C(C=C3)=CC=C3Br)=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=C2)=CC(Br)=C1 Chemical compound ClC1=CC(C2=NC(C(C=C3)=CC=C3Br)=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=C2)=CC(Br)=C1 JMIVLNVAZDHVHR-UHFFFAOYSA-N 0.000 description 1
- ZEMSYDUFAGWKJW-UHFFFAOYSA-N ClC1=CC(C2=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=CC(C(C=C3)=CC=C3C3=CC=CC=C3)=N2)=CC(Br)=C1 Chemical compound ClC1=CC(C2=NC(C(C=C3)=CC=C3C3=CC=CC=C3)=CC(C(C=C3)=CC=C3C3=CC=CC=C3)=N2)=CC(Br)=C1 ZEMSYDUFAGWKJW-UHFFFAOYSA-N 0.000 description 1
- 101000687716 Drosophila melanogaster SWI/SNF-related matrix-associated actin-dependent regulator of chromatin subfamily A containing DEAD/H box 1 homolog Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 101000687741 Mus musculus SWI/SNF-related matrix-associated actin-dependent regulator of chromatin subfamily A containing DEAD/H box 1 Proteins 0.000 description 1
- XFAZZQREFHAALG-UHFFFAOYSA-N N-{1-amino-6-[(5-nitro-2-furoyl)amino]-1-oxohexan-2-yl}-23-(indol-3-yl)-20-oxo-4,7,10,13,16-pentaoxa-19-azatricosan-1-amide Chemical compound C=1NC2=CC=CC=C2C=1CCCC(=O)NCCOCCOCCOCCOCCOCCC(=O)NC(C(=O)N)CCCCNC(=O)C1=CC=C([N+]([O-])=O)O1 XFAZZQREFHAALG-UHFFFAOYSA-N 0.000 description 1
- ZCQWOFVYLHDMMC-UHFFFAOYSA-N Oxazole Chemical compound C1=COC=N1 ZCQWOFVYLHDMMC-UHFFFAOYSA-N 0.000 description 1
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000282320 Panthera leo Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910004541 SiN Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 229910004166 TaN Inorganic materials 0.000 description 1
- 229910004158 TaO Inorganic materials 0.000 description 1
- 229910003071 TaON Inorganic materials 0.000 description 1
- 229910010282 TiON Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 125000000641 acridinyl group Chemical group C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- RJGDLRCDCYRQOQ-UHFFFAOYSA-N anthrone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3CC2=C1 RJGDLRCDCYRQOQ-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- XOYLJNJLGBYDTH-UHFFFAOYSA-M chlorogallium Chemical compound [Ga]Cl XOYLJNJLGBYDTH-UHFFFAOYSA-M 0.000 description 1
- 125000002676 chrysenyl group Chemical group C1(=CC=CC=2C3=CC=C4C=CC=CC4=C3C=CC12)* 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 description 1
- YLQWCDOCJODRMT-UHFFFAOYSA-N fluoren-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3C2=C1 YLQWCDOCJODRMT-UHFFFAOYSA-N 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N germanium monoxide Inorganic materials [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 125000005956 isoquinolyl group Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Inorganic materials [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 1
- XNUVVHVFAAQPQY-UHFFFAOYSA-L manganese(2+) quinolin-8-olate Chemical compound N1=CC=CC2=CC=CC(=C12)[O-].[Mn+2].N1=CC=CC2=CC=CC(=C12)[O-] XNUVVHVFAAQPQY-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WCPAKWJPBJAGKN-UHFFFAOYSA-N oxadiazole Chemical compound C1=CON=N1 WCPAKWJPBJAGKN-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JGBZTJWQMWZVNX-UHFFFAOYSA-N palladium;tricyclohexylphosphane Chemical compound [Pd].C1CCCCC1P(C1CCCCC1)C1CCCCC1.C1CCCCC1P(C1CCCCC1)C1CCCCC1 JGBZTJWQMWZVNX-UHFFFAOYSA-N 0.000 description 1
- FVDOBFPYBSDRKH-UHFFFAOYSA-N perylene-3,4,9,10-tetracarboxylic acid Chemical compound C=12C3=CC=C(C(O)=O)C2=C(C(O)=O)C=CC=1C1=CC=C(C(O)=O)C2=C1C3=CC=C2C(=O)O FVDOBFPYBSDRKH-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 1
- 125000005412 pyrazyl group Chemical group 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 125000005493 quinolyl group Chemical group 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- IBBLKSWSCDAPIF-UHFFFAOYSA-N thiopyran Chemical compound S1C=CC=C=C1 IBBLKSWSCDAPIF-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- KWQNQSDKCINQQP-UHFFFAOYSA-K tri(quinolin-8-yloxy)gallane Chemical compound C1=CN=C2C(O[Ga](OC=3C4=NC=CC=C4C=CC=3)OC=3C4=NC=CC=C4C=CC=3)=CC=CC2=C1 KWQNQSDKCINQQP-UHFFFAOYSA-K 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 125000003960 triphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C3=CC=CC=C3C12)* 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- HTPBWAPZAJWXKY-UHFFFAOYSA-L zinc;quinolin-8-olate Chemical compound [Zn+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 HTPBWAPZAJWXKY-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
Definitions
- the present invention relates to a pyrimidine compound, a material for an organic electroluminescence device containing a pyrimidine compound, and an organic electroluminescence device.
- Patent Documents 1 and 2 disclose pyrimidine compounds that are materials for organic electroluminescent devices.
- one aspect of the present invention is directed to providing a new pyrimidine compound that contributes to the formation of an organic electroluminescent device capable of reducing the driving voltage and improving the current efficiency.
- Still another aspect of the present invention is directed to providing an organic electroluminescence device with reduced driving voltage and improved current efficiency.
- one of X 1 and X 2 is a nitrogen atom and the other is C—H;
- Ar 1 and Ar 2 are each independently represents a phenyl group, a biphenylyl group, or a naphthyl group;
- Ar 3 and Ar 4 are each independently an aryl group having 6 to 20 carbon atoms, or represents a heteroaryl group having 4 to 20 carbon atoms;
- L 1 and L 2 are each independently represents a direct bond, phenylene, pyridylene or naphthylene;
- Ring A is pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
- n is 1 or 2;
- two L1's may be the same or different
- Ar 1 and Ar 2 are identical.
- the pyrimidine compound according to . 3. 1. At least one of Ar 1 and Ar 2 is a 4-biphenylyl group. or 2.
- the pyrimidine compound according to . 4. 1. represented by formulas (E1) to (E10); ⁇ 3.
- a new pyrimidine compound that contributes to the formation of an organic electroluminescent device capable of reducing driving voltage and improving current efficiency.
- FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescence device according to one aspect of the present disclosure
- FIG. 3 is a schematic cross-sectional view showing another example of the layered structure of the organic electroluminescence device according to one aspect of the present disclosure (structure of Device Example-1).
- a pyrimidine compound according to one aspect of the present invention is a pyrimidine compound represented by formula (1).
- one of X 1 and X 2 is a nitrogen atom and the other is C—H;
- Ar 1 and Ar 2 are each independently represents a phenyl group, a biphenylyl group, or a naphthyl group;
- Ar 3 and Ar 4 are each independently an aryl group having 6 to 20 carbon atoms, or represents a heteroaryl group having 4 to 20 carbon atoms;
- L 1 and L 2 are each independently represents a direct bond, phenylene, pyridylene or naphthylene;
- Ring A is pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
- n is 1 or 2;
- two L1's may be the same or different
- Ar 1 and Ar 2 are preferably a biphenylyl group or a naphthyl group, more preferably a 4-biphenylyl group.
- Ar 1 and Ar 2 are preferably the same.
- Ar 3 and Ar 4 are each independently an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms.
- aryl groups having 6 to 20 carbon atoms include phenyl group, naphthyl group, phenanthryl group, anthonyl group, pyrenyl group, pyranyl group, fluorenyl group, dimethylfluorenyl group, triphenylenyl group, fluoranthenyl group and chrysenyl. and the like.
- heteroaryl groups having 4 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a pyrazyl group, a quinolyl group, an isoquinolyl group, a nadityridinyl group and an acridinyl group.
- Ar 3 and Ar 4 are preferably a phenyl group, a naphthyl group, a phenanthryl group, or a pyridyl group.
- Ring A is pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and Ar 3 and L 1 are each bonded to two adjacent carbon atoms of the pyridine ring.
- Ring A is specifically represented by formulas (A-1) and (A-2).
- each dashed line independently indicates the position where Ar 3 or L 1 is substituted.
- the pyridine ring is substituted with one or more groups selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group. good too.
- a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 5 carbon atoms and a CN group are preferable, and a phenyl group, a pyridyl group, a naphthyl group and an alkyl group having 1 to 5 carbon atoms are more preferable, and a phenyl group.
- pyridyl group, naphthyl group and methyl group are more preferred, and phenyl group, pyridyl group and methyl group are particularly preferred.
- L 1 and L 2 each independently represent a direct bond, phenylene, pyridylene or naphthylene.
- L 1 and L 2 are each independently a direct bond, phenylene, or pyridylene.
- One of X 1 and X 2 is a nitrogen atom and the other is CH.
- Pyrimidine compounds can be used, for example, in organic electronic devices such as organic electroluminescence devices and photoelectric devices.
- a material for an organic electroluminescence device according to one aspect of the present invention contains the pyrimidine compound.
- a pyrimidine compound can be used, for example, as an electron transport material for an organic electroluminescence device.
- the structural reason why the pyrimidine compound according to one aspect of the present invention exhibits a low driving voltage as, for example, an electron-transporting material for an organic electroluminescence device is presumed to be as follows. ⁇ Structural reasons for low drive voltage>
- the triazine ring incorporates three highly electronegative nitrogen atoms into the ring structure to increase the electron affinity of the ring itself, thereby having a high electron transport property. Attempts have also been made to increase electron injection properties from the cathode by having a pyridine ring in the molecule of the triazine compound.
- the high electron affinity of the triazine ring can inhibit electron injection into the widely used light-emitting layer and hole-blocking layer.
- the pyridine ring further increases the electron affinity of the molecule and can inhibit electron injection into the light-emitting layer and the hole-blocking layer.
- the pyrimidine ring contains a plurality of nitrogen atoms like the triazine ring, but the number is smaller than that of the triazine ring, and the electron affinity is low, so electron injection into the light-emitting layer or the hole-blocking layer is promoted.
- the pyrimidine compound according to this aspect has Ar and L 1 bonded to the adjacent carbon atoms of the pyridine ring, thereby increasing the dihedral angle of the aromatic ring adjacent to the pyridine ring and increasing the electron affinity of the molecule. restrains it from rising. This makes it possible to improve the electron injection from the cathode while keeping the electron affinity low. This enhanced electron injection can exhibit high current efficiency.
- the pyrimidine ring itself has a large dipole moment.
- organic molecules In an organic thin film, it is known that when organic molecules have a dipole moment, the organic molecules spontaneously orient to form a film having an orderly structure resembling a crystal structure. It is generally known that highly amorphous films are required for organic films used in organic electroluminescence devices because films with high crystallinity cause defects in the film and hinder charge transport.
- the spontaneous orientation of the organic molecules raises the sublimation temperature. This promotes thermal decomposition during the production of the organic electroluminescence device, and eventually influences deterioration of the durability of the organic electroluminescence device due to contamination of decomposition products.
- a compound having a pyrimidine ring can promote electron injection into the light-emitting layer or the hole-blocking layer, but has the problem of suppressing electron transport in the film.
- the pyrimidine compound of one embodiment of the present invention Ar 3 and the ring A in formula (1) form a high steric hindrance, which suppresses the spontaneous orientation of molecules and has a high amorphous property. It is possible. Therefore, the pyrimidine compound, which is one embodiment of the present invention, promotes electron injection into the hole-blocking layer and does not suppress electron transport in the film, so that driving voltage can be reduced.
- the pyrimidine compound that is one embodiment of the present invention also contributes to lowering the sublimation temperature, it is possible to contribute to suppression of thermal decomposition of the material and suppression of deterioration in durability of the organic electroluminescent element.
- Organic electroluminescence device (hereinafter sometimes simply referred to as an organic electroluminescence device) according to one aspect of the present invention will be described below.
- An organic electroluminescent device contains a pyrimidine compound.
- the configuration of the organic electroluminescent element is not particularly limited, but includes, for example, the configurations (i) to (vi) shown below.
- anode/light emitting layer/cathode ii: anode/hole transport layer/light emitting layer/cathode (iii): anode/light emitting layer/electron transport layer/cathode (iv): anode/hole transport layer/ Emissive layer/electron transport layer/cathode (v): anode/hole injection layer/hole transport layer/emissive layer/electron transport layer/electron injection layer/cathode (vi): anode/hole injection layer/hole transport Layer/electron-blocking layer/light-emitting layer/hole-blocking layer/electron-transporting layer/electron-injecting layer/cathode
- the pyrimidine compound may be contained in any of the above layers, but the organic electroluminescent device exhibits excellent light-emitting properties.
- the pyrimidine compound is contained in one or more layers selected from the group consisting of a light-emitting layer, a hole-blocking layer, an electron-transporting layer, and an electron-injecting layer. is preferred.
- the organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type device configuration, but the organic electroluminescent device according to one aspect of the present invention is not limited to the bottom emission type device configuration. do not have. That is, the organic electroluminescence device according to one aspect of the present invention may have other known device configurations such as top emission type.
- FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescence device according to one aspect of the present invention.
- the organic electroluminescent device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8 in this order.
- some of these layers may be omitted, or conversely, other layers may be added.
- a hole-blocking layer may be provided between the light-emitting layer 5 and the electron-transporting layer 6, the hole-injecting layer 3 may be omitted, and the hole-transporting layer 4 may be provided directly on the anode 2. good too.
- a single layer having the functions of a plurality of layers such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of. Further, for example, each of the single-layer hole transport layer 4 and the single-layer electron transport layer 6 may be composed of a plurality of layers.
- ⁇ Layer containing pyrimidine compound> In the structural example shown in FIG. 1, the organic electroluminescence device 100 contains the above pyrimidine compound in one or more layers selected from the group consisting of the light-emitting layer 5, the electron transport layer 6 and the electron injection layer .
- the electron transport layer 6 preferably contains a pyrimidine compound.
- the pyrimidine compound may be contained in a plurality of layers included in the organic electroluminescence device.
- An organic electroluminescence device 100 in which the electron transport layer 6 contains a pyrimidine compound will be described below.
- the substrate 1 is not particularly limited, and substrates that can be used in ordinary organic electroluminescence devices can be used. For example, a glass plate, a quartz plate, a plastic plate and the like can be used.
- An anode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
- the material for the anode compounds that can be used in ordinary organic electroluminescence devices can be used. Examples include metals, alloys, electrically conductive compounds, and mixtures thereof with a large work function (eg, 4 eV or more). Specific examples of materials for the anode include metals such as Au; conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO. [Hole injection layer 3, hole transport layer 4] A hole injection layer 3 and a hole transport layer 4 are provided in this order from the anode 2 side between the anode 2 and a light emitting layer 5 to be described later.
- the material for the hole injection layer and the hole transport layer has at least one of hole injection, hole transport, and electron barrier properties.
- Materials for the hole injection layer and the hole transport layer may be either organic or inorganic, and compounds that can be used in ordinary organic electroluminescence devices can be used.
- the hole injection layer and the hole transport layer may have a single structure composed of one or more materials, or may have a laminated structure composed of multiple layers of the same composition or different compositions.
- the hole-transporting layer 4 may have a laminated structure of two or more layers, and is provided in this order from the anode 2 side with a first hole-transporting layer 41 and a second hole-transporting layer 42 .
- the transport layer 42 can be used as an electron blocking layer in the configuration (vi) above.
- a light-emitting layer 5 is provided between the hole-transporting layer 4 and an electron-transporting layer 6, which will be described later.
- the light emitting layer may consist of a single small molecule material or a single polymer material, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from dopants and can have any color.
- the light-emitting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
- An electron transport layer 6 is provided between the light emitting layer 5 and an electron injection layer 7 which will be described later.
- the electron transport layer preferably contains a pyrimidine compound.
- the electron transport layer may further contain one or more selected from conventionally known electron transport materials.
- the pyrimidine compound When the pyrimidine compound is not contained in the electron-transporting layer but is contained in another layer, one or more selected from conventionally known electron-transporting materials can be used as the electron-transporting material constituting the electron-transporting layer.
- Alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinatolithium (Liq), bis(8-hydroxyquinolinato)zinc, and bis(8-hydroxyquinolinato)copper.
- bis(8-hydroxyquinolinato)manganese tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis (10-hydroxybenzo[h]quinolinate) beryllium, bis(10-hydroxybenzo[h]quinolinate)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinate)(o -cresolato) gallium, bis(2-methyl-8-quinolinato)-1-naphtholato aluminum, bis(2-methyl-8-quinolinato)-2-naphtholato gallium, and the like.
- the electron-transporting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
- An electron injection layer may be provided in the organic electroluminescence device according to this aspect for the purpose of improving electron injection properties and improving device characteristics (e.g., luminous efficiency, low voltage drive, or high durability).
- the electron transport layer 6 may have a laminated structure of two or more layers. can be used as the hole blocking layer in the configuration (vi) above.
- the pyrimidine compound according to one aspect of the present invention can be used in both or either one of the first electron-transporting layer and the second electron-transporting layer.
- An electron injection layer 7 is provided between the electron transport layer 6 and a cathode 8 which will be described later.
- compounds that can be used in ordinary organic electroluminescent devices can be used.
- examples thereof include organic compounds such as fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, and anthrone.
- Materials for the electron injection layer include various oxides and fluorides such as SiO 2 , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, C, and Yb. , nitrides, and oxynitrides. Pyrimidine compounds of the invention can also be used.
- Cathode 8 A cathode 8 is provided on the electron injection layer 7 .
- a metal with a small work function is, for example, a metal of 4 eV or less.
- a mixture of an electron-injecting metal and a second metal that has a higher work function and is more stable such as magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al 2 O 3 ) mixtures, lithium/aluminum mixtures, etc. are preferred.
- Each layer except for the electrodes (anode, cathode) described above is formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a LB (Langmuir-Blodgett method) method. be able to.
- the material for each layer may be used alone, or if necessary, it may be used together with a material such as a binder resin and a solvent.
- the film thickness of each layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 ⁇ m.
- the film thickness of the anode and cathode is preferably 1 ⁇ m or less, more preferably 10 nm or more and 200 nm or less.
- the formation of the layer containing the pyrimidine compound may be used in combination with the conventionally known electron-transporting material. Therefore, for example, a pyrimidine compound and a conventionally known electron-transporting material may be co-deposited, or a layer of a conventionally known electron-transporting material may be laminated on a layer of the pyrimidine compound.
- the organic electroluminescence element may be used as a kind of lamp for illumination or as a light source for exposure, a type of projection device for projecting an image onto a screen or the like, or a type of display for directly viewing still images or moving images. You may use it as a device (display).
- the driving method may be a simple matrix (passive matrix) method or an active matrix method. Further, by using two or more kinds of organic electroluminescent elements having different emission colors, it is possible to produce a full-color display device.
- each layer was produced in the following order according to the film forming conditions of each layer.
- hole injection layer 103 Sublimation-purified HTL-1 and NDP-9 were deposited at a rate of 0.15 nm/sec to a thickness of 10 nm to form a hole injection layer 103 .
- first hole transport layer 1051 A first hole transport layer 1051 was produced by forming a film of HTL purified by sublimation to a thickness of 85 nm at a rate of 0.15 nm/sec.
- Second hole transport layer 1052 Sublimation-purified EBL-1 was deposited at a rate of 0.15 nm/second to a thickness of 5 nm to form a second hole transport layer 1052 .
- Second hole transport layer 106 Sublimation-purified BH-1 and BD-1 were deposited at a ratio of 95:5 (mass ratio) to form a film having a thickness of 20 nm to prepare a light-emitting layer 106 .
- the deposition rate was 0.18 nm/sec.
- first electron transport layer 1071 Sublimation-purified HBL-1 was deposited at a rate of 0.05 nm/second to a thickness of 6 nm to prepare a first electron transport layer 1071 .
- second electron transport layer 1072 Compound E1 and Liq were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to form a second electron transport layer 1072 .
- the deposition rate was 0.15 nm/sec.
- cathode 108 Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and a cathode 108 was formed.
- ytterbium, silver/magnesium (mass ratio 9/1) and silver were deposited in this order to thicknesses of 2 nm, 12 nm and 90 nm, respectively, to form a three-layer structure.
- the deposition rate of ytterbium was 0.02 nm/second
- the deposition rate of silver/magnesium was 0.5 nm/second
- the deposition rate of silver was 0.2 nm/second.
- an organic electroluminescence device 100 having a light emitting area of 4 mm 2 as shown in FIG. 2 was produced.
- Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
- this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
- a bisphenol F-type epoxy resin manufactured by Nagase ChemteX Corporation
- the compound of the present invention can be used for organic electroluminescence devices and the like.
Abstract
Provided is a novel pyrimidine compound that facilitates the manufacture of an organic electroluminescent element in which driving voltage can be reduced and current efficiency can be increased. Also provided are a material for an organic electroluminescent element and an organic electroluminescent element that include said pyrimidine compound. A pyrimidine compound with a specific structure represented by formula (1), and a material for an organic electroluminescent element and an organic electroluminescent element that include said pyrimidine compound.
Description
本発明は、ピリミジン化合物、ピリミジン化合物を含む有機電界発光素子用材料および有機電界発光素子に関する。
The present invention relates to a pyrimidine compound, a material for an organic electroluminescence device containing a pyrimidine compound, and an organic electroluminescence device.
有機電界発光素子は、小型モバイル用途を中心に実用化が始まっている。しかしながら、更なる用途拡大には性能向上が必須であり、高電流効率、低駆動電圧、高い発光効率特性、長寿命特性を有する材料が求められている。特許文献１、２は、有機電界発光素子用の材料である、ピリミジン化合物を開示している。
Organic electroluminescent devices have begun to be put into practical use, mainly for small mobile applications. However, performance improvement is essential for further expansion of applications, and materials with high current efficiency, low driving voltage, high luminous efficiency characteristics, and long life characteristics are required. Patent Documents 1 and 2 disclose pyrimidine compounds that are materials for organic electroluminescent devices.
しかしながら、特許文献１～２にかかるピリミジン化合物は駆動電圧特性を十分に満たしているとはいえない。
However, it cannot be said that the pyrimidine compounds according to Patent Documents 1 and 2 sufficiently satisfy the driving voltage characteristics.
そこで、本発明の一態様は、新たなピリミジン化合物であって、駆動電圧を低減し、電流効率を向上し得る有機電界発光素子の形成に資する、新たなピリミジン化合物を提供することに向けられている。
Therefore, one aspect of the present invention is directed to providing a new pyrimidine compound that contributes to the formation of an organic electroluminescent device capable of reducing the driving voltage and improving the current efficiency. there is
さらに、本発明のさらに他の態様は、駆動電圧が低減され、電流効率を向上した有機電界発光素子を提供することに向けられている。
Furthermore, still another aspect of the present invention is directed to providing an organic electroluminescence device with reduced driving voltage and improved current efficiency.
本発明の一態様は、下記のものである。
１．式（１）で表されるピリミジン化合物： One aspect of the present invention is as follows.
1. A pyrimidine compound represented by formula (1):
１．式（１）で表されるピリミジン化合物： One aspect of the present invention is as follows.
1. A pyrimidine compound represented by formula (1):
式中、
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである；
Ａｒ１及びＡｒ２は、各々独立に、
フェニル基、ビフェニリル基、又は、ナフチル基を表す；
Ａｒ３及びＡｒ４は、各々独立に、
炭素数６～２０のアリール基、又は、
炭素数４～２０のヘテロアリール基を表す；
Ｌ１及びＬ２は、各々独立に、
直接結合、フェニレン、ピリジレン、又は、ナフチレンを表す；
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している；
ｎは１又は２である；
ｎが２のとき、２つのＬ１は互いに同一又は相異なっていてもよい。
２．Ａｒ１とＡｒ２が同一である１．に記載のピリミジン化合物。
３．Ａｒ１及びＡｒ２の少なくとも一方が４－ビフェニリル基である１．または２．に記載のピリミジン化合物。
４．式（Ｅ１）～（Ｅ１０）で表される、１．～３．のいずれかに記載のピリミジン化合物。 During the ceremony,
one of X 1 and X 2 is a nitrogen atom and the other is C—H;
Ar 1 and Ar 2 are each independently
represents a phenyl group, a biphenylyl group, or a naphthyl group;
Ar 3 and Ar 4 are each independently
an aryl group having 6 to 20 carbon atoms, or
represents a heteroaryl group having 4 to 20 carbon atoms;
L 1 and L 2 are each independently
represents a direct bond, phenylene, pyridylene or naphthylene;
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
n is 1 or 2;
When n is 2 , two L1's may be the same or different.
2. 1. Ar 1 and Ar 2 are identical. The pyrimidine compound according to .
3. 1. At least one of Ar 1 and Ar 2 is a 4-biphenylyl group. or 2. The pyrimidine compound according to .
4. 1. represented by formulas (E1) to (E10); ~3. The pyrimidine compound according to any one of .
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである；
Ａｒ１及びＡｒ２は、各々独立に、
フェニル基、ビフェニリル基、又は、ナフチル基を表す；
Ａｒ３及びＡｒ４は、各々独立に、
炭素数６～２０のアリール基、又は、
炭素数４～２０のヘテロアリール基を表す；
Ｌ１及びＬ２は、各々独立に、
直接結合、フェニレン、ピリジレン、又は、ナフチレンを表す；
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している；
ｎは１又は２である；
ｎが２のとき、２つのＬ１は互いに同一又は相異なっていてもよい。
２．Ａｒ１とＡｒ２が同一である１．に記載のピリミジン化合物。
３．Ａｒ１及びＡｒ２の少なくとも一方が４－ビフェニリル基である１．または２．に記載のピリミジン化合物。
４．式（Ｅ１）～（Ｅ１０）で表される、１．～３．のいずれかに記載のピリミジン化合物。 During the ceremony,
one of X 1 and X 2 is a nitrogen atom and the other is C—H;
Ar 1 and Ar 2 are each independently
represents a phenyl group, a biphenylyl group, or a naphthyl group;
Ar 3 and Ar 4 are each independently
an aryl group having 6 to 20 carbon atoms, or
represents a heteroaryl group having 4 to 20 carbon atoms;
L 1 and L 2 are each independently
represents a direct bond, phenylene, pyridylene or naphthylene;
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
n is 1 or 2;
When n is 2 , two L1's may be the same or different.
2. 1. Ar 1 and Ar 2 are identical. The pyrimidine compound according to .
3. 1. At least one of Ar 1 and Ar 2 is a 4-biphenylyl group. or 2. The pyrimidine compound according to .
4. 1. represented by formulas (E1) to (E10); ~3. The pyrimidine compound according to any one of .
５．陽極と、
陰極と、
少なくとも発光層を含む１以上の有機薄膜層と、を備え、
前記有機薄膜層の少なくとも１層が、１．～４．のいずれかに記載のピリミジン化合物を含有する有機電界発光素子 5. an anode;
a cathode;
and one or more organic thin film layers including at least a light-emitting layer,
At least one of the organic thin film layers comprises:1. ~ 4. An organic electroluminescence device containing the pyrimidine compound according to any one of
陰極と、
少なくとも発光層を含む１以上の有機薄膜層と、を備え、
前記有機薄膜層の少なくとも１層が、１．～４．のいずれかに記載のピリミジン化合物を含有する有機電界発光素子 5. an anode;
a cathode;
and one or more organic thin film layers including at least a light-emitting layer,
At least one of the organic thin film layers comprises:1. ~ 4. An organic electroluminescence device containing the pyrimidine compound according to any one of
本発明の一態様によれば、駆動電圧を低減し、電流効率を向上し得る有機電界発光素子の形成に資する、新たなピリミジン化合物を提供することができる。
According to one aspect of the present invention, it is possible to provide a new pyrimidine compound that contributes to the formation of an organic electroluminescent device capable of reducing driving voltage and improving current efficiency.
また、本発明の他の態様によれば、上記ピリミジン化合物を含む有機電界発光素子用材料、および有機電界発光素子用電子輸送材料を提供することができる。さらに、本発明のさらに他の態様によれば、駆動電圧が低減された有機電界発光素子を提供することができる。
Further, according to another aspect of the present invention, it is possible to provide a material for organic electroluminescence devices and an electron transport material for organic electroluminescence devices containing the pyrimidine compound. Furthermore, according to still another aspect of the present invention, it is possible to provide an organic electroluminescence device with reduced driving voltage.
以下、本発明の各態様について詳細に説明する。
Each aspect of the present invention will be described in detail below.
本発明の一態様にかかるピリミジン化合物は、式（１）で表されるピリミジン化合物である。
A pyrimidine compound according to one aspect of the present invention is a pyrimidine compound represented by formula (1).
式中、
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである；
Ａｒ１及びＡｒ２は、各々独立に、
フェニル基、ビフェニリル基、又は、ナフチル基を表す；
Ａｒ３及びＡｒ４は、各々独立に、
炭素数６～２０のアリール基、又は、
炭素数４～２０のヘテロアリール基を表す；
Ｌ１及びＬ２は、各々独立に、
直接結合、フェニレン、ピリジレン、又は、ナフチレンを表す；
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している；
ｎは１又は２である；
ｎが２のとき、２つのＬ１は互いに同一又は相異なっていてもよい。
［Ａｒ１及びＡｒ２について］
Ａｒ１及びＡｒ２は、各々独立に、フェニル基、ビフェニリル基、又は、ナフチル基である。 During the ceremony,
one of X 1 and X 2 is a nitrogen atom and the other is C—H;
Ar 1 and Ar 2 are each independently
represents a phenyl group, a biphenylyl group, or a naphthyl group;
Ar 3 and Ar 4 are each independently
an aryl group having 6 to 20 carbon atoms, or
represents a heteroaryl group having 4 to 20 carbon atoms;
L 1 and L 2 are each independently
represents a direct bond, phenylene, pyridylene or naphthylene;
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
n is 1 or 2;
When n is 2 , two L1's may be the same or different.
[Regarding Ar 1 and Ar 2 ]
Ar 1 and Ar 2 are each independently a phenyl group, a biphenylyl group, or a naphthyl group.
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである；
Ａｒ１及びＡｒ２は、各々独立に、
フェニル基、ビフェニリル基、又は、ナフチル基を表す；
Ａｒ３及びＡｒ４は、各々独立に、
炭素数６～２０のアリール基、又は、
炭素数４～２０のヘテロアリール基を表す；
Ｌ１及びＬ２は、各々独立に、
直接結合、フェニレン、ピリジレン、又は、ナフチレンを表す；
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している；
ｎは１又は２である；
ｎが２のとき、２つのＬ１は互いに同一又は相異なっていてもよい。
［Ａｒ１及びＡｒ２について］
Ａｒ１及びＡｒ２は、各々独立に、フェニル基、ビフェニリル基、又は、ナフチル基である。 During the ceremony,
one of X 1 and X 2 is a nitrogen atom and the other is C—H;
Ar 1 and Ar 2 are each independently
represents a phenyl group, a biphenylyl group, or a naphthyl group;
Ar 3 and Ar 4 are each independently
an aryl group having 6 to 20 carbon atoms, or
represents a heteroaryl group having 4 to 20 carbon atoms;
L 1 and L 2 are each independently
represents a direct bond, phenylene, pyridylene or naphthylene;
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
n is 1 or 2;
When n is 2 , two L1's may be the same or different.
[Regarding Ar 1 and Ar 2 ]
Ar 1 and Ar 2 are each independently a phenyl group, a biphenylyl group, or a naphthyl group.
Ａｒ１及びＡｒ２は、ビフェニリル基、ナフチル基であることが好ましく、さらに、４－ビフェニリル基であることが好ましい。
Ar 1 and Ar 2 are preferably a biphenylyl group or a naphthyl group, more preferably a 4-biphenylyl group.
Ａｒ１とＡｒ２は同一であることが好ましい。
［Ａｒ３及びＡｒ４について］
Ａｒ３及びＡｒ４は、各々独立に、炭素数６～２０のアリール基、または炭素数４～２０のヘテロアリール基である。 Ar 1 and Ar 2 are preferably the same.
[Regarding Ar 3 and Ar 4 ]
Ar 3 and Ar 4 are each independently an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms.
［Ａｒ３及びＡｒ４について］
Ａｒ３及びＡｒ４は、各々独立に、炭素数６～２０のアリール基、または炭素数４～２０のヘテロアリール基である。 Ar 1 and Ar 2 are preferably the same.
[Regarding Ar 3 and Ar 4 ]
Ar 3 and Ar 4 are each independently an aryl group having 6 to 20 carbon atoms or a heteroaryl group having 4 to 20 carbon atoms.
炭素数６～２０のアリール基の具体例としては、フェニル基、ナフチル基、フェナントリル基、アントニル基、ピレニル基、ピラニル基、フルオレニル基、ジメチルフルオレニル基、トリフェニレニル基、フルオランテニル基、クリセニル基などが挙げられる。
Specific examples of aryl groups having 6 to 20 carbon atoms include phenyl group, naphthyl group, phenanthryl group, anthonyl group, pyrenyl group, pyranyl group, fluorenyl group, dimethylfluorenyl group, triphenylenyl group, fluoranthenyl group and chrysenyl. and the like.
炭素数４～２０のヘテロアリール基の具体例としては、ピリジル基、ピリミジル基、ピラジル基、キノリル基、イソキノリル基、ナジチリジニル基、アクリジニル基などが挙げられる。
Specific examples of heteroaryl groups having 4 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a pyrazyl group, a quinolyl group, an isoquinolyl group, a nadityridinyl group and an acridinyl group.
Ａｒ３及びＡｒ４は、フェニル基、ナフチル基、フェナントリル基、又は、ピリジル基が好ましい。
［環Ａについて］
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している。 Ar 3 and Ar 4 are preferably a phenyl group, a naphthyl group, a phenanthryl group, or a pyridyl group.
[About Ring A]
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each bonded to two adjacent carbon atoms of the pyridine ring.
［環Ａについて］
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している。 Ar 3 and Ar 4 are preferably a phenyl group, a naphthyl group, a phenanthryl group, or a pyridyl group.
[About Ring A]
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each bonded to two adjacent carbon atoms of the pyridine ring.
環Ａは具体的には、式（Ａ－１）及び（Ａ－２）で表される。
Ring A is specifically represented by formulas (A-1) and (A-2).
式（Ａ－１）及び（Ａ－２）中、破線は各々独立に、Ａｒ３又はＬ１が置換されている位置を示す。ピリジン環はＡｒ３及びＬ１の他に、フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群より選択される１つ以上の基で置換されていてもよい。これらのうち、フェニル基、ピリジル基、ナフチル基、炭素数１～５のアルキル基及びＣＮ基が好ましく、フェニル基、ピリジル基、ナフチル基及び炭素数１～５のアルキル基がより好ましく、フェニル基、ピリジル基、ナフチル基及びメチル基が更に好ましく、フェニル基、ピリジル基、メチル基が特に好ましい。
［Ｌ１及びＬ２について］
Ｌ１及びＬ２は、各々独立に、直接結合、フェニレン、ピリジレン、ナフチレンを表す。Ｌ１及びＬ２は、各々独立に、直接結合、フェニレン、ピリジレンであることが好ましい。
［Ｘ１及びＸ２について］
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである。 In formulas (A-1) and (A-2), each dashed line independently indicates the position where Ar 3 or L 1 is substituted. In addition to Ar 3 and L 1 , the pyridine ring is substituted with one or more groups selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group. good too. Among these, a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 5 carbon atoms and a CN group are preferable, and a phenyl group, a pyridyl group, a naphthyl group and an alkyl group having 1 to 5 carbon atoms are more preferable, and a phenyl group. , pyridyl group, naphthyl group and methyl group are more preferred, and phenyl group, pyridyl group and methyl group are particularly preferred.
[Regarding L 1 and L 2 ]
L 1 and L 2 each independently represent a direct bond, phenylene, pyridylene or naphthylene. Preferably, L 1 and L 2 are each independently a direct bond, phenylene, or pyridylene.
[About X 1 and X 2 ]
One of X 1 and X 2 is a nitrogen atom and the other is CH.
［Ｌ１及びＬ２について］
Ｌ１及びＬ２は、各々独立に、直接結合、フェニレン、ピリジレン、ナフチレンを表す。Ｌ１及びＬ２は、各々独立に、直接結合、フェニレン、ピリジレンであることが好ましい。
［Ｘ１及びＸ２について］
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである。 In formulas (A-1) and (A-2), each dashed line independently indicates the position where Ar 3 or L 1 is substituted. In addition to Ar 3 and L 1 , the pyridine ring is substituted with one or more groups selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group. good too. Among these, a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 5 carbon atoms and a CN group are preferable, and a phenyl group, a pyridyl group, a naphthyl group and an alkyl group having 1 to 5 carbon atoms are more preferable, and a phenyl group. , pyridyl group, naphthyl group and methyl group are more preferred, and phenyl group, pyridyl group and methyl group are particularly preferred.
[Regarding L 1 and L 2 ]
L 1 and L 2 each independently represent a direct bond, phenylene, pyridylene or naphthylene. Preferably, L 1 and L 2 are each independently a direct bond, phenylene, or pyridylene.
[About X 1 and X 2 ]
One of X 1 and X 2 is a nitrogen atom and the other is CH.
以下、ピリミジン化合物の具体的な例を示す。なお、本発明はこれらに限定されるものではない。
Specific examples of pyrimidine compounds are shown below. In addition, this invention is not limited to these.
また駆動電圧低減の点から、以下に示す構造のものが好ましい。
Also, from the viewpoint of driving voltage reduction, the structure shown below is preferable.
ピリミジン化合物は、例えば、有機電界発光素子や光電素子等の有機電子素子用途に用いることができる。
＜有機電界発光素子用材料＞
本発明の一態様にかかる有機電界発光素子用材料は、上記ピリミジン化合物を含有する。ピリミジン化合物は、例えば、有機電界発光素子用電子輸送材料として用いることができる。 Pyrimidine compounds can be used, for example, in organic electronic devices such as organic electroluminescence devices and photoelectric devices.
<Materials for Organic Electroluminescent Devices>
A material for an organic electroluminescence device according to one aspect of the present invention contains the pyrimidine compound. A pyrimidine compound can be used, for example, as an electron transport material for an organic electroluminescence device.
＜有機電界発光素子用材料＞
本発明の一態様にかかる有機電界発光素子用材料は、上記ピリミジン化合物を含有する。ピリミジン化合物は、例えば、有機電界発光素子用電子輸送材料として用いることができる。 Pyrimidine compounds can be used, for example, in organic electronic devices such as organic electroluminescence devices and photoelectric devices.
<Materials for Organic Electroluminescent Devices>
A material for an organic electroluminescence device according to one aspect of the present invention contains the pyrimidine compound. A pyrimidine compound can be used, for example, as an electron transport material for an organic electroluminescence device.
本発明の一態様に係るピリミジン化合物が、例えば有機電界発光素子用電子輸送材料として、低い駆動電圧を示す構造的な理由は、以下に挙げるものであると推測される。
＜低い駆動電圧を示す構造的な理由＞
トリアジン環は、電子陰性度の高い窒素原子を環構成に３個組み込み、環自体の電子親和力を高くすることで、高い電子輸送性を有する。また、トリアジン化合物の分子内にピリジン環を有することで陰極からの電子注入性を高める試みがなされている。 The structural reason why the pyrimidine compound according to one aspect of the present invention exhibits a low driving voltage as, for example, an electron-transporting material for an organic electroluminescence device is presumed to be as follows.
<Structural reasons for low drive voltage>
The triazine ring incorporates three highly electronegative nitrogen atoms into the ring structure to increase the electron affinity of the ring itself, thereby having a high electron transport property. Attempts have also been made to increase electron injection properties from the cathode by having a pyridine ring in the molecule of the triazine compound.
＜低い駆動電圧を示す構造的な理由＞
トリアジン環は、電子陰性度の高い窒素原子を環構成に３個組み込み、環自体の電子親和力を高くすることで、高い電子輸送性を有する。また、トリアジン化合物の分子内にピリジン環を有することで陰極からの電子注入性を高める試みがなされている。 The structural reason why the pyrimidine compound according to one aspect of the present invention exhibits a low driving voltage as, for example, an electron-transporting material for an organic electroluminescence device is presumed to be as follows.
<Structural reasons for low drive voltage>
The triazine ring incorporates three highly electronegative nitrogen atoms into the ring structure to increase the electron affinity of the ring itself, thereby having a high electron transport property. Attempts have also been made to increase electron injection properties from the cathode by having a pyridine ring in the molecule of the triazine compound.
しかしながら、トリアジン環の高い電子親和力は一般的に広く用いられている発光層や正孔阻止層への電子注入を阻害し得る。また、ピリジン環は分子の電子親和力をさらに高くするため発光層や正孔阻止層への電子注入を阻害し得る。
However, the high electron affinity of the triazine ring can inhibit electron injection into the widely used light-emitting layer and hole-blocking layer. In addition, the pyridine ring further increases the electron affinity of the molecule and can inhibit electron injection into the light-emitting layer and the hole-blocking layer.
一方、ピリミジン環は、トリアジン環と同様に窒素原子を複数個含むが、その数がトリアジン環と比べて少なく、電子親和力が低いため、発光層または正孔阻止層への電子注入が促進される。また、本態様に係るピリミジン化合物は、ピリジン環の隣接する炭素上にＡｒおよびＬ１が結合していることで、ピリジン環と隣接する芳香環の二面角を大きくし、分子の電子親和力が高くなることを抑制している。これにより電子親和力を低く保ったまま陰極からの電子注入性を高めることを可能としている。この促進された電子注入により高い電流効率を示すことができる。
On the other hand, the pyrimidine ring contains a plurality of nitrogen atoms like the triazine ring, but the number is smaller than that of the triazine ring, and the electron affinity is low, so electron injection into the light-emitting layer or the hole-blocking layer is promoted. . In addition, the pyrimidine compound according to this aspect has Ar and L 1 bonded to the adjacent carbon atoms of the pyridine ring, thereby increasing the dihedral angle of the aromatic ring adjacent to the pyridine ring and increasing the electron affinity of the molecule. restrains it from rising. This makes it possible to improve the electron injection from the cathode while keeping the electron affinity low. This enhanced electron injection can exhibit high current efficiency.
一方、ピリミジン環はトリアジン環と異なり、それ自体が大きな双極子モーメントを有する。有機薄膜において、有機分子が双極子モーメントを有する場合、有機分子が自発的に配向し結晶構造に似た秩序性を有する膜になることが知られている。結晶性の高い膜は膜中に欠陥を生じ、電荷輸送の障害になるため、有機電界発光素子に用いられる有機膜においては高いアモルファス性が求められることが一般的に知られている。
On the other hand, unlike the triazine ring, the pyrimidine ring itself has a large dipole moment. In an organic thin film, it is known that when organic molecules have a dipole moment, the organic molecules spontaneously orient to form a film having an orderly structure resembling a crystal structure. It is generally known that highly amorphous films are required for organic films used in organic electroluminescence devices because films with high crystallinity cause defects in the film and hinder charge transport.
また、有機分子同士が自発配向することによって、昇華温度が高くなる。このことは有機電界発光素子作製時の熱分解を促進させ、ひいては分解物の混入による有機電界発光素子の耐久性低下に影響する。
In addition, the spontaneous orientation of the organic molecules raises the sublimation temperature. This promotes thermal decomposition during the production of the organic electroluminescence device, and eventually influences deterioration of the durability of the organic electroluminescence device due to contamination of decomposition products.
すなわち、ピリミジン環を有する化合物は、発光層または正孔阻止層への電子注入性を促進させうるが、膜中の電子輸送が抑制されてしまうという課題を有する。
That is, a compound having a pyrimidine ring can promote electron injection into the light-emitting layer or the hole-blocking layer, but has the problem of suppressing electron transport in the film.
それに対して、本発明の一態様であるピリミジン化合物は、式（１）中のＡｒ３と環Ａが高い立体障害を形成するため、分子の自発配向を抑制し、高いアモルファス性を有することが可能である。したがって、本発明の一態様であるピリミジン化合物は、正孔阻止層への電子注入性を促進しつつ、膜中の電子輸送も抑制されないため、駆動電圧を低減させることが可能である。
On the other hand, in the pyrimidine compound of one embodiment of the present invention, Ar 3 and the ring A in formula (1) form a high steric hindrance, which suppresses the spontaneous orientation of molecules and has a high amorphous property. It is possible. Therefore, the pyrimidine compound, which is one embodiment of the present invention, promotes electron injection into the hole-blocking layer and does not suppress electron transport in the film, so that driving voltage can be reduced.
また、本発明の一態様であるピリミジン化合物は、昇華温度の低下にも寄与するため、材料の熱分解の抑制、有機電界発光素子の耐久性低下の抑制にも寄与することが可能である。
In addition, since the pyrimidine compound that is one embodiment of the present invention also contributes to lowering the sublimation temperature, it is possible to contribute to suppression of thermal decomposition of the material and suppression of deterioration in durability of the organic electroluminescent element.
＜有機電界発光素子＞
以下、本発明の一態様にかかる有機電界発光素子（以下、単に有機電界発光素子と称することがある）について説明する。 <Organic electroluminescent device>
An organic electroluminescence device (hereinafter sometimes simply referred to as an organic electroluminescence device) according to one aspect of the present invention will be described below.
以下、本発明の一態様にかかる有機電界発光素子（以下、単に有機電界発光素子と称することがある）について説明する。 <Organic electroluminescent device>
An organic electroluminescence device (hereinafter sometimes simply referred to as an organic electroluminescence device) according to one aspect of the present invention will be described below.
本発明の一態様にかかる有機電界発光素子は、ピリミジン化合物を含有する。
An organic electroluminescent device according to one aspect of the present invention contains a pyrimidine compound.
有機電界発光素子の構成については特に限定されるものではないが、例えば、以下に示す（ｉ）～（ｖｉ）の構成が挙げられる。
The configuration of the organic electroluminescent element is not particularly limited, but includes, for example, the configurations (i) to (vi) shown below.
（ｉ）：陽極／発光層／陰極
（ｉｉ）：陽極／正孔輸送層／発光層／陰極
（ｉｉｉ）：陽極／発光層／電子輸送層／陰極
（ｉｖ）：陽極／正孔輸送層／発光層／電子輸送層／陰極
（ｖ）：陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極
（ｖｉ）：陽極／正孔注入層／正孔輸送層／電子阻止層／発光層／正孔阻止層／電子輸送層／電子注入層／陰極
ピリミジン化合物は、上記のいずれの層に含まれていてもよいが、有機電界発光素子の発光特性に優れる点で、発光層および該発光層と陰極との間の層からなる群より選ばれる１層以上に含まれることが好ましい。したがって、上記（ｉ）～（ｖｉ）に示された構成の場合、ピリミジン化合物が、発光層、正孔阻止層、電子輸送層、および電子注入層からなる群より選ばれる１層以上に含まれることが好ましい。 (i): anode/light emitting layer/cathode (ii): anode/hole transport layer/light emitting layer/cathode (iii): anode/light emitting layer/electron transport layer/cathode (iv): anode/hole transport layer/ Emissive layer/electron transport layer/cathode (v): anode/hole injection layer/hole transport layer/emissive layer/electron transport layer/electron injection layer/cathode (vi): anode/hole injection layer/hole transport Layer/electron-blocking layer/light-emitting layer/hole-blocking layer/electron-transporting layer/electron-injecting layer/cathode The pyrimidine compound may be contained in any of the above layers, but the organic electroluminescent device exhibits excellent light-emitting properties. In that respect, it is preferably contained in one or more layers selected from the group consisting of the light-emitting layer and layers between the light-emitting layer and the cathode. Therefore, in the case of the configurations shown in (i) to (vi) above, the pyrimidine compound is contained in one or more layers selected from the group consisting of a light-emitting layer, a hole-blocking layer, an electron-transporting layer, and an electron-injecting layer. is preferred.
（ｉｉ）：陽極／正孔輸送層／発光層／陰極
（ｉｉｉ）：陽極／発光層／電子輸送層／陰極
（ｉｖ）：陽極／正孔輸送層／発光層／電子輸送層／陰極
（ｖ）：陽極／正孔注入層／正孔輸送層／発光層／電子輸送層／電子注入層／陰極
（ｖｉ）：陽極／正孔注入層／正孔輸送層／電子阻止層／発光層／正孔阻止層／電子輸送層／電子注入層／陰極
ピリミジン化合物は、上記のいずれの層に含まれていてもよいが、有機電界発光素子の発光特性に優れる点で、発光層および該発光層と陰極との間の層からなる群より選ばれる１層以上に含まれることが好ましい。したがって、上記（ｉ）～（ｖｉ）に示された構成の場合、ピリミジン化合物が、発光層、正孔阻止層、電子輸送層、および電子注入層からなる群より選ばれる１層以上に含まれることが好ましい。 (i): anode/light emitting layer/cathode (ii): anode/hole transport layer/light emitting layer/cathode (iii): anode/light emitting layer/electron transport layer/cathode (iv): anode/hole transport layer/ Emissive layer/electron transport layer/cathode (v): anode/hole injection layer/hole transport layer/emissive layer/electron transport layer/electron injection layer/cathode (vi): anode/hole injection layer/hole transport Layer/electron-blocking layer/light-emitting layer/hole-blocking layer/electron-transporting layer/electron-injecting layer/cathode The pyrimidine compound may be contained in any of the above layers, but the organic electroluminescent device exhibits excellent light-emitting properties. In that respect, it is preferably contained in one or more layers selected from the group consisting of the light-emitting layer and layers between the light-emitting layer and the cathode. Therefore, in the case of the configurations shown in (i) to (vi) above, the pyrimidine compound is contained in one or more layers selected from the group consisting of a light-emitting layer, a hole-blocking layer, an electron-transporting layer, and an electron-injecting layer. is preferred.
以下、本発明の一態様にかかる有機電界発光素子を、上記（ｖ）の構成を例に挙げて、図１を参照しながらより詳細に説明する。
Hereinafter, the organic electroluminescence device according to one aspect of the present invention will be described in more detail with reference to FIG. 1, taking the above configuration (v) as an example.
なお、図１に示す有機電界発光素子は、いわゆるボトムエミッション型の素子構成を有するものであるが、本発明の一態様にかかる有機電界発光素子はボトムエミッション型の素子構成に限定されるものではない。すなわち、本発明の一態様にかかる有機電界発光素子は、トップエミッション型など、他の公知の素子構成であってもよい。
The organic electroluminescent device shown in FIG. 1 has a so-called bottom emission type device configuration, but the organic electroluminescent device according to one aspect of the present invention is not limited to the bottom emission type device configuration. do not have. That is, the organic electroluminescence device according to one aspect of the present invention may have other known device configurations such as top emission type.
図１は、本発明の一態様にかかる有機電界発光素子の積層構成の一例を示す概略断面図である。
FIG. 1 is a schematic cross-sectional view showing an example of a laminated structure of an organic electroluminescence device according to one aspect of the present invention.
有機電界発光素子１００は、基板１、陽極２、正孔注入層３、正孔輸送層４、発光層５、電子輸送層６、電子注入層７、および陰極８をこの順で備える。ただし、これらの層のうちの一部の層が省略されていてもよく、また逆に他の層が追加されていてもよい。例えば、発光層５と電子輸送層６との間に正孔阻止層が設けられていてもよく、正孔注入層３が省略され、陽極２上に正孔輸送層４が直接設けられていてもよい。
The organic electroluminescent device 100 includes a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7, and a cathode 8 in this order. However, some of these layers may be omitted, or conversely, other layers may be added. For example, a hole-blocking layer may be provided between the light-emitting layer 5 and the electron-transporting layer 6, the hole-injecting layer 3 may be omitted, and the hole-transporting layer 4 may be provided directly on the anode 2. good too.
また、例えば電子注入層の機能と電子輸送層の機能とを単一の層で併せ持つ電子注入・輸送層のような、複数の層が有する機能を併せ持った単一の層を、当該複数の層の代わりに備えた構成であってもよい。さらに、例えば単層の正孔輸送層４、単層の電子輸送層６が、それぞれ複数層からなっていてもよい。
＜ピリミジン化合物を含有する層＞
図１に示される構成例において有機電界発光素子１００は、発光層５、電子輸送層６および電子注入層７からなる群より選ばれる１層以上に上記ピリミジン化合物を含む。特に、電子輸送層６がピリミジン化合物を含むことが好ましい。なお、ピリミジン化合物は、有機電界発光素子が備える複数の層に含まれていてもよい。 Further, a single layer having the functions of a plurality of layers, such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of. Further, for example, each of the single-layerhole transport layer 4 and the single-layer electron transport layer 6 may be composed of a plurality of layers.
<Layer containing pyrimidine compound>
In the structural example shown in FIG. 1, theorganic electroluminescence device 100 contains the above pyrimidine compound in one or more layers selected from the group consisting of the light-emitting layer 5, the electron transport layer 6 and the electron injection layer . In particular, the electron transport layer 6 preferably contains a pyrimidine compound. In addition, the pyrimidine compound may be contained in a plurality of layers included in the organic electroluminescence device.
＜ピリミジン化合物を含有する層＞
図１に示される構成例において有機電界発光素子１００は、発光層５、電子輸送層６および電子注入層７からなる群より選ばれる１層以上に上記ピリミジン化合物を含む。特に、電子輸送層６がピリミジン化合物を含むことが好ましい。なお、ピリミジン化合物は、有機電界発光素子が備える複数の層に含まれていてもよい。 Further, a single layer having the functions of a plurality of layers, such as an electron injection/transport layer having both the function of an electron injection layer and the function of an electron transport layer in a single layer. It may be a configuration provided instead of. Further, for example, each of the single-layer
<Layer containing pyrimidine compound>
In the structural example shown in FIG. 1, the
以下においては、電子輸送層６がピリミジン化合物を含む有機電界発光素子１００について説明する。
［基板１］
基板１としては特に限定はなく、通常の有機電界発光素子に使用できる基板を使用することができる。例えばガラス板、石英板、プラスチック板などが挙げられる。
［陽極２］
基板１上（正孔注入層３側）には陽極２が設けられている。 Anorganic electroluminescence device 100 in which the electron transport layer 6 contains a pyrimidine compound will be described below.
[Substrate 1]
Thesubstrate 1 is not particularly limited, and substrates that can be used in ordinary organic electroluminescence devices can be used. For example, a glass plate, a quartz plate, a plastic plate and the like can be used.
[Anode 2]
Ananode 2 is provided on the substrate 1 (on the hole injection layer 3 side).
［基板１］
基板１としては特に限定はなく、通常の有機電界発光素子に使用できる基板を使用することができる。例えばガラス板、石英板、プラスチック板などが挙げられる。
［陽極２］
基板１上（正孔注入層３側）には陽極２が設けられている。 An
[Substrate 1]
The
[Anode 2]
An
陽極の材料としては、通常の有機電界発光素子に使用できる化合物を使用することができる。例えば仕事関数の大きい（例えば４ｅＶ以上）金属、合金、電気伝導性化合物およびこれらの混合物が挙げられる。陽極の材料の具体例としては、Ａｕなどの金属；ＣｕＩ、酸化インジウム－スズ（ＩＴＯ；Ｉｎｄｉｕｍ Ｔｉｎ Ｏｘｉｄｅ）、ＳｎＯ２、ＺｎＯなどの導電性透明材料が挙げられる。
［正孔注入層３、正孔輸送層４］
陽極２と後述する発光層５との間には、陽極２側から、正孔注入層３、正孔輸送層４がこの順で設けられている。 As the material for the anode, compounds that can be used in ordinary organic electroluminescence devices can be used. Examples include metals, alloys, electrically conductive compounds, and mixtures thereof with a large work function (eg, 4 eV or more). Specific examples of materials for the anode include metals such as Au; conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO.
[Hole injection layer 3, hole transport layer 4]
Ahole injection layer 3 and a hole transport layer 4 are provided in this order from the anode 2 side between the anode 2 and a light emitting layer 5 to be described later.
［正孔注入層３、正孔輸送層４］
陽極２と後述する発光層５との間には、陽極２側から、正孔注入層３、正孔輸送層４がこの順で設けられている。 As the material for the anode, compounds that can be used in ordinary organic electroluminescence devices can be used. Examples include metals, alloys, electrically conductive compounds, and mixtures thereof with a large work function (eg, 4 eV or more). Specific examples of materials for the anode include metals such as Au; conductive transparent materials such as CuI, indium tin oxide (ITO), SnO 2 and ZnO.
[
A
正孔注入層、正孔輸送層の材料としては、正孔注入性、正孔輸送性、電子障壁性の少なくともいずれかを有するものである。正孔注入層、正孔輸送層の材料は、有機物、無機物のいずれであってもよく、通常の有機電界発光素子に使用できる化合物を使用することができる。
The material for the hole injection layer and the hole transport layer has at least one of hole injection, hole transport, and electron barrier properties. Materials for the hole injection layer and the hole transport layer may be either organic or inorganic, and compounds that can be used in ordinary organic electroluminescence devices can be used.
正孔注入層、正孔輸送層は、一種または二種以上の材料からなる単構造であってもよく、同一組成または異種組成の複数層からなる積層構造であってもよい。
The hole injection layer and the hole transport layer may have a single structure composed of one or more materials, or may have a laminated structure composed of multiple layers of the same composition or different compositions.
正孔輸送層４は、２層以上の積層構造であってもよく、陽極２側から、第一正孔輸送層４１、第二正孔輸送層４２の順で設けられ、この第二正孔輸送層４２は上記（ｖｉ）の構成における電子阻止層として使用することができる。
［発光層５］
正孔輸送層４と後述する電子輸送層６との間には、発光層５が設けられている。 The hole-transportinglayer 4 may have a laminated structure of two or more layers, and is provided in this order from the anode 2 side with a first hole-transporting layer 41 and a second hole-transporting layer 42 . The transport layer 42 can be used as an electron blocking layer in the configuration (vi) above.
[Light emitting layer 5]
A light-emittinglayer 5 is provided between the hole-transporting layer 4 and an electron-transporting layer 6, which will be described later.
［発光層５］
正孔輸送層４と後述する電子輸送層６との間には、発光層５が設けられている。 The hole-transporting
[Light emitting layer 5]
A light-emitting
発光層の材料としては、通常の有機電界発光素子に使用できる発光材料を使用することができる。例えば燐光発光材料、蛍光発光材料、熱活性化遅延蛍光発光材料が挙げられる。
As the material for the light-emitting layer, light-emitting materials that can be used in ordinary organic electroluminescent devices can be used. Examples thereof include phosphorescent materials, fluorescent materials, and heat-activated delayed fluorescent materials.
発光層は、単一の低分子材料または単一のポリマー材料からなっていてもよいが、より一般的には、ゲスト化合物でドーピングされたホスト材料からなっている。発光は主としてドーパントから生じ、任意の色を有することができる。
The light emitting layer may consist of a single small molecule material or a single polymer material, but more commonly consists of a host material doped with a guest compound. Emission comes primarily from dopants and can have any color.
また、発光材料は発光層のみに含有されることに限定されるものではない。例えば、発光材料は、発光層に隣接した層（正孔輸送層４、または電子輸送層６）が含有していてもよい。これによってさらに有機電界発光素子の発光効率を高めることができる。
Also, the luminescent material is not limited to being contained only in the luminescent layer. For example, the light-emitting material may be contained in a layer adjacent to the light-emitting layer (hole-transporting layer 4 or electron-transporting layer 6). This can further increase the luminous efficiency of the organic electroluminescence device.
発光層は、一種または二種以上の材料からなる単層構造であってもよく、同一組成または異種組成の複数層からなる積層構造であってもよい。
［電子輸送層６］
発光層５と後述する電子注入層７との間には、電子輸送層６が設けられている。 The light-emitting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
[Electron transport layer 6]
Anelectron transport layer 6 is provided between the light emitting layer 5 and an electron injection layer 7 which will be described later.
［電子輸送層６］
発光層５と後述する電子注入層７との間には、電子輸送層６が設けられている。 The light-emitting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
[Electron transport layer 6]
An
電子輸送層は、ピリミジン化合物を含むことが好ましい。また、電子輸送層は、ピリミジン化合物に加えてさらに従来公知の電子輸送材料から選ばれる１種以上を含んでいてもよい。
The electron transport layer preferably contains a pyrimidine compound. In addition to the pyrimidine compound, the electron transport layer may further contain one or more selected from conventionally known electron transport materials.
なお、ピリミジン化合物が電子輸送層に含まれず、他の層に含まれる場合は、従来公知の電子輸送材料から選ばれる１種以上を、電子輸送層を構成する電子輸送材料として用いることができる。
When the pyrimidine compound is not contained in the electron-transporting layer but is contained in another layer, one or more selected from conventionally known electron-transporting materials can be used as the electron-transporting material constituting the electron-transporting layer.
従来公知の電子輸送性材料としては、アルカリ金属錯体、アルカリ土類金属錯体、土類金属錯体等が挙げられる。アルカリ金属錯体、アルカリ土類金属錯体、土類金属錯体としては、例えば、８－ヒドロキシキノリナートリチウム（Ｌｉｑ）、ビス（８－ヒドロキシキノリナート）亜鉛、ビス（８－ヒドロキシキノリナート）銅、ビス（８－ヒドロキシキノリナート）マンガン、トリス（８－ヒドロキシキノリナート）アルミニウム、トリス（２－メチル－８－ヒドロキシキノリナート）アルミニウム、トリス（８－ヒドロキシキノリナート）ガリウム、ビス（１０－ヒドロキシベンゾ［ｈ］キノリナート）ベリリウム、ビス（１０－ヒドロキシベンゾ［ｈ］キノリナート）亜鉛、ビス（２－メチル－８－キノリナート）クロロガリウム、ビス（２－メチル－８－キノリナート）（ｏ－クレゾラート）ガリウム、ビス（２－メチル－８－キノリナート）－１－ナフトラートアルミニウム、ビス（２－メチル－８－キノリナート）－２－ナフトラートガリウム等が挙げられる。
Conventionally known electron-transporting materials include alkali metal complexes, alkaline earth metal complexes, earth metal complexes, and the like. Alkali metal complexes, alkaline earth metal complexes, and earth metal complexes include, for example, 8-hydroxyquinolinatolithium (Liq), bis(8-hydroxyquinolinato)zinc, and bis(8-hydroxyquinolinato)copper. , bis(8-hydroxyquinolinato)manganese, tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis (10-hydroxybenzo[h]quinolinate) beryllium, bis(10-hydroxybenzo[h]quinolinate)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinate)(o -cresolato) gallium, bis(2-methyl-8-quinolinato)-1-naphtholato aluminum, bis(2-methyl-8-quinolinato)-2-naphtholato gallium, and the like.
電子輸送層は、一種または二種以上の材料からなる単層構造であってもよく、同一組成または異種組成の複数層からなる積層構造であってもよい。
The electron-transporting layer may have a single-layer structure composed of one or more materials, or may have a laminated structure composed of multiple layers having the same composition or different compositions.
本態様にかかる有機電界発光素子においては、電子注入性を向上させ、素子特性（例えば、発光効率、低電圧駆動、または高耐久性）を向上させる目的で、電子注入層を設けてもよい。
An electron injection layer may be provided in the organic electroluminescence device according to this aspect for the purpose of improving electron injection properties and improving device characteristics (e.g., luminous efficiency, low voltage drive, or high durability).
電子輸送層６は、２層以上の積層構造であってもよく、発光層５側から、第一電子輸送層６１、第二電子輸送層６２の順で設けられ、この第一電子輸送層６１は上記（ｖｉ）の構成における正孔阻止層として使用することができる。
The electron transport layer 6 may have a laminated structure of two or more layers. can be used as the hole blocking layer in the configuration (vi) above.
本発明の一態様にかかるピリミジン化合物は第一電子輸送層及び第二電子輸送層の両方、またはいずれか一方に使用することができる。
［電子注入層７］
電子輸送層６と後述する陰極８との間には、電子注入層７が設けられている。 The pyrimidine compound according to one aspect of the present invention can be used in both or either one of the first electron-transporting layer and the second electron-transporting layer.
[Electron injection layer 7]
An electron injection layer 7 is provided between theelectron transport layer 6 and a cathode 8 which will be described later.
［電子注入層７］
電子輸送層６と後述する陰極８との間には、電子注入層７が設けられている。 The pyrimidine compound according to one aspect of the present invention can be used in both or either one of the first electron-transporting layer and the second electron-transporting layer.
[Electron injection layer 7]
An electron injection layer 7 is provided between the
電子注入層の材料としては、通常の有機電界発光素子に使用できる化合物を使用することができる。例えば、フルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等の有機化合物が挙げられる。
As the material for the electron injection layer, compounds that can be used in ordinary organic electroluminescent devices can be used. Examples thereof include organic compounds such as fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, and anthrone.
また、電子注入層の材料としては、ＳｉＯ２、ＡｌＯ、ＳｉＮ、ＳｉＯＮ、ＡｌＯＮ、ＧｅＯ、ＬｉＯ、ＬｉＯＮ、ＴｉＯ、ＴｉＯＮ、ＴａＯ、ＴａＯＮ、ＴａＮ、ＬｉＦ、Ｃ、Ｙｂなどの各種酸化物、フッ化物、窒化物、酸化窒化物等の無機化合物も挙げられる。本発明のピリミジン化合物を使用することもできる。
［陰極８］
電子注入層７上には陰極８が設けられている。 Materials for the electron injection layer include various oxides and fluorides such as SiO 2 , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, C, and Yb. , nitrides, and oxynitrides. Pyrimidine compounds of the invention can also be used.
[Cathode 8]
A cathode 8 is provided on the electron injection layer 7 .
［陰極８］
電子注入層７上には陰極８が設けられている。 Materials for the electron injection layer include various oxides and fluorides such as SiO 2 , AlO, SiN, SiON, AlON, GeO, LiO, LiON, TiO, TiON, TaO, TaON, TaN, LiF, C, and Yb. , nitrides, and oxynitrides. Pyrimidine compounds of the invention can also be used.
[Cathode 8]
A cathode 8 is provided on the electron injection layer 7 .
陰極の材料としては、通常の有機電界発光素子に使用できる化合物を使用することができる。例えば、仕事関数の小さい金属（以下、電子注入性金属とも称する）、合金、電気伝導性化合物、およびこれらの混合物が挙げられる。ここで、仕事関数の小さい金属とは、例えば、４ｅＶ以下の金属である。
As the cathode material, compounds that can be used in ordinary organic electroluminescent devices can be used. Examples include metals with a small work function (hereinafter also referred to as electron-injecting metals), alloys, electrically conductive compounds, and mixtures thereof. Here, a metal with a small work function is, for example, a metal of 4 eV or less.
電子注入性金属とこれより仕事関数の値が大きく安定な金属である第二金属との混合物、例えばマグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ２Ｏ３）混合物、リチウム／アルミニウム混合物などが好ましい。
［各層の形成方法］
以上説明した、電極（陽極、陰極）を除く各層は、例えば、真空蒸着法、スピンコート法、キャスト法、ＬＢ（Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ ｍｅｔｈｏｄ）法などの公知の方法によって薄膜化することにより、形成することができる。各層の材料は、それ単独で用いてもよく、必要に応じて結着樹脂などの材料、溶剤と共に用いてもよい。 A mixture of an electron-injecting metal and a second metal that has a higher work function and is more stable, such as magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al 2 O 3 ) mixtures, lithium/aluminum mixtures, etc. are preferred.
[Method of Forming Each Layer]
Each layer except for the electrodes (anode, cathode) described above is formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a LB (Langmuir-Blodgett method) method. be able to. The material for each layer may be used alone, or if necessary, it may be used together with a material such as a binder resin and a solvent.
［各層の形成方法］
以上説明した、電極（陽極、陰極）を除く各層は、例えば、真空蒸着法、スピンコート法、キャスト法、ＬＢ（Ｌａｎｇｍｕｉｒ－Ｂｌｏｄｇｅｔｔ ｍｅｔｈｏｄ）法などの公知の方法によって薄膜化することにより、形成することができる。各層の材料は、それ単独で用いてもよく、必要に応じて結着樹脂などの材料、溶剤と共に用いてもよい。 A mixture of an electron-injecting metal and a second metal that has a higher work function and is more stable, such as magnesium/silver mixture, magnesium/aluminum mixture, magnesium/indium mixture, aluminum/aluminum oxide (Al 2 O 3 ) mixtures, lithium/aluminum mixtures, etc. are preferred.
[Method of Forming Each Layer]
Each layer except for the electrodes (anode, cathode) described above is formed by thinning by a known method such as a vacuum deposition method, a spin coating method, a casting method, or a LB (Langmuir-Blodgett method) method. be able to. The material for each layer may be used alone, or if necessary, it may be used together with a material such as a binder resin and a solvent.
このようにして形成された各層の膜厚については特に制限はなく、状況に応じて適宜選択することができるが、通常は５ｎｍ～５μｍの範囲である。
The film thickness of each layer thus formed is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm.
陽極および陰極は、電極材料を蒸着やスパッタリングなどの方法によって薄膜化することにより、形成することができる。蒸着やスパッタリングの際に所望の形状のマスクを介してパターンを形成してもよく、蒸着やスパッタリングなどによって薄膜を形成した後、フォトリソグラフィーで所望の形状のパターンを形成してもよい。
The anode and cathode can be formed by thinning the electrode material by a method such as vapor deposition or sputtering. A pattern may be formed through a mask of a desired shape during vapor deposition or sputtering, or a pattern of a desired shape may be formed by photolithography after forming a thin film by vapor deposition, sputtering, or the like.
陽極および陰極の膜厚は、１μｍ以下であることが好ましく、１０ｎｍ以上２００ｎｍ以下であることがより好ましい。
The film thickness of the anode and cathode is preferably 1 μm or less, more preferably 10 nm or more and 200 nm or less.
なお、ピリミジン化合物を含む層を形成するは、上記の従来公知の電子輸送性材料と併用してもよい。したがって、例えば、ピリミジン化合物と従来公知の電子輸送性材料とを共蒸着してもよく、ピリミジン化合物の層に従来公知の電子輸送性材料の層を積層してもよい。
It should be noted that the formation of the layer containing the pyrimidine compound may be used in combination with the conventionally known electron-transporting material. Therefore, for example, a pyrimidine compound and a conventionally known electron-transporting material may be co-deposited, or a layer of a conventionally known electron-transporting material may be laminated on a layer of the pyrimidine compound.
有機電界発光素子は、照明用や露光光源のような一種のランプとして使用してもよいし、画像をスクリーン等に投影するタイプのプロジェクション装置や、静止画像や動画像を直接視認するタイプの表示装置（ディスプレイ）として使用してもよい。
The organic electroluminescence element may be used as a kind of lamp for illumination or as a light source for exposure, a type of projection device for projecting an image onto a screen or the like, or a type of display for directly viewing still images or moving images. You may use it as a device (display).
動画再生用の表示装置として有機電界発光素を使用する場合、駆動方式としては、単純マトリクス（パッシブマトリクス）方式であってもよく、アクティブマトリクス方式であってもよい。また、異なる発光色を有する有機電界発光素子を２種以上使用することにより、フルカラー表示装置を作製することが可能である。
When using an organic electroluminescent element as a display device for reproducing moving images, the driving method may be a simple matrix (passive matrix) method or an active matrix method. Further, by using two or more kinds of organic electroluminescent elements having different emission colors, it is possible to produce a full-color display device.
以下、本開示を実施例に基づきさらに詳細に説明するが、本開示はこれらの実施例により何ら限定して解釈されるものではない。
Although the present disclosure will be described in more detail below based on examples, the present disclosure should not be construed as being limited by these examples.
１Ｈ－ＮＭＲスペクトルの測定は、Ｇｅｍｉｎｉ２００（バリアン社製）またはＢｒｕｋｅｒ ＡＳＣＥＮＤ ４００（４００ＭＨｚ；ＢＲＵＫＥＲ製）を用いて行った。
1 H-NMR spectra were measured using Gemini200 (manufactured by Varian) or Bruker ASCEND 400 (400 MHz; manufactured by BRUKER).
有機電界発光素子の発光特性は、室温下、作製した素子に直流電流を印加し、輝度計（製品名：ＢＭ－９，トプコンテクノハウス社製）を用いて評価した。
合成実施例－１（Ｅ１の合成） The luminous properties of the organic electroluminescent device were evaluated by applying a direct current to the fabricated device at room temperature and using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse Co., Ltd.).
Synthesis Example-1 (Synthesis of E1)
合成実施例－１（Ｅ１の合成） The luminous properties of the organic electroluminescent device were evaluated by applying a direct current to the fabricated device at room temperature and using a luminance meter (product name: BM-9, manufactured by Topcon Technohouse Co., Ltd.).
Synthesis Example-1 (Synthesis of E1)
アルゴン雰囲気下、２－（３－ブロモ－５－クロロフェニル）－４，６－ビス（４－ビフェニリル）ピリミジン（５．７４ｇ、１０ｍｍｏｌ）、フェニルボロン酸（１．３４ｇ、１１ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（１６．５ｍＬ）、テトラキス（トリフェニルホスフィン）パラジウム（２３１ｍｇ，０．２ｍｍｏｌ）をＴＨＦ（２００ｍＬ）に懸濁し、２７時間還流した。反応混合物をろ過し、ろ液を濃縮した。濃縮したろ液をメタノールに添加することで固体を析出させ、これをろ取することで目的の４，６－ビス（４－ビフェニリル）－２－（５－クロロビフェニル－３－イル）－ピリミジンを得た（収量５．１１ｇ、収率９０％）
アルゴン雰囲気下、４，６－ビス（４－ビフェニリル）－２－（５－クロロビフェニル－３－イル）－ピリミジン（２．０ｇ，３．５ｍｍｏｌ）、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－２－フェニルピリジン（１．１８ｇ，４．２ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（６．３ｍＬ）、酢酸パラジウム（１５．７ｍｇ，０．０７ｍｍｏｌ）および２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（ＸＰｈｏｓ，６７ｍｇ，０．１４ｍｍｏｌ）をＴＨＦ（３５ｍＬ）に懸濁し、１７時間還流した。放冷後、反応混合物に水を加えて固体をろ取し、水およびメタノールで洗浄することで２－［５－（２－フェニルピリジン－３－イル）－ビフェニル－３－イル］－４，６－ビス（４－ビフェニリル）ピリミジン（Ｅ１）を得た（収量２．３８ｇ，収率９９％）。
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．８８（ｓ，１Ｈ），８．７７（ｄｄ，Ｊ＝４．８，１．７Ｈｚ，１Ｈ），８．６９（ｓ，１Ｈ），８．３６（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），８．１２（ｓ，１Ｈ），８．００（ｄｄ，Ｊ＝７．７，１．７Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），７．７０－７．７２（ｍ，４Ｈ），７．３０－７．５５（ｍ，１８Ｈ）．
合成実施例－２（Ｅ２の合成） 2-(3-bromo-5-chlorophenyl)-4,6-bis(4-biphenylyl)pyrimidine (5.74 g, 10 mmol), phenylboronic acid (1.34 g, 11 mmol), 2M-phosphoric acid under an argon atmosphere. An aqueous potassium solution (16.5 mL) and tetrakis(triphenylphosphine)palladium (231 mg, 0.2 mmol) were suspended in THF (200 mL) and refluxed for 27 hours. The reaction mixture was filtered and the filtrate was concentrated. The concentrated filtrate is added to methanol to precipitate a solid, which is collected by filtration to give thetarget 4,6-bis(4-biphenylyl)-2-(5-chlorobiphenyl-3-yl)-pyrimidine. was obtained (yield 5.11 g, yield 90%)
Under an argon atmosphere, 4,6-bis(4-biphenylyl)-2-(5-chlorobiphenyl-3-yl)-pyrimidine (2.0 g, 3.5 mmol), 3-(4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-phenylpyridine (1.18 g, 4.2 mmol), 2M-potassium phosphate aqueous solution (6.3 mL), palladium acetate (15.7 mg, 0 .07 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos, 67 mg, 0.14 mmol) were suspended in THF (35 mL) and refluxed for 17 h. After allowing to cool, water was added to the reaction mixture, the solid was collected by filtration, and washed with water and methanol to give 2-[5-(2-phenylpyridin-3-yl)-biphenyl-3-yl]-4, 6-bis(4-biphenylyl)pyrimidine (E1) was obtained (yield 2.38 g, yield 99%).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.88 (s, 1H), 8.77 (dd, J = 4.8, 1.7 Hz, 1H), 8.69 (s, 1H), 8. 36 (d, J = 8.5Hz, 4H), 8.12 (s, 1H), 8.00 (dd, J = 7.7, 1.7Hz, 1H), 7.82 (d, J = 8 .5Hz, 4H), 7.70-7.72 (m, 4H), 7.30-7.55 (m, 18H).
Synthesis Example-2 (Synthesis of E2)
アルゴン雰囲気下、４，６－ビス（４－ビフェニリル）－２－（５－クロロビフェニル－３－イル）－ピリミジン（２．０ｇ，３．５ｍｍｏｌ）、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－２－フェニルピリジン（１．１８ｇ，４．２ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（６．３ｍＬ）、酢酸パラジウム（１５．７ｍｇ，０．０７ｍｍｏｌ）および２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（ＸＰｈｏｓ，６７ｍｇ，０．１４ｍｍｏｌ）をＴＨＦ（３５ｍＬ）に懸濁し、１７時間還流した。放冷後、反応混合物に水を加えて固体をろ取し、水およびメタノールで洗浄することで２－［５－（２－フェニルピリジン－３－イル）－ビフェニル－３－イル］－４，６－ビス（４－ビフェニリル）ピリミジン（Ｅ１）を得た（収量２．３８ｇ，収率９９％）。
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．８８（ｓ，１Ｈ），８．７７（ｄｄ，Ｊ＝４．８，１．７Ｈｚ，１Ｈ），８．６９（ｓ，１Ｈ），８．３６（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），８．１２（ｓ，１Ｈ），８．００（ｄｄ，Ｊ＝７．７，１．７Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），７．７０－７．７２（ｍ，４Ｈ），７．３０－７．５５（ｍ，１８Ｈ）．
合成実施例－２（Ｅ２の合成） 2-(3-bromo-5-chlorophenyl)-4,6-bis(4-biphenylyl)pyrimidine (5.74 g, 10 mmol), phenylboronic acid (1.34 g, 11 mmol), 2M-phosphoric acid under an argon atmosphere. An aqueous potassium solution (16.5 mL) and tetrakis(triphenylphosphine)palladium (231 mg, 0.2 mmol) were suspended in THF (200 mL) and refluxed for 27 hours. The reaction mixture was filtered and the filtrate was concentrated. The concentrated filtrate is added to methanol to precipitate a solid, which is collected by filtration to give the
Under an argon atmosphere, 4,6-bis(4-biphenylyl)-2-(5-chlorobiphenyl-3-yl)-pyrimidine (2.0 g, 3.5 mmol), 3-(4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-phenylpyridine (1.18 g, 4.2 mmol), 2M-potassium phosphate aqueous solution (6.3 mL), palladium acetate (15.7 mg, 0 .07 mmol) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos, 67 mg, 0.14 mmol) were suspended in THF (35 mL) and refluxed for 17 h. After allowing to cool, water was added to the reaction mixture, the solid was collected by filtration, and washed with water and methanol to give 2-[5-(2-phenylpyridin-3-yl)-biphenyl-3-yl]-4, 6-bis(4-biphenylyl)pyrimidine (E1) was obtained (yield 2.38 g, yield 99%).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.88 (s, 1H), 8.77 (dd, J = 4.8, 1.7 Hz, 1H), 8.69 (s, 1H), 8. 36 (d, J = 8.5Hz, 4H), 8.12 (s, 1H), 8.00 (dd, J = 7.7, 1.7Hz, 1H), 7.82 (d, J = 8 .5Hz, 4H), 7.70-7.72 (m, 4H), 7.30-7.55 (m, 18H).
Synthesis Example-2 (Synthesis of E2)
アルゴン雰囲気下、４－（３－ブロモ－５－クロロフェニル）－２－（４－ブロモフェニル）－６－（４－ビフェニリル）ピリミジン（２．０ｇ、３．４７ｍｍｏｌ）、フェニルボロン酸（０．９３ｇ、７．６３ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（１０．４ｍＬ）、テトラキス（トリフェニルホスフィン）パラジウム（８０ｍｇ，０．０６９ｍｍｏｌ）をＴＨＦ（３５ｍＬ）に懸濁し、１９時間還流した。反応混合物をろ過し、ろ液を濃縮した。濃縮したろ液をメタノールに添加することで固体を析出させ、これをろ取することで目的の２，４－ビス（４－ビフェニリル）－４－（５－クロロビフェニル－３－イル）－ピリミジンを得た（収量１．９１ｇ、収率９６％）
アルゴン雰囲気下、２，４－ビス（４－ビフェニリル）－４－（５－クロロビフェニル－３－イル）－ピリミジン（１．８１ｇ，３．１７ｍｍｏｌ）、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－２－フェニルピリジン（０．９８２ｇ，３．４９ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（４．８ｍＬ）、酢酸パラジウム（１４ｍｇ，０．０６３ｍｍｏｌ）および２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（ＸＰｈｏｓ，６１ｍｇ，０．１２７ｍｍｏｌ）をＴＨＦ（３２ｍＬ）に懸濁し、１５時間還流した。放冷後、反応混合物に水を加えて固体をろ取し、水およびメタノールで洗浄することで２－［５－（２－フェニルピリジン－３－イル）－ビフェニル－３－イル］－４，６－ビス（４－ビフェニリル）ピリミジン（Ｅ２）を得た（収量３．１８ｇ，収率９２％）。
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．７８（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．７６（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．４１（ｓ，１Ｈ），８．３６（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．０４（ｓ，１Ｈ），７．９８（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．７９（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．７８（ｓ，１Ｈ），７．６１（ｓ．１Ｈ），７．３５－７．５４（ｍ，１７Ｈ）．
合成実施例－３（Ｅ９の合成） Under an argon atmosphere, 4-(3-bromo-5-chlorophenyl)-2-(4-bromophenyl)-6-(4-biphenylyl)pyrimidine (2.0 g, 3.47 mmol), phenylboronic acid (0.93 g , 7.63 mmol), 2M aqueous potassium phosphate solution (10.4 mL), and tetrakis(triphenylphosphine)palladium (80 mg, 0.069 mmol) were suspended in THF (35 mL) and refluxed for 19 hours. The reaction mixture was filtered and the filtrate was concentrated. The concentrated filtrate is added to methanol to precipitate a solid, which is collected by filtration to give the desired 2,4-bis(4-biphenylyl)-4-(5-chlorobiphenyl-3-yl)-pyrimidine. was obtained (yield 1.91 g, yield 96%)
Under an argon atmosphere, 2,4-bis(4-biphenylyl)-4-(5-chlorobiphenyl-3-yl)-pyrimidine (1.81 g, 3.17 mmol), 3-(4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-phenylpyridine (0.982 g, 3.49 mmol), 2M-potassium phosphate aqueous solution (4.8 mL), palladium acetate (14 mg, 0.063 mmol) ) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos, 61 mg, 0.127 mmol) were suspended in THF (32 mL) and refluxed for 15 hours. After allowing to cool, water was added to the reaction mixture, the solid was collected by filtration, and washed with water and methanol to give 2-[5-(2-phenylpyridin-3-yl)-biphenyl-3-yl]-4, 6-bis(4-biphenylyl)pyrimidine (E2) was obtained (3.18 g, 92% yield).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.78 (d, J = 4.7 Hz, 1 H), 8.76 (d, J = 8.8 Hz, 2 H), 8.41 (s, 1 H), 8.36 (d, J = 8.6Hz, 2H), 8.04 (s, 1H), 7.98 (d, J = 7.7Hz, 1H), 7.82 (d, J = 8.6Hz , 2H), 7.79 (d, J=8.6Hz, 2H), 7.78 (s, 1H), 7.61 (s.1H), 7.35-7.54 (m, 17H).
Synthesis Example-3 (Synthesis of E9)
アルゴン雰囲気下、２，４－ビス（４－ビフェニリル）－４－（５－クロロビフェニル－３－イル）－ピリミジン（１．８１ｇ，３．１７ｍｍｏｌ）、３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－２－フェニルピリジン（０．９８２ｇ，３．４９ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（４．８ｍＬ）、酢酸パラジウム（１４ｍｇ，０．０６３ｍｍｏｌ）および２－ジシクロヘキシルホスフィノ－２’，４’，６’－トリイソプロピルビフェニル（ＸＰｈｏｓ，６１ｍｇ，０．１２７ｍｍｏｌ）をＴＨＦ（３２ｍＬ）に懸濁し、１５時間還流した。放冷後、反応混合物に水を加えて固体をろ取し、水およびメタノールで洗浄することで２－［５－（２－フェニルピリジン－３－イル）－ビフェニル－３－イル］－４，６－ビス（４－ビフェニリル）ピリミジン（Ｅ２）を得た（収量３．１８ｇ，収率９２％）。
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．７８（ｄ，Ｊ＝４．７Ｈｚ，１Ｈ），８．７６（ｄ，Ｊ＝８．８Ｈｚ，２Ｈ），８．４１（ｓ，１Ｈ），８．３６（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），８．０４（ｓ，１Ｈ），７．９８（ｄ，Ｊ＝７．７Ｈｚ，１Ｈ），７．８２（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．７９（ｄ，Ｊ＝８．６Ｈｚ，２Ｈ），７．７８（ｓ，１Ｈ），７．６１（ｓ．１Ｈ），７．３５－７．５４（ｍ，１７Ｈ）．
合成実施例－３（Ｅ９の合成） Under an argon atmosphere, 4-(3-bromo-5-chlorophenyl)-2-(4-bromophenyl)-6-(4-biphenylyl)pyrimidine (2.0 g, 3.47 mmol), phenylboronic acid (0.93 g , 7.63 mmol), 2M aqueous potassium phosphate solution (10.4 mL), and tetrakis(triphenylphosphine)palladium (80 mg, 0.069 mmol) were suspended in THF (35 mL) and refluxed for 19 hours. The reaction mixture was filtered and the filtrate was concentrated. The concentrated filtrate is added to methanol to precipitate a solid, which is collected by filtration to give the desired 2,4-bis(4-biphenylyl)-4-(5-chlorobiphenyl-3-yl)-pyrimidine. was obtained (yield 1.91 g, yield 96%)
Under an argon atmosphere, 2,4-bis(4-biphenylyl)-4-(5-chlorobiphenyl-3-yl)-pyrimidine (1.81 g, 3.17 mmol), 3-(4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl)-2-phenylpyridine (0.982 g, 3.49 mmol), 2M-potassium phosphate aqueous solution (4.8 mL), palladium acetate (14 mg, 0.063 mmol) ) and 2-dicyclohexylphosphino-2′,4′,6′-triisopropylbiphenyl (XPhos, 61 mg, 0.127 mmol) were suspended in THF (32 mL) and refluxed for 15 hours. After allowing to cool, water was added to the reaction mixture, the solid was collected by filtration, and washed with water and methanol to give 2-[5-(2-phenylpyridin-3-yl)-biphenyl-3-yl]-4, 6-bis(4-biphenylyl)pyrimidine (E2) was obtained (3.18 g, 92% yield).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.78 (d, J = 4.7 Hz, 1 H), 8.76 (d, J = 8.8 Hz, 2 H), 8.41 (s, 1 H), 8.36 (d, J = 8.6Hz, 2H), 8.04 (s, 1H), 7.98 (d, J = 7.7Hz, 1H), 7.82 (d, J = 8.6Hz , 2H), 7.79 (d, J=8.6Hz, 2H), 7.78 (s, 1H), 7.61 (s.1H), 7.35-7.54 (m, 17H).
Synthesis Example-3 (Synthesis of E9)
アルゴン雰囲気下、２－クロロ－４，６－ビス（４－ビフェニリル）ピリミジン（１．４０ｇ、３．３ｍｍｏｌ）、（５，５－ジメチル－１，３，２－ジオキサボリナン－２－イル）－３，５－ビス（２－フェニルピリジン－３－イル）ベンゼン（１．９９ｇ、４．０ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（５．０ｍＬ）、テトラキス（トリフェニルホスフィン）パラジウム（７７．２ｍｇ，０．０６７ｍｍｏｌ）をＴＨＦ（１７ｍＬ）に懸濁し、５時間還流した。反応混合物に水およびメタノールを加えたのちにろ過し、ろ取物を水及びメタノールで洗浄した。得られた固体をトルエンで再結晶することで、目的の４，６－ビス（４－ビフェニリル）－２－［３，５－ビス（２－フェニルピリジン－３－イル）フェニル］－ピリミジン（Ｅ９）を得た（収量２．０５ｇ、収率８０％）。
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．７３（ｄ，Ｊ＝４．７Ｈ，２Ｈ），８．４７（ｓ，２Ｈ），８．２３（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），８．０５（ｓ，１Ｈ），７．７９（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），７．６９－７．７２（ｍ，４Ｈ），７．６１（ｄ，Ｊ＝７．７Ｈｚ，２Ｈ），７．４０－７．５３（ｍ，１０Ｈ），７．２７－７．３７（ｍ，８Ｈ），７．２１（ｓ，１Ｈ）．
合成実施例－４（Ｅ１０の合成） 2-chloro-4,6-bis(4-biphenylyl)pyrimidine (1.40 g, 3.3 mmol), (5,5-dimethyl-1,3,2-dioxaboolinan-2-yl)-3 under argon atmosphere , 5-bis(2-phenylpyridin-3-yl)benzene (1.99 g, 4.0 mmol), 2M-potassium phosphate aqueous solution (5.0 mL), tetrakis(triphenylphosphine) palladium (77.2 mg, 0 .067 mmol) was suspended in THF (17 mL) and refluxed for 5 hours. After water and methanol were added to the reaction mixture, the mixture was filtered, and the filtrate was washed with water and methanol. The resulting solid was recrystallized from toluene to give thetarget 4,6-bis(4-biphenylyl)-2-[3,5-bis(2-phenylpyridin-3-yl)phenyl]-pyrimidine (E9 ) was obtained (2.05 g, 80% yield).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.73 (d, J = 4.7H, 2H), 8.47 (s, 2H), 8.23 (d, J = 8.5Hz, 4H), 8.05 (s, 1H), 7.79 (d, J = 8.5Hz, 4H), 7.69-7.72 (m, 4H), 7.61 (d, J = 7.7Hz, 2H) ), 7.40-7.53 (m, 10H), 7.27-7.37 (m, 8H), 7.21 (s, 1H).
Synthesis Example-4 (Synthesis of E10)
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．７３（ｄ，Ｊ＝４．７Ｈ，２Ｈ），８．４７（ｓ，２Ｈ），８．２３（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），８．０５（ｓ，１Ｈ），７．７９（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），７．６９－７．７２（ｍ，４Ｈ），７．６１（ｄ，Ｊ＝７．７Ｈｚ，２Ｈ），７．４０－７．５３（ｍ，１０Ｈ），７．２７－７．３７（ｍ，８Ｈ），７．２１（ｓ，１Ｈ）．
合成実施例－４（Ｅ１０の合成） 2-chloro-4,6-bis(4-biphenylyl)pyrimidine (1.40 g, 3.3 mmol), (5,5-dimethyl-1,3,2-dioxaboolinan-2-yl)-3 under argon atmosphere , 5-bis(2-phenylpyridin-3-yl)benzene (1.99 g, 4.0 mmol), 2M-potassium phosphate aqueous solution (5.0 mL), tetrakis(triphenylphosphine) palladium (77.2 mg, 0 .067 mmol) was suspended in THF (17 mL) and refluxed for 5 hours. After water and methanol were added to the reaction mixture, the mixture was filtered, and the filtrate was washed with water and methanol. The resulting solid was recrystallized from toluene to give the
1 H-NMR (400 MHz, CDCl 3 ): δ 8.73 (d, J = 4.7H, 2H), 8.47 (s, 2H), 8.23 (d, J = 8.5Hz, 4H), 8.05 (s, 1H), 7.79 (d, J = 8.5Hz, 4H), 7.69-7.72 (m, 4H), 7.61 (d, J = 7.7Hz, 2H) ), 7.40-7.53 (m, 10H), 7.27-7.37 (m, 8H), 7.21 (s, 1H).
Synthesis Example-4 (Synthesis of E10)
アルゴン雰囲気下、４，６－ビス（４－ビフェニリル）－２－［３－（４，４，５，５－テトラメチル－１，３，２－ジオキサボロラン－２－イル）－５－クロロビフェニル－３－イル］－ピリミジン（２．００ｇ、３．０ｍｍｏｌ）、３－クロロ－５－メチル－２－フェニルピリジン（０．７４ｇ、３．６ｍｍｏｌ）、２Ｍ－リン酸カリウム水溶液（４．５ｍＬ）、ビス（トリシクロヘキシルホスフィン）パラジウムジクロライド（４４．６ｍｇ，０．０６ｍｍｏｌ）をＴＨＦ（３０ｍＬ）に懸濁し、２時間還流した。反応混合物に水およびメタノールを加えたのちにろ過し、ろ取物を水及びメタノールで洗浄した。得られた固体をトルエンで再結晶することで、目的の２－［５－（５－メチル－２－フェニルピリジン－３－イル）－ビフェニル－３－イル］－４，６－ビス（４－ビフェニリル）ピリミジン（Ｅ１０）を得た（収量１．２５ｇ、収率５９％）
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．８２（ｓ，１Ｈ），８．６６（ｓ，１Ｈ），８．６０（ｄ，Ｊ＝２．１Ｈｚ，１Ｈ），８．３６（ｄ，Ｊ＝６．７Ｈｚ，４Ｈ），８．１２（ｓ，１Ｈ），７．８２（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），７．８０（ｄ，Ｊ＝２．１Ｈｚ，１Ｈ），７．６９－７．７２（ｍ，４Ｈ），７．２７－７．５３（ｍ，１７Ｈ），２．５０（ｓ，３Ｈ）．
また、下記実験例で使用した環状アジン化合物については、前記合成実施例で示される製造法と同様の手段により合成した。 Under an argon atmosphere, 4,6-bis(4-biphenylyl)-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-chlorobiphenyl- 3-yl]-pyrimidine (2.00 g, 3.0 mmol), 3-chloro-5-methyl-2-phenylpyridine (0.74 g, 3.6 mmol), 2M aqueous potassium phosphate solution (4.5 mL), Bis(tricyclohexylphosphine)palladium dichloride (44.6 mg, 0.06 mmol) was suspended in THF (30 mL) and refluxed for 2 hours. After water and methanol were added to the reaction mixture, the mixture was filtered, and the filtrate was washed with water and methanol. The obtained solid was recrystallized from toluene to give the target 2-[5-(5-methyl-2-phenylpyridin-3-yl)-biphenyl-3-yl]-4,6-bis(4- Biphenylyl)pyrimidine (E10) was obtained (yield 1.25 g, 59% yield).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.82 (s, 1H), 8.66 (s, 1H), 8.60 (d, J = 2.1Hz, 1H), 8.36 (d, J = 6.7 Hz, 4H), 8.12 (s, 1H), 7.82 (d, J = 8.5Hz, 4H), 7.80 (d, J = 2.1Hz, 1H), 7. 69-7.72 (m, 4H), 7.27-7.53 (m, 17H), 2.50 (s, 3H).
Moreover, the cyclic azine compounds used in the following experimental examples were synthesized by means similar to the production method shown in the synthesis examples.
１Ｈ－ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３）：δ８．８２（ｓ，１Ｈ），８．６６（ｓ，１Ｈ），８．６０（ｄ，Ｊ＝２．１Ｈｚ，１Ｈ），８．３６（ｄ，Ｊ＝６．７Ｈｚ，４Ｈ），８．１２（ｓ，１Ｈ），７．８２（ｄ，Ｊ＝８．５Ｈｚ，４Ｈ），７．８０（ｄ，Ｊ＝２．１Ｈｚ，１Ｈ），７．６９－７．７２（ｍ，４Ｈ），７．２７－７．５３（ｍ，１７Ｈ），２．５０（ｓ，３Ｈ）．
また、下記実験例で使用した環状アジン化合物については、前記合成実施例で示される製造法と同様の手段により合成した。 Under an argon atmosphere, 4,6-bis(4-biphenylyl)-2-[3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-5-chlorobiphenyl- 3-yl]-pyrimidine (2.00 g, 3.0 mmol), 3-chloro-5-methyl-2-phenylpyridine (0.74 g, 3.6 mmol), 2M aqueous potassium phosphate solution (4.5 mL), Bis(tricyclohexylphosphine)palladium dichloride (44.6 mg, 0.06 mmol) was suspended in THF (30 mL) and refluxed for 2 hours. After water and methanol were added to the reaction mixture, the mixture was filtered, and the filtrate was washed with water and methanol. The obtained solid was recrystallized from toluene to give the target 2-[5-(5-methyl-2-phenylpyridin-3-yl)-biphenyl-3-yl]-4,6-bis(4- Biphenylyl)pyrimidine (E10) was obtained (yield 1.25 g, 59% yield).
1 H-NMR (400 MHz, CDCl 3 ): δ 8.82 (s, 1H), 8.66 (s, 1H), 8.60 (d, J = 2.1Hz, 1H), 8.36 (d, J = 6.7 Hz, 4H), 8.12 (s, 1H), 7.82 (d, J = 8.5Hz, 4H), 7.80 (d, J = 2.1Hz, 1H), 7. 69-7.72 (m, 4H), 7.27-7.53 (m, 17H), 2.50 (s, 3H).
Moreover, the cyclic azine compounds used in the following experimental examples were synthesized by means similar to the production method shown in the synthesis examples.
有機電界発光素子の作製と性能評価に用いる化合物の構造式及びその略称を以下に示した。
The structural formulas and abbreviations of the compounds used for the production and performance evaluation of the organic electroluminescent device are shown below.
素子実施例－１（以下の有機電界発光素子の積層構成については、図２を参照されたい。）
（基板１０１、陽極１０２の用意）
陽極をその表面に備えた基板として、２ｍｍ幅の酸化インジウム－スズ（ＩＴＯ）膜（膜厚１１０ｎｍ）がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用意した。ついで、この基板をイソプロピルアルコールで洗浄した後、オゾン紫外線洗浄にて表面処理を行った。
（真空蒸着の準備）
洗浄後の表面処理が施された基板上に、真空蒸着法で各層の真空蒸着を行い、各層を積層形成した。 Device Example-1 (Refer to FIG. 2 for the layered structure of the following organic electroluminescent device.)
(Preparation ofsubstrate 101 and anode 102)
As a substrate having an anode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
(Preparation for vacuum deposition)
Each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.
（基板１０１、陽極１０２の用意）
陽極をその表面に備えた基板として、２ｍｍ幅の酸化インジウム－スズ（ＩＴＯ）膜（膜厚１１０ｎｍ）がストライプ状にパターンされたＩＴＯ透明電極付きガラス基板を用意した。ついで、この基板をイソプロピルアルコールで洗浄した後、オゾン紫外線洗浄にて表面処理を行った。
（真空蒸着の準備）
洗浄後の表面処理が施された基板上に、真空蒸着法で各層の真空蒸着を行い、各層を積層形成した。 Device Example-1 (Refer to FIG. 2 for the layered structure of the following organic electroluminescent device.)
(Preparation of
As a substrate having an anode on its surface, a glass substrate with an ITO transparent electrode, in which an indium-tin oxide (ITO) film (thickness: 110 nm) with a width of 2 mm was patterned in stripes, was prepared. Then, after washing the substrate with isopropyl alcohol, the surface was treated by ozone ultraviolet washing.
(Preparation for vacuum deposition)
Each layer was vacuum-deposited on the surface-treated substrate after cleaning by a vacuum deposition method to laminate each layer.
まず、真空蒸着槽内に前記ガラス基板を導入し、１．０×１０－４Ｐａまで減圧した。そして、以下の順で、各層の成膜条件に従ってそれぞれ作製した。
（正孔注入層１０３の作製）
昇華精製したＨＴＬ－１とＮＤＰ－９を０．１５ｎｍ／秒の速度で１０ｎｍ成膜し、正孔注入層１０３を作製した。
（第一正孔輸送層１０５１の作製）
昇華精製したＨＴＬを０．１５ｎｍ／秒の速度で８５ｎｍ成膜し、第一正孔輸送層１０５１を作製した。
（第二正孔輸送層１０５２の作製）
昇華精製したＥＢＬ－１を０．１５ｎｍ／秒の速度で５ｎｍ成膜し、第二正孔輸送層１０５２を作製した。
（発光層１０６の作製）
昇華精製したＢＨ－１とＢＤ－１とを９５：５（質量比）の割合で２０ｎｍ成膜し、発光層１０６を作製した。成膜速度は０．１８ｎｍ／秒であった。
（第一電子輸送層１０７１の作製）
昇華精製したＨＢＬ－１を０．０５ｎｍ／秒の速度で６ｎｍ成膜し、第一電子輸送層１０７１を作製した。
（第二電子輸送層１０７２の作製）
化合物Ｅ１およびＬｉｑを５０：５０（質量比）の割合で２５ｎｍ成膜し、第二電子輸送層１０７２を作製した。成膜速度は０．１５ｎｍ／秒であった。
（陰極１０８の作製）
最後に、基板上のＩＴＯストライプと直交するようにメタルマスクを配し、陰極１０８を成膜した。陰極はイッテルビウム、銀／マグネシウム（質量比９／１）と銀とを、この順番で、それぞれ２ｎｍ、１２ｎｍと９０ｎｍとで成膜し、３層構造とした。イッテルビウムの成膜速度は０．０２ｎｍ／秒、銀／マグネシウムの成膜速度は０．５ｎｍ／秒、銀の成膜速度は成膜速度０．２ｎｍ／秒であった。 First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 −4 Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.
(Preparation of hole injection layer 103)
Sublimation-purified HTL-1 and NDP-9 were deposited at a rate of 0.15 nm/sec to a thickness of 10 nm to form ahole injection layer 103 .
(Preparation of first hole transport layer 1051)
A firsthole transport layer 1051 was produced by forming a film of HTL purified by sublimation to a thickness of 85 nm at a rate of 0.15 nm/sec.
(Preparation of second hole transport layer 1052)
Sublimation-purified EBL-1 was deposited at a rate of 0.15 nm/second to a thickness of 5 nm to form a secondhole transport layer 1052 .
(Production of light-emitting layer 106)
Sublimation-purified BH-1 and BD-1 were deposited at a ratio of 95:5 (mass ratio) to form a film having a thickness of 20 nm to prepare a light-emittinglayer 106 . The deposition rate was 0.18 nm/sec.
(Preparation of first electron transport layer 1071)
Sublimation-purified HBL-1 was deposited at a rate of 0.05 nm/second to a thickness of 6 nm to prepare a firstelectron transport layer 1071 .
(Preparation of second electron transport layer 1072)
Compound E1 and Liq were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to form a secondelectron transport layer 1072 . The deposition rate was 0.15 nm/sec.
(Preparation of cathode 108)
Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and acathode 108 was formed. For the cathode, ytterbium, silver/magnesium (mass ratio 9/1) and silver were deposited in this order to thicknesses of 2 nm, 12 nm and 90 nm, respectively, to form a three-layer structure. The deposition rate of ytterbium was 0.02 nm/second, the deposition rate of silver/magnesium was 0.5 nm/second, and the deposition rate of silver was 0.2 nm/second.
（正孔注入層１０３の作製）
昇華精製したＨＴＬ－１とＮＤＰ－９を０．１５ｎｍ／秒の速度で１０ｎｍ成膜し、正孔注入層１０３を作製した。
（第一正孔輸送層１０５１の作製）
昇華精製したＨＴＬを０．１５ｎｍ／秒の速度で８５ｎｍ成膜し、第一正孔輸送層１０５１を作製した。
（第二正孔輸送層１０５２の作製）
昇華精製したＥＢＬ－１を０．１５ｎｍ／秒の速度で５ｎｍ成膜し、第二正孔輸送層１０５２を作製した。
（発光層１０６の作製）
昇華精製したＢＨ－１とＢＤ－１とを９５：５（質量比）の割合で２０ｎｍ成膜し、発光層１０６を作製した。成膜速度は０．１８ｎｍ／秒であった。
（第一電子輸送層１０７１の作製）
昇華精製したＨＢＬ－１を０．０５ｎｍ／秒の速度で６ｎｍ成膜し、第一電子輸送層１０７１を作製した。
（第二電子輸送層１０７２の作製）
化合物Ｅ１およびＬｉｑを５０：５０（質量比）の割合で２５ｎｍ成膜し、第二電子輸送層１０７２を作製した。成膜速度は０．１５ｎｍ／秒であった。
（陰極１０８の作製）
最後に、基板上のＩＴＯストライプと直交するようにメタルマスクを配し、陰極１０８を成膜した。陰極はイッテルビウム、銀／マグネシウム（質量比９／１）と銀とを、この順番で、それぞれ２ｎｍ、１２ｎｍと９０ｎｍとで成膜し、３層構造とした。イッテルビウムの成膜速度は０．０２ｎｍ／秒、銀／マグネシウムの成膜速度は０．５ｎｍ／秒、銀の成膜速度は成膜速度０．２ｎｍ／秒であった。 First, the glass substrate was introduced into a vacuum deposition tank, and the pressure was reduced to 1.0×10 −4 Pa. Then, each layer was produced in the following order according to the film forming conditions of each layer.
(Preparation of hole injection layer 103)
Sublimation-purified HTL-1 and NDP-9 were deposited at a rate of 0.15 nm/sec to a thickness of 10 nm to form a
(Preparation of first hole transport layer 1051)
A first
(Preparation of second hole transport layer 1052)
Sublimation-purified EBL-1 was deposited at a rate of 0.15 nm/second to a thickness of 5 nm to form a second
(Production of light-emitting layer 106)
Sublimation-purified BH-1 and BD-1 were deposited at a ratio of 95:5 (mass ratio) to form a film having a thickness of 20 nm to prepare a light-emitting
(Preparation of first electron transport layer 1071)
Sublimation-purified HBL-1 was deposited at a rate of 0.05 nm/second to a thickness of 6 nm to prepare a first
(Preparation of second electron transport layer 1072)
Compound E1 and Liq were deposited at a ratio of 50:50 (mass ratio) to a thickness of 25 nm to form a second
(Preparation of cathode 108)
Finally, a metal mask was placed perpendicular to the ITO stripes on the substrate, and a
以上により、図２に示すような発光面積４ｍｍ２有機電界発光素子１００を作製した。なお、それぞれの膜厚は、触針式膜厚測定計（ＤＥＫＴＡＫ、Ｂｒｕｋｅｒ社製）で測定した。
As described above, an organic electroluminescence device 100 having a light emitting area of 4 mm 2 as shown in FIG. 2 was produced. Each film thickness was measured with a stylus film thickness meter (DEKTAK, manufactured by Bruker).
さらに、この素子を酸素および水分濃度１ｐｐｍ以下の窒素雰囲気グローブボックス内で封止した。封止は、ガラス製の封止キャップと成膜基板（素子）とを、ビスフェノールＦ型エポキシ樹脂（ナガセケムテックス社製）を用いて行った。
Furthermore, this device was sealed in a nitrogen atmosphere glove box with an oxygen and moisture concentration of 1 ppm or less. Sealing was performed by using a bisphenol F-type epoxy resin (manufactured by Nagase ChemteX Corporation) between the glass sealing cap and the film formation substrate (element).
上記のようにして作製した有機電界発光素子に直流電流を印加し、電流密度１０ｍＡ／ｃｍ２を流した時の駆動電圧（Ｖ）、電流効率を測定した。なお、駆動電圧及び電流効率は、後述の素子比較例－１における結果を基準値（１００）とした相対値である。得られた測定結果を表１に示す。
（素子実施例－２～１０）
素子実施例－１において、化合物Ｅ１の代わりに化合物Ｅ２～Ｅ１０をそれぞれ用いた以外は、素子実施例－１と同じ方法で有機電界発光素子を作製し、評価した。得られた測定結果を表１に示す。
（素子比較例－１～３）
素子実施例－１において、化合物Ｅ１の代わりにＥＴＬ－１～ＥＴＬ－３をそれぞれ用いた以外は、素子実施例－１と同じ方法で有機電界発光素子を作製し、評価した。得られた測定結果を表１に示す。 A direct current was applied to the organic electroluminescence device produced as described above, and the driving voltage (V) and the current efficiency were measured when a current density of 10 mA/cm 2 was passed. The driving voltage and the current efficiency are relative values with the result of Device Comparative Example-1 described later as a reference value (100). Table 1 shows the measurement results obtained.
(Element Examples-2 to 10)
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-1, except that Compounds E2 to E10 were used in place of Compound E1 in Device Example-1. Table 1 shows the measurement results obtained.
(Comparative element examples -1 to 3)
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-1, except that ETL-1 to ETL-3 were used in place of Compound E1 in Device Example-1. Table 1 shows the measurement results obtained.
（素子実施例－２～１０）
素子実施例－１において、化合物Ｅ１の代わりに化合物Ｅ２～Ｅ１０をそれぞれ用いた以外は、素子実施例－１と同じ方法で有機電界発光素子を作製し、評価した。得られた測定結果を表１に示す。
（素子比較例－１～３）
素子実施例－１において、化合物Ｅ１の代わりにＥＴＬ－１～ＥＴＬ－３をそれぞれ用いた以外は、素子実施例－１と同じ方法で有機電界発光素子を作製し、評価した。得られた測定結果を表１に示す。 A direct current was applied to the organic electroluminescence device produced as described above, and the driving voltage (V) and the current efficiency were measured when a current density of 10 mA/cm 2 was passed. The driving voltage and the current efficiency are relative values with the result of Device Comparative Example-1 described later as a reference value (100). Table 1 shows the measurement results obtained.
(Element Examples-2 to 10)
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-1, except that Compounds E2 to E10 were used in place of Compound E1 in Device Example-1. Table 1 shows the measurement results obtained.
(Comparative element examples -1 to 3)
An organic electroluminescence device was produced and evaluated in the same manner as in Device Example-1, except that ETL-1 to ETL-3 were used in place of Compound E1 in Device Example-1. Table 1 shows the measurement results obtained.
本発明を詳細に、また特定の実施態様を参照して説明したが、本発明の本質と範囲を逸脱することなく様々な変更や修正を加えることができることは当業者にとって明らかである。
Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.
なお、２０２１年５月１９日に出願された日本国特許出願２０２１－０８４２３６号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。
In addition, the entire contents of the specification, claims, drawings and abstract of Japanese Patent Application No. 2021-084236 filed on May 19, 2021 are cited here as disclosure of the specification of the present invention. , is to be incorporated.
本発明の化合物は有機電界発光素子等に使用できる。
The compound of the present invention can be used for organic electroluminescence devices and the like.
１００ 有機電界発光素子
１ 基板
２ 陽極
３ 正孔注入層
４ 正孔輸送層
５ 発光層
６ 電子輸送層
７ 電子注入層
８ 陰極
１０１ 基板
１０２ 陽極
１０３ 正孔注入層
１０５１ 第一正孔輸送層
１０５２ 第二正孔輸送層
１０６ 発光層
１０７１ 第一電子輸送層
１０７２ 第二電子輸送層
１０８ 陰極 REFERENCE SIGNSLIST 100 Organic Electroluminescent Element 1 Substrate 2 Anode 3 Hole Injection Layer 4 Hole Transport Layer 5 Light Emitting Layer 6 Electron Transport Layer 7 Electron Injection Layer 8 Cathode 101 Substrate 102 Anode 103 Hole Injection Layer 1051 First Hole Transport Layer 1052 Second Two hole-transporting layers 106 Light-emitting layer 1071 First electron-transporting layer 1072 Second electron-transporting layer 108 Cathode
１ 基板
２ 陽極
３ 正孔注入層
４ 正孔輸送層
５ 発光層
６ 電子輸送層
７ 電子注入層
８ 陰極
１０１ 基板
１０２ 陽極
１０３ 正孔注入層
１０５１ 第一正孔輸送層
１０５２ 第二正孔輸送層
１０６ 発光層
１０７１ 第一電子輸送層
１０７２ 第二電子輸送層
１０８ 陰極 REFERENCE SIGNS
Claims (5)
- 式（１）で表されるピリミジン化合物：
Ｘ１及びＸ２は、いずれか一方が窒素原子であり、他方はＣ－Ｈである；
Ａｒ１及びＡｒ２は、各々独立に、
フェニル基、ビフェニリル基、又は、ナフチル基を表す；
Ａｒ３及びＡｒ４は、各々独立に、
炭素数６～２０のアリール基、又は、
炭素数４～２０のヘテロアリール基を表す；
Ｌ１及びＬ２は、各々独立に、
直接結合、フェニレン、ピリジレン、又は、ナフチレンを表す；
環Ａは、
フェニル基、ピリジル基、ナフチル基、炭素数１～１０のアルキル基、及びＣＮ基からなる群よりなる１つ以上の置換基を有していてもよいピリジンであり、かつ、
Ａｒ３及びＬ１は、各々ピリジン環の隣接する２つの炭素原子と結合している；
ｎは１又は２である；
ｎが２のとき、２つのＬ１は互いに同一又は相異なっていてもよい。 A pyrimidine compound represented by formula (1):
one of X 1 and X 2 is a nitrogen atom and the other is C—H;
Ar 1 and Ar 2 are each independently
represents a phenyl group, a biphenylyl group, or a naphthyl group;
Ar 3 and Ar 4 are each independently
an aryl group having 6 to 20 carbon atoms, or
represents a heteroaryl group having 4 to 20 carbon atoms;
L 1 and L 2 are each independently
represents a direct bond, phenylene, pyridylene or naphthylene;
Ring A is
pyridine optionally having one or more substituents selected from the group consisting of a phenyl group, a pyridyl group, a naphthyl group, an alkyl group having 1 to 10 carbon atoms, and a CN group, and
Ar 3 and L 1 are each attached to two adjacent carbon atoms of the pyridine ring;
n is 1 or 2;
When n is 2 , two L1's may be the same or different. - Ａｒ１とＡｒ２が同一である請求項１に記載のピリミジン化合物。 2. The pyrimidine compound of claim 1, wherein Ar 1 and Ar 2 are the same.
- Ａｒ１及びＡｒ２の少なくとも一方が４－ビフェニリル基である請求項１に記載のピリミジン化合物。 2. The pyrimidine compound according to claim 1, wherein at least one of Ar 1 and Ar 2 is a 4-biphenylyl group.
- 式（Ｅ１）～（Ｅ１０）で表される、請求項１に記載のピリミジン化合物。
- 陽極と、
陰極と、
少なくとも発光層を含む１以上の有機薄膜層と、を備え、
前記有機薄膜層の少なくとも１層が、請求項１～４のいずれか１項に記載のピリミジン化合物を含有する有機電界発光素子。 an anode;
a cathode;
and one or more organic thin film layers including at least a light-emitting layer,
An organic electroluminescence device, wherein at least one of the organic thin film layers contains the pyrimidine compound according to any one of claims 1 to 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2021-084236 | 2021-05-19 | ||
| JP2021084236 | 2021-05-19 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2022244689A1 true WO2022244689A1 (en) | 2022-11-24 |
Family
ID=84140431
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP2022/020179 WO2022244689A1 (en) | 2021-05-19 | 2022-05-13 | Pyrimidine compound, material for organic electroluminescent element, and organic electroluminescent element |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2022179374A (en) |
| WO (1) | WO2022244689A1 (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014098043A1 (en) * | 2012-12-17 | 2014-06-26 | 東ソー株式会社 | Pyrimidine compound, and organic electroluminescent element containing same |
| US20140367656A1 (en) * | 2013-06-12 | 2014-12-18 | Samsung Display Co., Ltd. | Organic light-emitting diode |
| KR20170058625A (en) * | 2015-11-19 | 2017-05-29 | 주식회사 랩토 | pyrimidine derivatives substituted with aryl- or heteroaryl-substituted phenyl group, and organic electroluminescent device including the same |
| WO2017179809A1 (en) * | 2016-04-11 | 2017-10-19 | 주식회사 두산 | Organic light-emitting compound and organic electroluminescent element using same |
| JP2020164503A (en) * | 2019-03-27 | 2020-10-08 | 東ソー株式会社 | Triazine compound having ortho structure |
| JP2021070682A (en) * | 2019-10-24 | 2021-05-06 | 東ソー株式会社 | Triazine compound having pyridyl group |
| JP2021155378A (en) * | 2020-03-30 | 2021-10-07 | 東ソー株式会社 | Triazine compound |
-
2022
- 2022-05-09 JP JP2022076828A patent/JP2022179374A/en active Pending
- 2022-05-13 WO PCT/JP2022/020179 patent/WO2022244689A1/en unknown
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014098043A1 (en) * | 2012-12-17 | 2014-06-26 | 東ソー株式会社 | Pyrimidine compound, and organic electroluminescent element containing same |
| US20140367656A1 (en) * | 2013-06-12 | 2014-12-18 | Samsung Display Co., Ltd. | Organic light-emitting diode |
| KR20170058625A (en) * | 2015-11-19 | 2017-05-29 | 주식회사 랩토 | pyrimidine derivatives substituted with aryl- or heteroaryl-substituted phenyl group, and organic electroluminescent device including the same |
| WO2017179809A1 (en) * | 2016-04-11 | 2017-10-19 | 주식회사 두산 | Organic light-emitting compound and organic electroluminescent element using same |
| JP2020164503A (en) * | 2019-03-27 | 2020-10-08 | 東ソー株式会社 | Triazine compound having ortho structure |
| JP2021070682A (en) * | 2019-10-24 | 2021-05-06 | 東ソー株式会社 | Triazine compound having pyridyl group |
| JP2021155378A (en) * | 2020-03-30 | 2021-10-07 | 東ソー株式会社 | Triazine compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2022179374A (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9997726B2 (en) | Dibenzothiophene-containing materials in phosphorescent light emitting diodes | |
| KR102213030B1 (en) | Novel boron compounds and Organic light emitting diode including the same | |
| US11937495B2 (en) | Organic light emitting element, composition and membrane | |
| US8013330B2 (en) | Compound for organic electroluminescent device and organic electroluminescent device | |
| US10014480B2 (en) | Heterocyclic compounds and organic electroluminescent devices using the same | |
| WO2011105161A1 (en) | Organic electroluminescent element | |
| KR101092006B1 (en) | Anthracene derivatives and organic light-emitting diode including the same | |
| US11251378B2 (en) | Organic light-emitting diode having alleviated luminance reduction in low dynamic range | |
| US10483467B2 (en) | Organic light emitting diode | |
| JP2010523648A (en) | Material for organic photoelectric device including hole transport unit and electron transport unit, and organic photoelectric device including the same | |
| US20110140044A1 (en) | Organosulfur compound, process for producing the same, and organic electroluminescence element using the same | |
| JP7181397B2 (en) | Novel boron compound and organic light-emitting device containing the same | |
| JP7308695B2 (en) | Bisazine compound | |
| KR101233375B1 (en) | Novel compound for organic photoelectric device and organic photoelectric device including the same | |
| JP2020164503A (en) | Triazine compound having ortho structure | |
| JP7361564B2 (en) | Triazine compounds containing Group 14 elements | |
| WO2022244689A1 (en) | Pyrimidine compound, material for organic electroluminescent element, and organic electroluminescent element | |
| JP7450432B2 (en) | triazine compounds | |
| KR102149449B1 (en) | Novel organic compounds for organic light-emitting diode and organic light-emitting diode including the same | |
| JPWO2004096743A1 (en) | Organic electroluminescence device | |
| WO2012005342A1 (en) | Novel organic compound and organic light-emitting device including the same | |
| WO2022131135A1 (en) | Pyrimidine compound and organic electroluminescent element | |
| WO2023090404A1 (en) | Condensed ring fluorene compound, material for organic electroluminescent element, and organic electroluminescent element | |
| JP2018115151A (en) | Triazine compound having benzimidazole group | |
| KR20190139492A (en) | organic light-emitting diode with High efficiency |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 22804601 Country of ref document: EP Kind code of ref document: A1 |
|
| NENP | Non-entry into the national phase |
Ref country code: DE |