JP4710268B2 - Pyromethene compound, light emitting device material and light emitting device using the same - Google Patents
Pyromethene compound, light emitting device material and light emitting device using the same Download PDFInfo
- Publication number
- JP4710268B2 JP4710268B2 JP2004209554A JP2004209554A JP4710268B2 JP 4710268 B2 JP4710268 B2 JP 4710268B2 JP 2004209554 A JP2004209554 A JP 2004209554A JP 2004209554 A JP2004209554 A JP 2004209554A JP 4710268 B2 JP4710268 B2 JP 4710268B2
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- light emitting
- compound
- emitting device
- hydrogen
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- 239000000463 material Substances 0.000 title claims description 133
- 150000001875 compounds Chemical class 0.000 title claims description 81
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 35
- 239000002019 doping agent Substances 0.000 claims description 33
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 32
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 24
- 239000001257 hydrogen Substances 0.000 claims description 24
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 6
- 229910052731 fluorine Inorganic materials 0.000 claims description 6
- 239000011737 fluorine Substances 0.000 claims description 6
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 239000010410 layer Substances 0.000 description 26
- 239000000843 powder Substances 0.000 description 21
- 238000000859 sublimation Methods 0.000 description 21
- 230000008022 sublimation Effects 0.000 description 21
- 125000001424 substituent group Chemical group 0.000 description 20
- 238000000354 decomposition reaction Methods 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- -1 diamine compound Chemical class 0.000 description 17
- 238000005160 1H NMR spectroscopy Methods 0.000 description 15
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- 238000002844 melting Methods 0.000 description 11
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- 238000000295 emission spectrum Methods 0.000 description 10
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- 238000010438 heat treatment Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 9
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 238000007740 vapor deposition Methods 0.000 description 8
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
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- XHXFXVLFKHQFAL-UHFFFAOYSA-N phosphoryl trichloride Chemical compound ClP(Cl)(Cl)=O XHXFXVLFKHQFAL-UHFFFAOYSA-N 0.000 description 6
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- 0 CB(*)C=C1C(C([Al])=C2C([Al])=C(C)C(*)=C=*2)=C(*)C(*)=C1C1C(*)C1 Chemical compound CB(*)C=C1C(C([Al])=C2C([Al])=C(C)C(*)=C=*2)=C(*)C(*)=C1C1C(*)C1 0.000 description 5
- 238000010894 electron beam technology Methods 0.000 description 5
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- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- OKBSDYLCRUOJQK-UHFFFAOYSA-N 2,4-bis(4-tert-butylphenyl)-1h-pyrrole Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CNC(C=2C=CC(=CC=2)C(C)(C)C)=C1 OKBSDYLCRUOJQK-UHFFFAOYSA-N 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 4
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 125000003342 alkenyl group Chemical group 0.000 description 4
- 125000003545 alkoxy group Chemical group 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 125000000304 alkynyl group Chemical group 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 4
- 125000005013 aryl ether group Chemical group 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
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- 229910052697 platinum Inorganic materials 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 101150021206 HST3 gene Proteins 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 125000003172 aldehyde group Chemical group 0.000 description 3
- 150000001350 alkyl halides Chemical class 0.000 description 3
- 125000004414 alkyl thio group Chemical group 0.000 description 3
- 125000003277 amino group Chemical group 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 150000004832 aryl thioethers Chemical group 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000903 blocking effect Effects 0.000 description 3
- 125000003917 carbamoyl group Chemical group [H]N([H])C(*)=O 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 150000004775 coumarins Chemical class 0.000 description 3
- 125000000392 cycloalkenyl group Chemical group 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
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- 125000005401 siloxanyl group Chemical group 0.000 description 3
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 3
- 238000004544 sputter deposition Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
- NZGXEUWGGSDALJ-UHFFFAOYSA-N C1=CC=CC=C1C1=NC=CC=C1[Ir](C=1C(=NC=CC=1)C=1C=CC=CC=1)C1=CC=CN=C1C1=CC=CC=C1 Chemical class C1=CC=CC=C1C1=NC=CC=C1[Ir](C=1C(=NC=CC=1)C=1C=CC=CC=1)C1=CC=CN=C1C1=CC=CC=C1 NZGXEUWGGSDALJ-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- 101000832687 Cavia porcellus 3-alpha-hydroxysteroid sulfotransferase Proteins 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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- CDVPABAGURXNBJ-UHFFFAOYSA-N S1C(=CC=C1)C1=NC=CC=C1[Ir] Chemical class S1C(=CC=C1)C1=NC=CC=C1[Ir] CDVPABAGURXNBJ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- BUFLKQIQXZMRIL-UHFFFAOYSA-N [3,5-bis(4-tert-butylphenyl)-1h-pyrrol-2-yl]-phenylmethanone Chemical compound C1=CC(C(C)(C)C)=CC=C1C1=CC(C=2C=CC(=CC=2)C(C)(C)C)=C(C(=O)C=2C=CC=CC=2)N1 BUFLKQIQXZMRIL-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
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- 229940027991 antiseptic and disinfectant quinoline derivative Drugs 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
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- 238000010030 laminating Methods 0.000 description 2
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 2
- 125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 description 2
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- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
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- 229920005596 polymer binder Polymers 0.000 description 2
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- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
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- 238000006862 quantum yield reaction Methods 0.000 description 2
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- 239000011734 sodium Substances 0.000 description 2
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- 125000003107 substituted aryl group Chemical group 0.000 description 2
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- NGQSLSMAEVWNPU-YTEMWHBBSA-N 1,2-bis[(e)-2-phenylethenyl]benzene Chemical class C=1C=CC=CC=1/C=C/C1=CC=CC=C1\C=C\C1=CC=CC=C1 NGQSLSMAEVWNPU-YTEMWHBBSA-N 0.000 description 1
- MCVPLAHRHVRSKV-UHFFFAOYSA-N 1,2-bis[2,3-di(propan-2-yl)phenyl]perylene Chemical group CC(C)C1=CC=CC(C=2C(=C3C=4C=CC=C5C=CC=C(C=45)C=4C=CC=C(C3=4)C=2)C=2C(=C(C(C)C)C=CC=2)C(C)C)=C1C(C)C MCVPLAHRHVRSKV-UHFFFAOYSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- BCMCBBGGLRIHSE-UHFFFAOYSA-N 1,3-benzoxazole Chemical class C1=CC=C2OC=NC2=C1 BCMCBBGGLRIHSE-UHFFFAOYSA-N 0.000 description 1
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- FLBAYUMRQUHISI-UHFFFAOYSA-N 1,8-naphthyridine Chemical compound N1=CC=CC2=CC=CN=C21 FLBAYUMRQUHISI-UHFFFAOYSA-N 0.000 description 1
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- CVBUKMMMRLOKQR-UHFFFAOYSA-N 1-phenylbutane-1,3-dione Chemical compound CC(=O)CC(=O)C1=CC=CC=C1 CVBUKMMMRLOKQR-UHFFFAOYSA-N 0.000 description 1
- JFJNVIPVOCESGZ-UHFFFAOYSA-N 2,3-dipyridin-2-ylpyridine Chemical compound N1=CC=CC=C1C1=CC=CN=C1C1=CC=CC=N1 JFJNVIPVOCESGZ-UHFFFAOYSA-N 0.000 description 1
- BYOWYTDDDBVNTK-UHFFFAOYSA-N 2,4-bis(4-methoxyphenyl)-1h-pyrrole Chemical compound C1=CC(OC)=CC=C1C1=CNC(C=2C=CC(OC)=CC=2)=C1 BYOWYTDDDBVNTK-UHFFFAOYSA-N 0.000 description 1
- XKXLTKZRCGYWAO-UHFFFAOYSA-N 2,4-bis(4-methylphenyl)-1h-pyrrole Chemical compound C1=CC(C)=CC=C1C1=CNC(C=2C=CC(C)=CC=2)=C1 XKXLTKZRCGYWAO-UHFFFAOYSA-N 0.000 description 1
- YLYPIBBGWLKELC-RMKNXTFCSA-N 2-[2-[(e)-2-[4-(dimethylamino)phenyl]ethenyl]-6-methylpyran-4-ylidene]propanedinitrile Chemical compound C1=CC(N(C)C)=CC=C1\C=C\C1=CC(=C(C#N)C#N)C=C(C)O1 YLYPIBBGWLKELC-RMKNXTFCSA-N 0.000 description 1
- JQMFQLVAJGZSQS-UHFFFAOYSA-N 2-[4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]piperazin-1-yl]-N-(2-oxo-3H-1,3-benzoxazol-6-yl)acetamide Chemical compound C1C(CC2=CC=CC=C12)NC1=NC=C(C=N1)N1CCN(CC1)CC(=O)NC1=CC2=C(NC(O2)=O)C=C1 JQMFQLVAJGZSQS-UHFFFAOYSA-N 0.000 description 1
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Landscapes
- Electroluminescent Light Sources (AREA)
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Description
本発明は、蛍光色素として有用なピロメテン化合物およびそれを用いた発光素子に関するものである。 The present invention relates to a pyromethene compound useful as a fluorescent dye and a light emitting device using the same.
陰極から注入された電子と陽極から注入された正孔が両極に挟まれた有機蛍光体内で再結合する際に発光するという有機積層薄膜発光素子の研究が近年活発に行われている。この素子は、薄型、低駆動電圧下での高輝度発光、蛍光材料を選ぶことによる多色発光が特徴であり注目を集めている。 In recent years, research on an organic laminated thin film light emitting device in which light is emitted when electrons injected from a cathode and holes injected from an anode are recombined in an organic phosphor sandwiched between both electrodes has been actively conducted. This element is attracting attention because it is thin, has high luminance emission under a low driving voltage, and multicolor emission by selecting a fluorescent material.
この研究はコダック社のC.W.Tangらが有機積層薄膜素子が高輝度に発光することを示して以来、多くの研究機関が検討を行っている。コダック社の研究グループが提示した有機積層薄膜発光素子の代表的な構成は、ITOガラス基板上に正孔輸送性のジアミン化合物、発光層である8−ヒドロキシキノリンアルミニウム、そして陰極としてMg:Agを順次設けたものであり、10V程度の駆動電圧で1000cd/m2の緑色発光が可能であった(例えば、非特許文献1参照。)。現在の有機積層薄膜発光素子は、上記の素子構成要素の他に電子輸送層を設けているものなど構成を変えているものもある。 This study was conducted by Kodak C.I. W. Since Tang et al. Have shown that organic multilayer thin-film elements emit light with high brightness, many research institutions have studied. A typical structure of an organic laminated thin film light emitting device presented by a research group of Kodak Company is a hole transporting diamine compound on an ITO glass substrate, 8-hydroxyquinoline aluminum as a light emitting layer, and Mg: Ag as a cathode. These were sequentially provided, and green light emission of 1000 cd / m 2 was possible with a driving voltage of about 10 V (see, for example, Non-Patent Document 1). Some of the present organic laminated thin film light emitting elements have different configurations such as those provided with an electron transport layer in addition to the above element constituent elements.
多色発光の中でも赤色発光は、有用なる発光色として研究が進められている。従来、ビス(ジイソプロピルフェニル)ペリレンなどのペリレン系、ペリノン系、ポルフィリン系、Eu錯体などが赤色発光材料として知られている(例えば、非特許文献2参照。)。 Among multicolor emission, red emission is being studied as a useful emission color. Conventionally, perylene-based materials such as bis (diisopropylphenyl) perylene, perinone-based materials, porphyrin-based materials, Eu complexes, and the like are known as red light-emitting materials (for example, see Non-Patent Document 2).
また、赤色発光を得る手法として、ホスト材料の中に微量の赤色蛍光材料をドーパントとして混入させる方法も検討されている。ホスト材料としては、トリス(8−キノリノラト)アルミニウム錯体、ビス(10−ベンゾキノリノラト)ベリリウム錯体、ジアリールブタジエン誘導体、スチルベン誘導体、ベンズオキサゾール誘導体、ベンゾチアゾール誘導体などがあげられ、その中にドーパントとして4−(ジシアノメチレン)−2−メチル−6−(p−ジメチルアミノスチリル)−H−ピラン、金属フタロシアニン(MgPc、AlPcClなど)化合物、スクアリリウム化合物、ビオラントロン化合物を存在させることによって赤色発光を取り出していた。 In addition, as a technique for obtaining red light emission, a method of mixing a small amount of a red fluorescent material as a dopant in a host material has been studied. Examples of the host material include tris (8-quinolinolato) aluminum complex, bis (10-benzoquinolinolato) beryllium complex, diarylbutadiene derivative, stilbene derivative, benzoxazole derivative, benzothiazole derivative, and the like. Red light emission is extracted by the presence of 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -H-pyran, metal phthalocyanine (MgPc, AlPcCl, etc.) compounds, squarylium compounds, and violanthrone compounds. It was.
また、発光材料、特にドーパントとして、高輝度発光を示す化合物のピロメテン化合物が知られている(例えば、特許文献1参照。)。また、ピロメテン骨格に芳香環等を導入することにより、赤色発光を示すことも知られており、電流効率は最大のもので、5.1cd/Aである(例えば、特許文献2参照。)。
現在、さらなる発光効率や素子寿命の向上、消費電力の低下が求められており、従来技術に用いられる発光材料(ホスト材料、ドーパント材料)では、それらの特性が不十分である。特に、素子寿命は、長時間の通電による素子からの発熱により結晶化し、素子寿命が短くなってしまうものである。一方、この結晶化を抑えるためにアモルファス性を付与した材料は、昇華性が悪いために発光材料の真空蒸着温度(昇華温度と同義)が分解温度よりも高くなってしまい、真空蒸着時に分解や重合などの変性が起こってしまうという問題がある。また、フルカラーディスプレイに必要な三原色の内、緑色発光においては高性能の発光材料が見い出されているが、青色や赤色、特に赤色においては十分な特性、とりわけ高輝度、高色純度、長寿命である発光材料は得られていなかった。 Currently, further improvement in light emission efficiency and device life and reduction in power consumption are demanded, and light emitting materials (host materials and dopant materials) used in the prior art have insufficient properties. In particular, the device life is crystallized due to heat generated from the device by energization for a long time, and the device life is shortened. On the other hand, a material imparted with an amorphous property to suppress this crystallization has a poor sublimation property, so that the vacuum vapor deposition temperature (synonymous with the sublimation temperature) of the light emitting material becomes higher than the decomposition temperature. There is a problem that modification such as polymerization occurs. Of the three primary colors required for full-color displays, high-performance light-emitting materials have been found for green light emission, but blue and red, especially red, have sufficient characteristics, especially high brightness, high color purity, and long life. Some luminescent materials have not been obtained.
本発明は、かかる従来技術の問題を解決し、真空蒸着時に分解せずに成膜でき、発光効率が高く、色純度に優れ、素子寿命が長い発光素子を可能にする新規ピロメテン化合物、およびそれを用いた発光素子を提供する。 The present invention solves such problems of the prior art, a novel pyromethene compound capable of forming a light emitting element without being decomposed during vacuum deposition, having high luminous efficiency, excellent color purity, and having a long element lifetime, and the same Provided is a light emitting element using the above.
すなわち本発明は、一般式(1)で示されるピロメテン化合物である。 That is, the present invention is a pyromethene compound represented by the general formula (1).
(R1〜R2は水素である。R3〜R4はフッ素である。Ar1〜Ar 4 はパラ位がメチル基で置換されたフェニル基を表す。Ar5 は下記一般式(3)で表される。 (R 1 to R 2 are hydrogen .R 3 to R 4 is .A r 5 is the following formula .Ar 1 ~ Ar 4 is a fluorine para-position represents a phenyl group substituted with a methyl group (3 ).
(R11 およびR13は水素である。R 12 は、水素、メチル基、メトキシ基、t−ブチル基の中から選ばれる。R10とR14はそれぞれ同じでも異なっていてもよく、水素、メトキシ基の中から選ばれるが、R10とR14が同時に水素となるときは、R 12 はメチル基、メトキシ基、t−ブチル基から選ばれる。))
また本発明は、一般式(1)で示されるピロメテン化合物である。
(R 11 and R 13 are hydrogen. R 12 is selected from hydrogen, methyl group, methoxy group, and t-butyl group. R 10 and R 14 may be the same or different, Although selected from methoxy group, when R 10 and R 14 is hydrogen at the same time, R 12 is a methyl group, a methoxy group, selected et or t- butyl group.))
The present invention is a pyrromethene compound represented by the general formula (1).
(R1〜R2は水素である。R3〜R4はフッ素である。Ar1〜Ar 4 はパラ位がt−ブチル基で置換されたフェニル基を表す。Ar5 は下記一般式(4)で表される。 (R 1 to R 2 are hydrogen .R 3 to R 4 is .A r 5 is the following general formula .Ar 1 ~ Ar 4 is a fluorine represents a phenyl group para substituted with t- butyl group It is represented by (4).
(R16 およびR18は水素である。R 17 は、水素、メチル基、メトキシ基、t−ブチル基の中から選ばれる。R15とR19はそれぞれ同じであっても、異なっていてもよく、水素、メトキシ基から選ばれる。))
さらに本発明は陽極と陰極の間に発光層が存在し、電気エネルギーにより発光する発光素子であって、該発光素子が一般式(1)で示されるピロメテン化合物を含むことを特徴とする発光素子である。
(R 16 and R 18 are hydrogen. R 17 is selected from hydrogen, a methyl group, a methoxy group, and a t-butyl group. R 15 and R 19 may be the same or different. well, hydrogen is chosen et or methoxy group.))
Furthermore, the present invention is a light emitting device in which a light emitting layer exists between an anode and a cathode and emits light by electric energy, and the light emitting device contains a pyromethene compound represented by the general formula (1). It is.
本発明は、発光素子等に利用可能な高蛍光性のピロメテン化合物を提供できる。また、本発明のピロメテン化合物を用いることにより、真空蒸着時に分解や重合などの変性が起こらず、発光効率かつ高色純度かつ長寿命の発光素子を提供できる。 The present invention can provide a highly fluorescent pyromethene compound that can be used in a light-emitting element or the like. Further, by using the pyromethene compound of the present invention, it is possible to provide a light-emitting element that does not undergo modification such as decomposition or polymerization at the time of vacuum vapor deposition and has high luminous efficiency, high color purity, and long life.
一般的なピロメテン化合物は下記一般式(5)で示される。 A general pyromethene compound is represented by the following general formula (5).
R20、R21およびLは同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、複素環基、ハロゲン、ハロアルカン、ハロアルケン、ハロアルキン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Mはm価の金属を表し、ホウ素、ベリリウム、マグネシウム、クロム、鉄、ニッケル、銅、亜鉛、白金、アルミニウムから選ばれる少なくとも一種である。Ar6〜Ar10はアリール基を表す。 R 20 , R 21 and L may be the same or different and are hydrogen, alkyl, cycloalkyl, aralkyl, alkenyl, cycloalkenyl, alkynyl, hydroxyl, mercapto, alkoxy, alkylthio, aryl Ether group, arylthioether group, aryl group, heterocyclic group, halogen, haloalkane, haloalkene, haloalkyne, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl A fused ring formed between a group, an adjacent substituent and an aliphatic ring. M represents an m-valent metal and is at least one selected from boron, beryllium, magnesium, chromium, iron, nickel, copper, zinc, platinum, and aluminum. Ar 6 to Ar 10 represent an aryl group.
これらの置換基の内、アルキル基とは例えばメチル基、エチル基、プロピル基、ブチル基、t−ブチル基などの飽和脂肪族炭化水素基を示し、これは無置換でも置換されていてもかまわない。また、シクロアルキル基とは例えばシクロプロピル、シクロペンチル、シクロヘキシル、ノルボルニル、アダマンチルなどの飽和脂環式炭化水素基を示し、これは無置換でも置換されていてもかまわない。また、アラルキル基とは例えばベンジル基、フェニルエチル基などの脂肪族炭化水素を介した芳香族炭化水素基を示し、脂肪族炭化水素と芳香族炭化水素はいずれも無置換でも置換されていてもかまわない。また、アルケニル基とは例えばビニル基、アリル基、ブタジエニル基などの二重結合を含む不飽和脂肪族炭化水素基を示し、これは無置換でも置換されていてもかまわない。また、シクロアルケニル基とは例えばシクロペンテニル基、シクロペンタジエニル基、シクロヘキセン基などの二重結合を含む不飽和脂環式炭化水素基を示し、これは無置換でも置換されていてもかまわない。また、アルキニル基とは例えばアセチレニル基などの三重結合を含む不飽和脂肪族炭化水素基を示し、これは無置換でも置換されていてもかまわない。また、アルコキシ基とは例えばメトキシ基などのエーテル結合を介した脂肪族炭化水素基を示し、脂肪族炭化水素基は無置換でも置換されていてもかまわない。また、アルキルチオ基とはアルコキシ基のエーテル結合の酸素原子が硫黄原子に置換されたものである。また、アリールエーテル基とは例えばフェノキシ基などのエーテル結合を介した芳香族炭化水素基を示し、芳香族炭化水素基は無置換でも置換されていてもかまわない。また、アリールチオエーテル基とはアリールエーテル基のエーテル結合の酸素原子が硫黄原子に置換されたものである。また、アリール基とは例えばフェニル基、ナフチル基、ビフェニル基、フェナントリル基、ターフェニル基、ピレニル基などの芳香族炭化水素基を示し、これは無置換でも置換されていてもかまわない。また、複素環基とは例えばフリル基、チエニル基、オキサゾリル基、ピリジル基、キノリル基、カルバゾリル基などの炭素以外の原子を有する環状構造基を示し、これは無置換でも置換されていてもかまわない。ハロゲンとはフッ素、塩素、臭素、ヨウ素を示す。ハロアルカン、ハロアルケン、ハロアルキンとは例えばトリフルオロメチル基などの、前述のアルキル基、アルケニル基、アルキニル基の一部あるいは全部が、前述のハロゲンで置換されたものを示し、残りの部分は無置換でも置換されていてもかまわない。アルデヒド基、カルボニル基、エステル基、カルバモイル基、アミノ基には脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、複素環などで置換されたものも含み、さらに脂肪族炭化水素、脂環式炭化水素、芳香族炭化水素、複素環は無置換でも置換されていてもかまわない。シリル基とは例えばトリメチルシリル基などのケイ素化合物基を示し、これは無置換でも置換されていてもかまわない。シロキサニル基とは例えばトリメチルシロキサニル基などのエーテル結合を介したケイ素化合物基を示し、これは無置換でも置換されていてもかまわない。隣接置換基との間に形成される縮合環または脂肪族環は無置換でも置換されていてもかまわない。 Among these substituents, the alkyl group represents a saturated aliphatic hydrocarbon group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a t-butyl group, which may be unsubstituted or substituted. Absent. The cycloalkyl group represents a saturated alicyclic hydrocarbon group such as cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, and the like, which may be unsubstituted or substituted. The aralkyl group is an aromatic hydrocarbon group via an aliphatic hydrocarbon such as a benzyl group or a phenylethyl group, and both the aliphatic hydrocarbon and the aromatic hydrocarbon may be unsubstituted or substituted. It doesn't matter. The alkenyl group refers to an unsaturated aliphatic hydrocarbon group containing a double bond such as a vinyl group, an allyl group or a butadienyl group, which may be unsubstituted or substituted. The cycloalkenyl group refers to an unsaturated alicyclic hydrocarbon group containing a double bond such as a cyclopentenyl group, a cyclopentadienyl group, or a cyclohexene group, which may be unsubstituted or substituted. . The alkynyl group refers to an unsaturated aliphatic hydrocarbon group containing a triple bond such as an acetylenyl group, which may be unsubstituted or substituted. The alkoxy group refers to an aliphatic hydrocarbon group via an ether bond such as a methoxy group, and the aliphatic hydrocarbon group may be unsubstituted or substituted. The alkylthio group is a group in which an oxygen atom of an ether bond of an alkoxy group is substituted with a sulfur atom. The aryl ether group refers to an aromatic hydrocarbon group via an ether bond such as a phenoxy group, and the aromatic hydrocarbon group may be unsubstituted or substituted. The arylthioether group is a group in which the oxygen atom of the ether bond of the arylether group is substituted with a sulfur atom. The aryl group represents an aromatic hydrocarbon group such as a phenyl group, a naphthyl group, a biphenyl group, a phenanthryl group, a terphenyl group, or a pyrenyl group, which may be unsubstituted or substituted. The heterocyclic group is a cyclic structural group having an atom other than carbon, such as a furyl group, a thienyl group, an oxazolyl group, a pyridyl group, a quinolyl group, or a carbazolyl group, which may be unsubstituted or substituted. Absent. Halogen is fluorine, chlorine, bromine or iodine. Haloalkane, haloalkene, haloalkyne means, for example, a part or all of the above-mentioned alkyl group, alkenyl group, alkynyl group such as trifluoromethyl group substituted with the above-mentioned halogen, and the remaining part may be unsubstituted It may be replaced. Aldehyde groups, carbonyl groups, ester groups, carbamoyl groups, amino groups include those substituted with aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, heterocyclic rings, etc. The cyclic hydrocarbon, aromatic hydrocarbon and heterocyclic ring may be unsubstituted or substituted. A silyl group refers to a silicon compound group such as a trimethylsilyl group, which may be unsubstituted or substituted. The siloxanyl group refers to a silicon compound group via an ether bond such as a trimethylsiloxanyl group, which may be unsubstituted or substituted. The condensed ring or aliphatic ring formed between adjacent substituents may be unsubstituted or substituted.
また、一般式(5)で表される化合物の中で、本発明は分解温度が昇華温度より高いピロメテン化合物の一般式(1)で示されるホウ素錯体であり、蛍光量子収率が高いので、好ましい。 In addition, among the compounds represented by the general formula (5), the present invention is a boron complex represented by the general formula (1) of the pyromethene compound having a decomposition temperature higher than the sublimation temperature, and the fluorescence quantum yield is high. preferable.
R1〜R4は同じでも異なっていてもよく、水素、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、シクロアルケニル基、アルキニル基、水酸基、メルカプト基、アルコキシ基、アルキルチオ基、アリールエーテル基、アリールチオエーテル基、アリール基、複素環基、ハロゲン、ハロアルカン、ハロアルケン、ハロアルキン、シアノ基、アルデヒド基、カルボニル基、カルボキシル基、エステル基、カルバモイル基、アミノ基、ニトロ基、シリル基、シロキサニル基、隣接置換基との間に形成される縮合環および脂肪族環の中から選ばれる。Ar1〜Ar5はアリール基を表す。 R 1 to R 4 may be the same or different, and are hydrogen, alkyl group, cycloalkyl group, aralkyl group, alkenyl group, cycloalkenyl group, alkynyl group, hydroxyl group, mercapto group, alkoxy group, alkylthio group, aryl ether group. , Arylthioether group, aryl group, heterocyclic group, halogen, haloalkane, haloalkene, haloalkyne, cyano group, aldehyde group, carbonyl group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group, siloxanyl group, It is selected from fused rings and aliphatic rings formed between adjacent substituents. Ar 1 to Ar 5 represent an aryl group.
これらの置換基については上記一般式(5)の説明と同様である。 About these substituents, it is the same as that of description of the said General formula (5).
上記Ar1〜Ar4は無置換または置換アリール基を示すが、これらのAr1〜Ar4のうち少なくとも1つ、好ましくは2つ以上、さらに好ましくはすべてがメチル基、メトキシ基、t−ブチル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基で置換されていると、真空蒸着温度よりも高い耐熱性を維持し、かつ、薄膜中での分散性が向上し、高輝度発光が得られる。特に、発光特性と耐熱性の点から、Ar1〜Ar4はメチル基、メトキシ基、t−ブチル基が置換していることが好ましい。 Ar 1 to Ar 4 represents an unsubstituted or substituted aryl group. Among these Ar 1 to Ar 4 , at least one, preferably two or more, more preferably all are methyl, methoxy, t-butyl. Group, unsubstituted or phenyl group having at least one substituent selected from methyl, methoxy, and t-butyl, unsubstituted, or at least one substituted from methyl, methoxy, and t-butyl. When substituted with a phenoxy group having a group, heat resistance higher than the vacuum deposition temperature is maintained, dispersibility in the thin film is improved, and high luminance light emission is obtained. Particularly, Ar 1 to Ar 4 are preferably substituted with a methyl group, a methoxy group, or a t-butyl group from the viewpoints of light emission characteristics and heat resistance.
上記Ar5は無置換または置換アリール基を示すが、発光特性と耐熱性の点から下記の構造であることが好ましい。Ar5は、Ar1〜Ar4のうち少なくとも1つが、無置換あるいはメトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基の中から選ばれる1つ以上の置換基で置換されているとき、下記一般式(2)で表されることが好ましい。 Ar 5 represents an unsubstituted or substituted aryl group, and preferably has the following structure from the viewpoint of light emission characteristics and heat resistance. Ar 5 is a phenyl group, an unsubstituted or methyl group, a methoxy group, t, wherein at least one of Ar 1 to Ar 4 is unsubstituted or has at least one substituent selected from a methoxy group and a t-butyl group. -When substituted with one or more substituents selected from phenoxy groups having at least one substituent among butyl groups, it is preferably represented by the following general formula (2).
R5〜R9はそれぞれ同じでも異なっていてもよく、水素、メチル基、メトキシ基、t−ブチル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基の中から選ばれる。 R 5 to R 9 may be the same or different, and are at least one selected from hydrogen, methyl group, methoxy group, t-butyl group, unsubstituted or methyl group, methoxy group, t-butyl group It is selected from a phenyl group having a group, an unsubstituted group, or a phenoxy group having at least one substituent among a methyl group, a methoxy group, and a t-butyl group.
また、上記Ar5は、Ar1〜Ar4のうち少なくとも1つが、メチル基、メトキシ基の中から選ばれる1つ以上の置換基で置換されているとき、Ar5が下記一般式(3)で表されることが好ましい。 In Ar 5 , when at least one of Ar 1 to Ar 4 is substituted with one or more substituents selected from a methyl group and a methoxy group, Ar 5 is represented by the following general formula (3). It is preferable to be represented by
R11〜R13はそれぞれ同じでも異なっていてもよく、水素、メチル基、メトキシ基、t−ブチル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基の中から選ばれる。R10とR14はそれぞれ同じでも異なっていてもよく、水素、メトキシ基、t−ブチル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基の中から選ばれるが、R10とR14が同時に水素となるときは、R11〜R13の少なくとも1つはメチル基、メトキシ基、t−ブチル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基から選ばれる。 R 11 to R 13 may be the same or different, and are at least one selected from hydrogen, methyl group, methoxy group, t-butyl group, unsubstituted or methyl group, methoxy group, and t-butyl group It is selected from a phenyl group having a group, an unsubstituted group, or a phenoxy group having at least one substituent among a methyl group, a methoxy group, and a t-butyl group. R 10 and R 14 may be the same or different, and have at least one substituent selected from hydrogen, methoxy group, t-butyl group, unsubstituted or methyl group, methoxy group, and t-butyl group A phenyl group, an unsubstituted group, or a phenoxy group having at least one substituent is selected from a methyl group, a methoxy group, and a t-butyl group. When R 10 and R 14 are simultaneously hydrogen, R 11 At least one of ˜R 13 is a methyl group, a methoxy group, a t-butyl group, an unsubstituted group or a phenyl group having at least one substituent selected from a methyl group, a methoxy group, and a t-butyl group, an unsubstituted group, or A phenoxy group having at least one substituent is selected from a methyl group, a methoxy group, and a t-butyl group.
また、上記のAr5は、Ar1〜Ar4のうち少なくとも1つがt−ブチル基で置換されているとき、Ar5が下記一般式(4)で表されることが好ましい。 Further, Ar 5 described above, when it is substituted with at least one of t- butyl group among Ar 1 to Ar 4, Ar 5 is is preferably represented by the following general formula (4).
R16〜R18はそれぞれ同じでも異なっていてもよく、水素、メチル基、メトキシ基、t−ブチル基、無置換あるいはメトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基の中から選ばれる。R15とR19はそれぞれ同じであっても、異なっていてもよく、水素、メトキシ基、t−ブチル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から選ばれる少なくとも1つの置換基を有するフェニル基、無置換あるいはメチル基、メトキシ基、t−ブチル基の中から少なくとも1つの置換基を有するフェノキシ基から選ばれる。 R 16 to R 18 may be the same or different, and have at least one substituent selected from hydrogen, methyl group, methoxy group, t-butyl group, unsubstituted or methoxy group, t-butyl group It is selected from a phenyl group, an unsubstituted group, or a phenoxy group having at least one substituent among a methyl group, a methoxy group, and a t-butyl group. R 15 and R 19 may be the same or different from each other, and at least one selected from hydrogen, methoxy group, t-butyl group, unsubstituted or methyl group, methoxy group, and t-butyl group It is selected from a phenyl group having a substituent, an unsubstituted group, or a phenoxy group having at least one substituent among a methyl group, a methoxy group, and a t-butyl group.
材料の入手しやすさや、合成の容易さを考えると上記一般式(1)のR3およびR4はともにフッ素であることが好ましい。上記のようなピロメテン化合物として具体的には以下のような化合物があげられる。 Considering the availability of materials and the ease of synthesis, it is preferable that R 3 and R 4 in the general formula (1) are both fluorine. Specific examples of the above-mentioned pyromethene compound include the following compounds.
本発明のピロメテン化合物は、例えば以下の方法により製造することができる。 The pyromethene compound of the present invention can be produced, for example, by the following method.
下記一般式(6)で表される化合物と一般式(7)で表される化合物をオキシ塩化リン存在下、1,2−ジクロロエタン中で加熱した後、下記一般式(8)で表される化合物をトリエチルアミン存在下、1,2−ジクロロエタン中で反応させることにより、一般式(1)の化合物を得ることができる。ここで、Ar1〜Ar5、R1〜R4は前記と同じである。Jはハロゲンを表す。 The compound represented by the following general formula (6) and the compound represented by the general formula (7) are heated in 1,2-dichloroethane in the presence of phosphorus oxychloride, and then represented by the following general formula (8). The compound of general formula (1) can be obtained by reacting the compound in 1,2-dichloroethane in the presence of triethylamine. Here, Ar 1 to Ar 5 and R 1 to R 4 are the same as described above. J represents halogen.
また、本発明の一般式(1)で表されるピロメテン化合物は、真空蒸着温度、つまり昇華温度よりも分解温度が高いことがよい。昇華温度は分解温度よりも10℃以上、さらに好ましくは20℃以上、さらに好ましくは30℃以上高いことが、真空蒸着プロセスの許容幅が広がる点から好ましい。真空蒸着温度より分解温度が低いと、成膜中に分解や重合などの変性が起こってしまうという問題が生じる。特に、一般式(1)で表されるピロメテン化合物をドーパント材料として用いる場合、ホスト材料などに比べて蒸着源の中で長時間加熱されるので、耐熱性が高いことが好ましい。また、蒸着源の中で溶融すると、昇華性が低下して変性する可能性が高いので、融点は高いことが好ましい。融点は200℃以上、好ましくは250℃以上、さらに好ましくは300℃以上である。 The pyromethene compound represented by the general formula (1) of the present invention preferably has a decomposition temperature higher than the vacuum deposition temperature, that is, the sublimation temperature. The sublimation temperature is preferably 10 ° C. or more, more preferably 20 ° C. or more, more preferably 30 ° C. or more higher than the decomposition temperature from the viewpoint of widening the allowable range of the vacuum deposition process. When the decomposition temperature is lower than the vacuum deposition temperature, there arises a problem that modification such as decomposition or polymerization occurs during film formation. In particular, when the pyromethene compound represented by the general formula (1) is used as a dopant material, it is preferable that heat resistance is high because it is heated for a long time in a vapor deposition source as compared with a host material or the like. In addition, when melted in the vapor deposition source, it is highly possible that the sublimation property is deteriorated and the material is denatured. Therefore, the melting point is preferably high. The melting point is 200 ° C. or higher, preferably 250 ° C. or higher, more preferably 300 ° C. or higher.
本発明において、一般式(1)で表されるピロメテン化合物は発光素子材料として、好適に用いられる。 In the present invention, the pyromethene compound represented by the general formula (1) is suitably used as a light emitting device material.
本発明の発光素子材料は、一般式(1)で表されるピロメテン化合物のみからなるものであっても良いし、材料のハンドリング性等の理由により、適宜、その他の材料を添加しても良い。 The light emitting device material of the present invention may be composed only of the pyromethene compound represented by the general formula (1), or other materials may be appropriately added for reasons such as material handling properties. .
次に、本発明の発光素子について詳細に説明する。陽極は、光を取り出すために透光性であれば良く、使用する素材としては、酸化錫、酸化インジウム、酸化錫インジウム(ITO)などの導電性金属酸化物、あるいは金、銀、クロムなどの金属、ヨウ化銅、硫化銅などの無機導電性物質、ポリチオフェン、ポリピロール、ポリアニリンなどの導電性ポリマなど特に限定されるものでないが、ITOガラスやネサガラスを用いることが特に望ましい。 Next, the light emitting device of the present invention will be described in detail. The anode may be translucent in order to extract light, and the materials used are conductive metal oxides such as tin oxide, indium oxide and indium tin oxide (ITO), or gold, silver, chromium, etc. There are no particular limitations on inorganic conductive materials such as metals, copper iodide and copper sulfide, and conductive polymers such as polythiophene, polypyrrole and polyaniline, but it is particularly desirable to use ITO glass or Nesa glass.
透明電極である陽極の抵抗は、素子の発光に十分な電流が供給できればよいので限定されないが、素子の消費電力の観点からは低抵抗であることが望ましい。例えば、300Ω/□以下のITO基板であれば素子電極として機能するが、現在では10Ω/□程度の基板の供給も可能になっていることから、低抵抗品を使用することが特に望ましい。ITOの厚みは、抵抗値に合わせて任意に選ぶ事ができるが、通常100〜300nmの間で用いられることが多い。また、ガラス基板はソーダライムガラス、無アルカリガラスなどが用いられ、また厚みも機械的強度を保つのに十分な厚みがあればよいので、0.5mm以上あれば十分である。ガラスの材質については、ガラスからの溶出イオンが少ない方がよいので無アルカリガラスが好ましいが、SiO2などのバリアコートを施したソーダライムガラスなど市販されているガラスを使用できる。ITO膜形成方法は、電子線ビーム法、スパッタリング法、化学反応法などを使用することができ、特に制限を受けるものではない。 The resistance of the anode, which is a transparent electrode, is not limited as long as a current sufficient for light emission of the element can be supplied. For example, an ITO substrate of 300Ω / □ or less functions as an element electrode, but since it is now possible to supply a substrate of about 10Ω / □, it is particularly desirable to use a low resistance product. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually used in a range of 100 to 300 nm. Further, soda lime glass, non-alkali glass or the like is used for the glass substrate, and the thickness of the glass substrate only needs to be sufficient to maintain the mechanical strength, so 0.5 mm or more is sufficient. The glass material is preferably non-alkali glass because it is better to have less ions eluted from the glass, but commercially available glass such as soda lime glass with a barrier coat such as SiO 2 can be used. As the ITO film forming method, an electron beam method, a sputtering method, a chemical reaction method, or the like can be used, and there is no particular limitation.
陰極に使用する素材は、電子を本有機物層に効率良く注入できる物質であれば特に限定されず、例えば、白金、金、銀、銅、鉄、錫、亜鉛、アルミニウム、インジウム、クロム、リチウム、ナトリウム、カリウム、カルシウム、マグネシウムなどを使用することができる。電子注入効率をあげて素子特性を向上させるためには、リチウム、ナトリウム、カリウム、カルシウム、マグネシウムまたはこれらの低仕事関数金属を含む合金が有効である。しかし、これらの低仕事関数金属は、一般に大気中で不安定であることが多く、例えば、有機層に微量のリチウムやマグネシウム(例えば、真空蒸着の膜厚計表示で1nm以下)をドーピングして安定性の高い電極を使用する方法が好ましい例として挙げることができるが、フッ化リチウムのような無機塩の使用も可能であることから特にこれらに限定されるものではない。さらに、電極保護のために、白金、金、銀、銅、鉄、錫、アルミニウム、インジウムなどの金属、またはこれらの金属を用いた合金、そしてシリカ、チタニア、窒化ケイ素などの無機物、ポリビニルアルコール、塩化ビニル、炭化水素系高分子などを積層することが好ましい例として挙げられる。これらの電極の作製法についてもも、抵抗加熱、電子線ビーム、スパッタリング、イオンプレーティング、コーティングなど、導通を取ることができれば特に制限されない。 The material used for the cathode is not particularly limited as long as it is a substance that can efficiently inject electrons into the organic layer. For example, platinum, gold, silver, copper, iron, tin, zinc, aluminum, indium, chromium, lithium, Sodium, potassium, calcium, magnesium and the like can be used. Lithium, sodium, potassium, calcium, magnesium, or alloys containing these low work function metals are effective for increasing the electron injection efficiency and improving device characteristics. However, these low work function metals are generally unstable in the atmosphere. For example, the organic layer is doped with a small amount of lithium or magnesium (for example, 1 nm or less in the vacuum gauge thickness gauge display). A method using a highly stable electrode can be mentioned as a preferable example, but an inorganic salt such as lithium fluoride can also be used, and the method is not particularly limited thereto. Furthermore, for electrode protection, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, and inorganic materials such as silica, titania and silicon nitride, polyvinyl alcohol, Preferred examples include laminating vinyl chloride and hydrocarbon polymers. The method for producing these electrodes is not particularly limited as long as conduction can be achieved, such as resistance heating, electron beam, sputtering, ion plating, and coating.
本発明の発光素子に含まれる発光素子材料としては、自ら発光するもの、その発光を助けるもののいずれかに該当し、発光に関与している化合物を指すものである。具体的には、正孔輸送材料、発光材料、電子輸送材料などが該当する。 The light-emitting element material contained in the light-emitting element of the present invention corresponds to either a substance that emits light by itself or a substance that assists light emission, and refers to a compound that participates in light emission. Specifically, hole transport materials, light emitting materials, electron transport materials, and the like are applicable.
また、本発明の発光素子は発光素子用材料を含む層により形成され、例えば、1)正孔輸送層/発光層、2)正孔輸送層/発光層/電子輸送層、3)発光層/電子輸送層、そして、4)以上の組合わせ物質を一層に混合した形態のいずれであってもよい。即ち、素子構成としては、上記1)〜3)の多層積層構造の他に4)のように発光材料単独または発光材料と正孔輸送材料や電子輸送材料を含む層を一層設けるだけでもよい。 The light emitting device of the present invention is formed of a layer containing a material for a light emitting device, for example, 1) hole transport layer / light emitting layer, 2) hole transport layer / light emitting layer / electron transport layer, 3) light emitting layer / Any of the electron transport layer and 4) a combination of the above-mentioned combined substances in one layer may be used. That is, as the element structure, in addition to the multilayer laminated structure of the above 1) to 3), only the light emitting material alone or a layer containing the light emitting material and the hole transport material or electron transport material may be provided as in 4).
正孔輸送層は、正孔輸送材料の一種または二種以上を積層、混合するか正孔輸送性物質と高分子結着剤の混合物により形成することができる。正孔輸送性物質としては、例えば、N,N’−ジフェニル−N,N’−ジ(3−メチルフェニル)−4,4’−ジフェニル−1,1’−ジアミン、N,N’−ジナフチル−N,N’−ジフェニル−4,4’−ジフェニル−1,1’−ジアミンなどのトリフェニルアミン類、ビス(N−アリルカルバゾール)またはビス(N−アルキルカルバゾール)類、ピラゾリン誘導体、スチルベン系化合物、ヒドラゾン系化合物、オキサジアゾール誘導体やフタロシアニン誘導体、ポルフィリン誘導体に代表される複素環化合物、ポリマー系では前記単量体を側鎖に有するポリカーボネートやスチレン誘導体、ポリビニルカルバゾール、ポリシランなどが好ましく使用される。ただし、素子作製に必要な薄膜を形成し、陽極から正孔が注入できて、さらに正孔を輸送できる化合物であれば特に限定されるものではない。 The hole transport layer can be formed by laminating and mixing one or more hole transport materials or a mixture of a hole transport material and a polymer binder. Examples of the hole transporting material include N, N′-diphenyl-N, N′-di (3-methylphenyl) -4,4′-diphenyl-1,1′-diamine, N, N′-dinaphthyl. -N, N'-diphenyl-4,4'-diphenyl-1,1'-diamine and other triphenylamines, bis (N-allylcarbazole) or bis (N-alkylcarbazole) s, pyrazoline derivatives, stilbene series Compounds, hydrazone compounds, oxadiazole derivatives, phthalocyanine derivatives, heterocyclic compounds typified by porphyrin derivatives, and polymer systems are preferably polycarbonates, styrene derivatives, polyvinylcarbazole, polysilane, etc. having the above monomers in the side chain. The However, there is no particular limitation as long as it is a compound that can form a thin film necessary for device fabrication, inject holes from the anode, and further transport holes.
本発明における発光層は、発光材料(ホスト材料、ドーパント材料)により形成され、これはホスト材料とドーパント材料との混合物であっても、ホスト材料単独であっても、いずれでもよい。ホスト材料とドーパント材料は、それぞれ一種類であっても、複数の組み合わせであっても、いずれでもよい。ドーパント材料はホスト材料の全体に含まれていても、部分的に含まれていても、いずれであってもよい。ドーパント材料は積層されていても、分散されていても、いずれであってもよい。 The light emitting layer in the present invention is formed of a light emitting material (host material, dopant material), which may be a mixture of a host material and a dopant material or a host material alone. Each of the host material and the dopant material may be one kind or a plurality of combinations. The dopant material may be included in the host material as a whole, or may be included partially. The dopant material may be either laminated or dispersed.
本発明ピロメテン化合物は発光材料として好適に用いられる。ホスト材料として用いてもよいが、蛍光量子収率が高いことや、発光スペクトルの半値幅が小さいことから、ドーパント材料として好適に用いられる。 The pyromethene compound of the present invention is suitably used as a light emitting material. Although it may be used as a host material, it is preferably used as a dopant material because it has a high fluorescence quantum yield and a small half-value width of an emission spectrum.
ドーピング量は、多すぎると濃度消光現象が起きるため、ホスト物質に対して10重量%以下で用いることが好ましく、更に好ましくは2重量%以下である。ドーピング方法としては、ホスト材料との共蒸着法によって形成することができるが、ホスト材料と予め混合してから同時に蒸着しても良い。また、ドーパント材料はホスト材料の全体に含まれていても、部分的に含まれていても、いずれであってもよい。ドーパント材料は積層されていても、分散されていても、いずれであってもよい。さらに、ピロメテン化合物は、極めて微量でも発光することから微量のピロメテン化合物をホスト材料にサンドイッチ状に挟んで使用することも可能である。この場合、一層でも二層以上ホスト材料と積層しても良い。発光材料に添加するドーパント材料は、前記ピロメテン化合物一種のみに限る必要はなく、複数のピロメテン化合物を混合して用いたり、既知のドーパント材料の一種類以上をピロメテン化合物と混合して用いてもよい。具体的には従来から知られている、ビス(ジイソプロピルフェニル)ペリレンテトラカルボン酸イミドなどのナフタルイミド誘導体、ペリノン誘導体、アセチルアセトンやベンゾイルアセトンとフェナントロリンなどを配位子とするEu錯体などの希土類錯体、4−(ジシアノメチレン)−2−メチル−6−(p−ジメチルアミノスチリル)−4H−ピランやその類縁体、マグネシウムフタロシアニン、アルミニウムクロロフタロシアニンなどの金属フタロシアニン誘導体、ローダミン化合物、デアザフラビン誘導体、クマリン誘導体、キナクリドン誘導体、フェノキサジン誘導体、オキサジン化合物、ポルフィリン白金錯体やトリス(2−フェニルピリジル)イリジウム錯体、トリス{2−(2−チオフェニル)ピリジル}イリジウム錯体などのイリジウム錯体などを共存させることができるが特にこれらに限定されるものではない。 If the doping amount is too large, a concentration quenching phenomenon occurs, so that it is preferably used in an amount of 10% by weight or less, more preferably 2% by weight or less based on the host material. As a doping method, it can be formed by a co-evaporation method with a host material, but it may be pre-mixed with the host material and then simultaneously deposited. Further, the dopant material may be included in the entire host material, or may be included partially. The dopant material may be either laminated or dispersed. Furthermore, since the pyromethene compound emits light even in a very small amount, it is also possible to use a very small amount of the pyromethene compound sandwiched between the host materials. In this case, one or more layers may be laminated with the host material. The dopant material added to the light emitting material need not be limited to only one pyromethene compound, and a plurality of pyromethene compounds may be mixed and used, or one or more kinds of known dopant materials may be mixed with a pyromethene compound. . Specifically, conventionally known rare earth complexes such as naphthalimide derivatives such as bis (diisopropylphenyl) perylenetetracarboxylic imide, perinone derivatives, Eu complexes having acetylacetone, benzoylacetone and phenanthroline as ligands, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran and its analogs, metal phthalocyanine derivatives such as magnesium phthalocyanine and aluminum chlorophthalocyanine, rhodamine compounds, deazaflavin derivatives, coumarin derivatives, Quinacridone derivatives, phenoxazine derivatives, oxazine compounds, porphyrin platinum complexes, tris (2-phenylpyridyl) iridium complexes, tris {2- (2-thiophenyl) pyridyl} iridium complexes What iridium complex, etc. can coexist but not particularly limited thereto.
ホスト材料としては特に限定されるものではないが、以前から発光体として知られていたアントラセンやピレンなどの縮合環誘導体、トリス(8−キノリノラト)アルミニウムをはじめとする金属キレート化オキシノイド化合物、ビススチリルアントラセン誘導体やジスチリルベンゼン誘導体などのビススチリル誘導体、テトラフェニルブタジエン誘導体、クマリン誘導体、オキサジアゾール誘導体、ピロロピリジン誘導体、ペリノン誘導体、シクロペンタジエン誘導体、オキサジアゾール誘導体、チアジアゾロピリジン誘導体、ピロロピロール誘導体、4,4’−ビス(カルバゾリル−N−イル)−4,4’−ジフェニルやN,N’−ジフェニル−3,3’−ビスカルバゾールなどのカルバゾール誘導体、N,N’−ジフェニル−N,N’−ジ(3−メチルフェニル)−4,4’−ジフェニル−1,1’−ジアミンなどのトリフェニルアミン化合物、インドール誘導体、トリアゾール、オキサジアゾール、イミダゾールなどのアゾール誘導体、フェナントロリン誘導体、キノリン誘導体、ナフチリジン誘導体、ビピリジン、ターピリジンなどのオリゴピリジン誘導体、ポルフィリン白金錯体やトリス(2−フェニルピリジル)イリジウム錯体、トリス{2−(2−チオフェニル)ピリジル}イリジウム錯体などのイリジウム錯体など、ポリマー系では、ポリフェニレンビニレン誘導体、ポリパラフェニレン誘導体、そして、ポリチオフェン誘導体などが使用できる。 The host material is not particularly limited, but has previously been known as a phosphor, fused ring derivatives such as anthracene and pyrene, metal chelated oxinoid compounds including tris (8-quinolinolato) aluminum, bisstyryl Bisstyryl derivatives such as anthracene derivatives and distyrylbenzene derivatives, tetraphenylbutadiene derivatives, coumarin derivatives, oxadiazole derivatives, pyrrolopyridine derivatives, perinone derivatives, cyclopentadiene derivatives, oxadiazole derivatives, thiadiazolopyridine derivatives, pyrrolopyrrole derivatives , Carbazole derivatives such as 4,4′-bis (carbazolyl-N-yl) -4,4′-diphenyl and N, N′-diphenyl-3,3′-biscarbazole, N, N′-diphenyl-N, N ' Triphenylamine compounds such as di (3-methylphenyl) -4,4'-diphenyl-1,1'-diamine, indole derivatives, azole derivatives such as triazole, oxadiazole, imidazole, phenanthroline derivatives, quinoline derivatives, naphthyridine In the polymer system, polyphenylene vinylene such as derivatives, oligopyridine derivatives such as bipyridine and terpyridine, iridium complexes such as porphyrin platinum complex, tris (2-phenylpyridyl) iridium complex, and tris {2- (2-thiophenyl) pyridyl} iridium complex Derivatives, polyparaphenylene derivatives, polythiophene derivatives and the like can be used.
本発明における電子輸送性材料としては、電界を与えられた電極間において陰極からの電子を効率良く輸送することが必要で、電子注入効率が高く、注入された電子を効率良く輸送することが望ましい。そのためには電子親和力が大きく、しかも電子移動度が大きく、さらに安定性に優れ、トラップとなる不純物が製造時および使用時に発生しにくい物質であることが要求される。このような条件を満たす物質として、8−ヒドロキシキノリンアルミニウムに代表されるキノリノール誘導体化合物、トロポロン化合物、フラボノール化合物、ペリレン誘導体、ペリノン誘導体、ナフタレン誘導体、クマリン誘導体、オキサジアゾール誘導体、アルダジン誘導体、ビススチリル誘導体、ピラジン誘導体、フェナントロリン誘導体、キノリン誘導体、芳香族リンオキサイド化合物などがあるが特に限定されるものではない。これらの電子輸送材料は単独でも用いられるが、異なる電子輸送材料と積層または混合して使用しても構わない。 As the electron transporting material in the present invention, it is necessary to efficiently transport electrons from the cathode between electrodes to which an electric field is applied, and it is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. . For this purpose, it is required that the material has a high electron affinity, a high electron mobility, excellent stability, and a substance that does not easily generate trapping impurities during manufacturing and use. As substances satisfying such conditions, quinolinol derivative compounds represented by 8-hydroxyquinoline aluminum, tropolone compounds, flavonol compounds, perylene derivatives, perinone derivatives, naphthalene derivatives, coumarin derivatives, oxadiazole derivatives, aldazine derivatives, bisstyryl derivatives , Pyrazine derivatives, phenanthroline derivatives, quinoline derivatives, aromatic phosphorus oxide compounds and the like, but are not particularly limited. These electron transport materials are used alone, but may be laminated or mixed with different electron transport materials.
正孔阻止層とは、電界を与えられた電極間において陽極からの正孔が陰極からの電子と再結合することなく移動するのを防止するための層であり、各層を構成する材料の種類によっては、この層を挿入することにより正孔と電子の再結合確率が増加し、発光効率の向上が望める場合がある。したがって、正孔阻止性材料としては正孔輸送性材料よりも最高占有分子軌道レベルがエネルギー的に低く、隣接する層を構成する材料とエキサイプレックスを生成しにくいことが望まれる。陽極からの正孔の移動を効率よく阻止できる化合物が好ましく、電子輸送能の高い材料が正孔阻止能も高いことから、上記電子輸送材料が好ましい例として挙げられる。 The hole blocking layer is a layer for preventing the holes from the anode from moving between the electrodes to which an electric field is applied without recombining with the electrons from the cathode, and the kind of material constituting each layer. Depending on the case, insertion of this layer may increase the probability of recombination of holes and electrons, and may improve the light emission efficiency. Therefore, it is desirable that the hole-occluding material has a lower maximum occupied molecular orbital level than the hole-transporting material in terms of energy, and it is difficult to generate an exciplex with the material constituting the adjacent layer. A compound that can efficiently block the movement of holes from the anode is preferable, and a material having a high electron transporting capability also has a high hole blocking capability. Therefore, the electron transporting material is a preferable example.
以上の正孔輸送層、発光層、電子輸送層、正孔阻止層は単独または二種類以上の材料を積層、混合するか、高分子結着剤としてポリ塩化ビニル、ポリカーボネート、ポリスチレン、ポリ(N−ビニルカルバゾール)、ポリメチルメタクリレート、ポリブチルメタクリレート、ポリエステル、ポリスルフォン、ポリフェニレンオキサイド、ポリブタジエン、炭化水素樹脂、ケトン樹脂、フェノキシ樹脂、ポリサルフォン、ポリアミド、エチルセルロース、酢酸ビニル、ABS樹脂、ポリウレタン樹脂などの溶剤可溶性樹脂や、フェノール樹脂、キシレン樹脂、石油樹脂、ユリア樹脂、メラミン樹脂、不飽和ポリエステル樹脂、アルキド樹脂、エポキシ樹脂、シリコーン樹脂などの硬化性樹脂などに分散させて用いることも可能である。 The above hole transport layer, light-emitting layer, electron transport layer, and hole blocking layer may be a single material or a laminate of two or more materials, mixed, or a polymer binder such as polyvinyl chloride, polycarbonate, polystyrene, poly (N -Vinylcarbazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polysulfone, polyamide, ethyl cellulose, vinyl acetate, ABS resin, polyurethane resin, etc. It can also be used by being dispersed in a soluble resin, a curable resin such as a phenol resin, a xylene resin, a petroleum resin, a urea resin, a melamine resin, an unsaturated polyester resin, an alkyd resin, an epoxy resin, or a silicone resin.
発光材料の薄膜形成方法は、抵抗加熱真空蒸着、電子ビーム真空蒸着、スパッタリング、分子積層法、コーティング法など特に限定されるものではないが、通常は、抵抗加熱真空蒸着、電子ビーム真空蒸着が特性面で好ましい。層の厚みは、発光材料の抵抗値にもよるので限定することはできないが、1〜1000nmの間から選ばれる。 The thin film forming method of the light emitting material is not particularly limited, such as resistance heating vacuum deposition, electron beam vacuum deposition, sputtering, molecular lamination method, coating method, etc., but resistance heating vacuum deposition and electron beam vacuum deposition are usually characteristics. In terms of surface. The thickness of the layer depends on the resistance value of the light emitting material and cannot be limited, but is selected from 1 to 1000 nm.
電気エネルギーとは主に直流電流を指すが、パルス電流や交流電流を用いることも可能である。電流値および電圧値は特に制限はないが、素子の消費電力、寿命を考慮するとできるだけ低いエネルギーで最大の輝度が得られるようにするべきである。 Electrical energy mainly refers to direct current, but pulsed current or alternating current can also be used. The current value and the voltage value are not particularly limited, but the maximum luminance should be obtained with the lowest possible energy in consideration of the power consumption and lifetime of the element.
本発明におけるマトリクスとは、表示のための画素が格子状に配置されたものをいい、画素の集合で文字や画像を表示する。画素の形状、サイズは用途によって決まる。例えばパソコン、モニター、テレビの画像および文字表示には、通常一辺が300μm以下の四角形の画素が用いられるし、表示パネルのような大型ディスプレイの場合は、一辺がmmオーダーの画素を用いることになる。モノクロ表示の場合は、同じ色の画素を配列すればよいが、カラー表示の場合には、赤、緑、青の画素を並べて表示させる。この場合、典型的にはデルタタイプとストライプタイプがある。そして、このマトリクスの駆動方法としては、線順次駆動方法やアクティブマトリックスのどちらでもよい。線順次駆動の方が構造が簡単であるという利点があるが、動作特性を考慮した場合、アクティブマトリックスの方が優れる場合があるので、これも用途によって使い分けることが必要である。 The matrix in the present invention refers to a matrix in which pixels for display are arranged in a lattice pattern, and displays characters and images by a set of pixels. The shape and size of the pixel are determined by the application. For example, a rectangular pixel with a side of 300 μm or less is normally used for displaying images and characters on a personal computer, monitor, television, etc. In a large display such as a display panel, a pixel with a side of mm order is used. . In monochrome display, pixels of the same color may be arranged. However, in color display, red, green, and blue pixels are displayed side by side. In this case, there are typically a delta type and a stripe type. The matrix driving method may be either a line sequential driving method or an active matrix. The line-sequential driving has an advantage that the structure is simple. However, the active matrix may be superior in consideration of the operation characteristics, so that it is necessary to properly use it depending on the application.
本発明におけるセグメントタイプとは、予め決められた情報を表示するようにパターンを形成し、決められた領域を発光させることになる。例えば、デジタル時計や温度計における時刻や温度表示、オーディオ機器や電磁調理器などの動作状態表示、自動車のパネル表示などがあげられる。そして、前記マトリクス表示とセグメント表示は同じパネルの中に共存していてもよい。 The segment type in the present invention means that a pattern is formed so as to display predetermined information, and a predetermined region is caused to emit light. For example, the time and temperature display in a digital clock or a thermometer, the operation status display of an audio device or an electromagnetic cooker, the panel display of an automobile, etc. The matrix display and the segment display may coexist in the same panel.
以下、実施例および比較例をあげて本発明を説明するが、本発明はこれらの例によって限定されるものではない。なお、下記の各実施例にある化合物の番号は前記に記載した化合物の番号を指すものである。また構造分析に関する評価方法を下記に示す。 EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated, this invention is not limited by these examples. In addition, the number of the compound in each following Example points out the number of the compound described above. The evaluation method for structural analysis is shown below.
1H−NMRは超伝導FTNMR EX−270(日本電子(株)製)を用い、重クロロホルム溶液にて測定を行った。 1 H-NMR was measured with a deuterated chloroform solution using superconducting FTNMR EX-270 (manufactured by JEOL Ltd.).
元素分析は、CHNコーダーMT−3型(柳本製作所(株)製)、イオンクロマトグラフィーDX320(日本ダイオネクス(株)製)およびシーケンシャル型ICP発光分光分析装置SPS4000(セイコーインスツルメンツ(株)製)を用いて測定を行った。 Elemental analysis is performed using a CHN coder MT-3 type (manufactured by Yanagimoto Seisakusho Co., Ltd.), ion chromatography DX320 (manufactured by Nippon Dionex Co., Ltd.) and a sequential ICP emission spectroscopic analyzer SPS4000 (manufactured by Seiko Instruments Inc.). And measured.
マススペクトルはJMS−DX303(日本電子(株)製)を用いて測定を行った。 Mass spectrum was measured using JMS-DX303 (manufactured by JEOL Ltd.).
融点の測定は、示差走査熱量計(島津製作所(株)製DSC−50)により、窒素雰囲気中、昇温速度2℃/分で測定した。 The melting point was measured with a differential scanning calorimeter (DSC-50 manufactured by Shimadzu Corporation) in a nitrogen atmosphere at a heating rate of 2 ° C./min.
蛍光スペクトルはF−2500形蛍光分光光度計(日立製作所(株)製)を用いた。 For the fluorescence spectrum, an F-2500 type fluorescence spectrophotometer (manufactured by Hitachi, Ltd.) was used.
輝度は輝度計(トプコン社製、BM−8)を視野角0.2度、レスポンス1msの条件で用いて測定した。 The luminance was measured using a luminance meter (Topcon, BM-8) under the conditions of a viewing angle of 0.2 degrees and a response of 1 ms.
素子寿命の指標として輝度半減時間を下記のように測定した。4mA/cm2の一定電流で発光させ、その後、発光輝度が半減した時間を測定した。 The luminance half time was measured as follows as an index of element lifetime. Light was emitted at a constant current of 4 mA / cm 2 , and then the time when the light emission luminance was reduced by half was measured.
真空度1×10−4Pa以下で、蒸着源の温度を10℃ずつ上げていき、蒸着膜の堆積速度が0.1nm/秒以上になった時の蒸着源の温度を昇華温度とした。使用した蒸着源は、窒化アルミニウム製のルツボで、円筒状で容量は10ccのものを用いた。ルツボの底に熱電対があり、ルツボ底部の温度を測定した。 The temperature of the vapor deposition source was increased by 10 ° C. at a degree of vacuum of 1 × 10 −4 Pa or less, and the temperature of the vapor deposition source when the deposition rate of the vapor deposition film reached 0.1 nm / second or more was defined as the sublimation temperature. The vapor deposition source used was an aluminum nitride crucible having a cylindrical shape and a capacity of 10 cc. There was a thermocouple at the bottom of the crucible, and the temperature at the bottom of the crucible was measured.
ピロメテン化合物の分解試験は、上記昇華温度において窒素雰囲気下で24時間加熱して、加熱前後でのHPLC純度変化が1%以上のものを分解したと判断した。つまり、この測定で分解していない材料は、分解温度が昇華温度より高い。 In the decomposition test of the pyromethene compound, it was judged that heating was performed in the above sublimation temperature under a nitrogen atmosphere for 24 hours, and the HPLC purity change before and after heating was decomposed by 1% or more. That is, the material not decomposed by this measurement has a decomposition temperature higher than the sublimation temperature.
HPLCの測定は、(株)島津製作所製CLASS−VPを用い、流速は1.0ml/min、カラムは関東化学(株)製マイティシルRP−8GP、カラム温度45℃、解析は254nmで行った。 HPLC measurement was performed using CLASS-VP manufactured by Shimadzu Corporation, the flow rate was 1.0 ml / min, the column was Mightysil RP-8GP manufactured by Kanto Chemical Co., Ltd., the column temperature was 45 ° C., and the analysis was performed at 254 nm. .
下記実施例、比較例で使用する材料を下記に示す。 The materials used in the following examples and comparative examples are shown below.
実施例1
化合物〔3〕の合成方法
1,2−ジクロロエタン30ml中に、2−(4−t−ブチルベンゾイル)−3,5−ビス(4−メチルフェニル)ピロール4.1g(0.01モル)、2,4−ビス(4−メチルフェニル)ピロール2.5g(0.01モル)、オキシ塩化リン1.5gを入れ、加熱環流下12時間反応させた。室温に冷却した後、ジイソプロピルエチルアミン5.2g、三フッ化ホウ素ジエチルエーテル錯体5.6gを加え、6時間撹拌した。50mlの水を加え、ジクロロメタンを投入後、有機層を抽出し、濃縮して、シリカゲルを用いたカラムクロマトグラフィーによる精製をした後、さらに昇華精製を行い、赤紫色粉末4.3gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):1.07(s,9H),2.13(s,6H),2.39(s,6H),6.47(t,4H),6.63(s,8H),6.75(d,2H),7.23(d,4H),7.80(d,4H)
また、元素分析結果は、組成式C47H43BF2N2として以下のとおりであった。なお括弧内は理論値である。C:82.3%(82.5%)、H:6.3%(6.3%)、B:1.6%(1.6%)、F:6.3%(5.6%)、N:4.2%(4.1%)。
Example 1
Synthesis method of compound [3] In 30 ml of 1,2-dichloroethane, 4.1 g (0.01 mol) of 2- (4-tert-butylbenzoyl) -3,5-bis (4-methylphenyl) pyrrole, 2 , 4-bis (4-methylphenyl) pyrrole (2.5 g, 0.01 mol) and phosphorus oxychloride (1.5 g) were added and reacted for 12 hours under heating and reflux. After cooling to room temperature, 5.2 g of diisopropylethylamine and 5.6 g of boron trifluoride diethyl ether complex were added and stirred for 6 hours. 50 ml of water was added, dichloromethane was added, the organic layer was extracted, concentrated, purified by column chromatography using silica gel, and further purified by sublimation to obtain 4.3 g of reddish purple powder. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 1.07 (s, 9H), 2.13 (s, 6H), 2.39 (s, 6H), 6.47 (t, 4H), 6.63 (s, 8H), 6.75 (d, 2H), 7.23 (d, 4H), 7.80 (d, 4H)
The results of elemental analysis were as follows as the composition formula C 47 H 43 BF 2 N 2 . The values in parentheses are theoretical values. C: 82.3% (82.5%), H: 6.3% (6.3%), B: 1.6% (1.6%), F: 6.3% (5.6%) ), N: 4.2% (4.1%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=684であった。以上のことから、上記生成物である赤紫色粉末は、化合物〔3〕であることが確認された。ピロメテン化合物の分解試験結果、融点、昇華温度は表1に示した。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 684. From the above, it was confirmed that the reddish purple powder as the product was the compound [3]. The decomposition test results, melting point and sublimation temperature of the pyromethene compound are shown in Table 1.
実施例2
化合物〔4〕の合成方法
2−(2,6−ジメトキシベンゾイル)−3,5−ビス(4−メチルフェニル)ピロール4.1g(0.01モル)、2,4−ビス(4−メチルフェニル)ピロール2.5gを用い、化合物〔3〕と同様に合成した。赤紫色粉末0.7gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):2.14(s,6H),2.37(s,6H),3.50(s,6H),5.61(d,2H),6.35(s,2H),6.35(t,1H),6.55(q,8H),7.22(d,4H),7.82(d,4H)
また、元素分析結果は、組成式C45H39BF2N2O2として以下のとおりであった。なお括弧内は理論値である。C:78.6%(78.5%)、H:5.7%(5.7%)、B:1.6%(1.6%)、F:5.4%(5.5%)、N:4.2%(4.1%)。
Example 2
Synthesis method of compound [4] 4.1 g (0.01 mol) of 2- (2,6-dimethoxybenzoyl) -3,5-bis (4-methylphenyl) pyrrole, 2,4-bis (4-methylphenyl) ) 2.5 g of pyrrole was synthesized in the same manner as compound [3]. 0.7 g of reddish purple powder was obtained. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 2.14 (s, 6H), 2.37 (s, 6H), 3.50 (s, 6H), 5.61 (d, 2H), 6.35 (s, 2H), 6.35 (t, 1H), 6.55 (q, 8H), 7.22 (d, 4H), 7.82 (d, 4H)
Elemental analysis results were as follows as the composition formula C 45 H 39 BF 2 N 2 O 2. The values in parentheses are theoretical values. C: 78.6% (78.5%), H: 5.7% (5.7%), B: 1.6% (1.6%), F: 5.4% (5.5%) ), N: 4.2% (4.1%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=687であった。以上のことから、上記生成物である赤紫色粉末は、化合物〔4〕であることが確認された。ピロメテン化合物の分解試験結果、融点、昇華温度は表1に示した。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 687. From the above, it was confirmed that the reddish purple powder as the product was the compound [4]. The decomposition test results, melting point and sublimation temperature of the pyromethene compound are shown in Table 1.
実施例3
化合物〔24〕の合成方法
2−ベンゾイル−3,5−ビス(4−t−ブチルフェニル)ピロール4.4g、2,4−ビス(4−t−ブチルフェニル)ピロール3.3gを用い、化合物〔3〕と同様に合成した。赤色粉末4.4gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):1.18(s,18H),1.35(s,18H),6.40(t,2H),6.53-6.66(m,7H),6.77-6.84(m,6H),7.46(d,4H),7.86(d,4H)
また、元素分析結果は、組成式C55H59BF2N2として以下のとおりであった。なお括弧内は理論値である。C:83.1%(82.9%)、H:7.7%(7.5%)、B:1.3%(1.4%)、F:4.3%(4.8%)、N:3.5%(3.5%)。
Example 3
Method of synthesizing compound [24] Using 4.4 g of 2-benzoyl-3,5-bis (4-t-butylphenyl) pyrrole and 3.3 g of 2,4-bis (4-t-butylphenyl) pyrrole, compound Synthesized as in [3]. 4.4 g of red powder was obtained. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 1.18 (s, 18H), 1.35 (s, 18H), 6.40 (t, 2H), 6.53-6.66 (m, 7H), 6.77-6.84 (m, 6H), 7.46 (d, 4H), 7.86 (d, 4H)
The results of elemental analysis were as follows as the composition formula C 55 H 59 BF 2 N 2 . The values in parentheses are theoretical values. C: 83.1% (82.9%), H: 7.7% (7.5%), B: 1.3% (1.4%), F: 4.3% (4.8%) ), N: 3.5% (3.5%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=796であった。以上のことから、上記生成物である赤色粉末は、化合物〔24〕であることが確認された。ピロメテン化合物の分解試験結果、融点、昇華温度は表1に示した。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 796. From the above, it was confirmed that the red powder as the product was the compound [24]. The decomposition test results, melting point and sublimation temperature of the pyromethene compound are shown in Table 1.
実施例4
化合物〔25〕の合成方法
2−(4−メチルベンゾイル)−3,5−ビス(4−t−ブチルフェニル)ピロール4.5g、2,4−ビス(4−t−ブチルフェニル)ピロール3.3gを用い、化合物〔3〕と同様に合成した。赤色粉末4gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):1.20(s,18H),1.35(s,18H),1.94(s,3H),6.22(d,2H),6.52(s,2H),6.68(q,6H),6.86(d,4H),7.45(d,4H),7.85(d,4H)
また、元素分析結果は、組成式C56H61BF2N2として以下のとおりであった。なお括弧内は理論値である。C:83.2%(82.9%)、H:7.6%(7.6%)、B:1.3%(1.33%)、F:4.0%(4.7%)、N:3.6%(3.5%)。
Example 4
2. Synthesis method of compound [25] 4.5 g of 2- (4-methylbenzoyl) -3,5-bis (4-tert-butylphenyl) pyrrole, 2,4-bis (4-tert-butylphenyl) pyrrole Using 3 g, the compound was synthesized in the same manner as Compound [3]. 4 g of red powder was obtained. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 1.20 (s, 18H), 1.35 (s, 18H), 1.94 (s, 3H), 6.22 (d, 2H), 6.52 (s, 2H), 6.68 (q, 6H), 6.86 (d, 4H), 7.45 (d, 4H), 7.85 (d, 4H)
The results of elemental analysis were as follows as the composition formula C 56 H 61 BF 2 N 2 . The values in parentheses are theoretical values. C: 83.2% (82.9%), H: 7.6% (7.6%), B: 1.3% (1.33%), F: 4.0% (4.7%) ), N: 3.6% (3.5%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=810であった。以上のことから、上記生成物である赤色粉末は、化合物〔25〕であることが確認された。ピロメテン化合物の分解試験結果、融点、昇華温度は表1に示した。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 810. From the above, it was confirmed that the red powder as the product was the compound [25]. The decomposition test results, melting point and sublimation temperature of the pyromethene compound are shown in Table 1.
実施例5
化合物〔26〕の合成方法
2−(4−メトキシベンゾイル)−3,5−ビス(4−t−ブチルフェニル)ピロール4.7g、2,4−ビス(4−t−ブチルフェニル)ピロール3.3gを用い、化合物〔3〕と同様に合成した。赤色粉末5gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):1.20(s,18H),1.35(s,18H),3.51(s,3H),5.94(d,2H),6.54(s,2H),6.69(t,6H),6.89(d,4H),7.45(d,4H),7.85(d,4H)
また、元素分析結果は、組成式C56H61BF2N2Oとして以下のとおりであった。なお括弧内は理論値である。C:81.3%(81.3%)、H:7.5%(7.4%)、B:1.3%(1.3%)、F:5.3%(4.6%)、N:3.4%(3.4%)。
Example 5
2. Synthesis method of compound [26] 2- (4-methoxybenzoyl) -3,5-bis (4-t-butylphenyl) pyrrole 4.7 g, 2,4-bis (4-t-butylphenyl) pyrrole Using 3 g, the compound was synthesized in the same manner as Compound [3]. 5 g of red powder was obtained. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 1.20 (s, 18H), 1.35 (s, 18H), 3.51 (s, 3H), 5.94 (d, 2H), 6.54 (s, 2H), 6.69 (t, 6H), 6.89 (d, 4H), 7.45 (d, 4H), 7.85 (d, 4H)
Elemental analysis results were as follows as the composition formula C 56 H 61 BF 2 N 2 O. The values in parentheses are theoretical values. C: 81.3% (81.3%), H: 7.5% (7.4%), B: 1.3% (1.3%), F: 5.3% (4.6%) ), N: 3.4% (3.4%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=826であった。以上のことから、上記生成物である赤色粉末は、化合物〔26〕であることが確認された。ピロメテン化合物の分解試験結果、融点、昇華温度は表1に示した。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 826. From the above, it was confirmed that the red powder as the product was the compound [26]. The decomposition test results, melting point and sublimation temperature of the pyromethene compound are shown in Table 1.
実施例6
化合物〔29〕の合成方法
2−(2,6−ジメトキシベンゾイル)−3,5−ビス(4−t−ブチルフェニル)ピロール5.0g、2,4−ビス(4−t−ブチルフェニル)ピロール3.3gを用い、化合物〔3〕と同様に合成した。赤紫色粉末0.3gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):1.20(s,18H),1.35(s,18H),3.50(s,6H),5.56(d,2H),6.40-6.48(m,3H),6.72(d,4H),6.85(d,4H),7.43(d,4H),7.87(d,4H)
また、元素分析結果は、組成式C57H63BF2N2O2として以下のとおりであった。なお括弧内は理論値である。C:79.9%(79.9%)、H:7.5%(7.4%)、B:1.2%(1.3%)、F:4.0%(4.4%)、N:3.4%(3.3%)。
Example 6
Synthesis Method of Compound [29] 2- (2,6-Dimethoxybenzoyl) -3,5-bis (4-tert-butylphenyl) pyrrole 5.0 g, 2,4-bis (4-tert-butylphenyl) pyrrole Synthesis was performed in the same manner as Compound [3] using 3.3 g. 0.3 g of reddish purple powder was obtained. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 1.20 (s, 18H), 1.35 (s, 18H), 3.50 (s, 6H), 5.56 (d, 2H), 6.40-6.48 (m, 3H) , 6.72 (d, 4H), 6.85 (d, 4H), 7.43 (d, 4H), 7.87 (d, 4H)
The results of elemental analysis were as follows as the composition formula C 57 H 63 BF 2 N 2 O 2 . The values in parentheses are theoretical values. C: 79.9% (79.9%), H: 7.5% (7.4%), B: 1.2% (1.3%), F: 4.0% (4.4%) ), N: 3.4% (3.3%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=856であった。以上のことから、上記生成物である赤紫色粉末は、化合物〔29〕であることが確認された。ピロメテン化合物の分解試験結果、融点、昇華温度は表1に示した。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 856. From the above, it was confirmed that the reddish purple powder as the product was the compound [29]. The decomposition test results, melting point and sublimation temperature of the pyromethene compound are shown in Table 1.
比較例1
ドーパント材料である下記に示すDPT1のピロメテン化合物の分解試験結果、融点、昇華温度を表1に示した。
Comparative Example 1
Table 1 shows the decomposition test results, melting point and sublimation temperature of the DPT1 pyromethene compound shown below, which is a dopant material.
比較例2
ドーパント材料である下記に示すDPT2のピロメテン化合物の分解試験結果、融点、昇華温度を表1に示した。
Comparative Example 2
Table 1 shows the decomposition test results, melting point, and sublimation temperature of the DPT2 pyromethene compound shown below, which is a dopant material.
実施例7
化合物〔3〕を用いた発光素子を次のように作製した。ITO透明導電膜を150nm堆積させたガラス基板(旭硝子(株)製、15Ω/□、電子ビーム蒸着品)を30×40mmに切断、エッチングを行った。得られた基板をアセトン、“セミコクリン56”で各々15分間超音波洗浄してから、超純水で洗浄した。続いてイソプロピルアルコールで15分間超音波洗浄してから熱メタノールに15分間浸漬させて乾燥させた。この基板を素子を作製する直前に1時間UV−オゾン処理し、真空蒸着装置内に設置して、装置内の真空度が5×10−5Pa以下になるまで排気した。抵抗加熱法によって、まず正孔注入材料として、銅フタロシアニン(CuPc)を10nm蒸着した。次に、正孔輸送材料としてN,N’−ジナフチル−N,N’−ジフェニル−4,4’−ジフェニル−1,1’−ジアミン(HTL1)を50nm蒸着した。次にホスト材料として前記HST1、ドーパンド材料として化合物〔3〕を用いて、ドーパント濃度が1wt%になるように40nmの厚さに共蒸着し、電子輸送材料として前記ETL1を35nmの厚さに積層した。次に電子注入材料として、リチウムを0.5nm、銀を150nm蒸着して陰極とし、5×5mm角の素子を作製した。ここで言う膜厚は水晶発振式膜厚モニター表示値である。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が610nm、発光効率は4.8cd/Aの赤色発光が得られた。この素子は、1000時間たっても輝度半減に至らなかった。
Example 7
A light emitting device using the compound [3] was produced as follows. A glass substrate on which an ITO transparent conductive film was deposited to a thickness of 150 nm (Asahi Glass Co., Ltd., 15Ω / □, electron beam evaporated product) was cut into 30 × 40 mm and etched. The obtained substrate was ultrasonically washed with acetone and “Semicocrine 56” for 15 minutes, respectively, and then washed with ultrapure water. Subsequently, it was ultrasonically cleaned with isopropyl alcohol for 15 minutes and then immersed in hot methanol for 15 minutes to dry. This substrate was subjected to UV-ozone treatment for 1 hour immediately before producing the device, placed in a vacuum deposition apparatus, and evacuated until the degree of vacuum in the apparatus became 5 × 10 −5 Pa or less. First, copper phthalocyanine (CuPc) was deposited as a hole injecting material by a resistance heating method to a thickness of 10 nm. Next, 50 nm of N, N′-dinaphthyl-N, N′-diphenyl-4,4′-diphenyl-1,1′-diamine (HTL1) was deposited as a hole transport material. Next, using the HST1 as a host material and the compound [3] as a dopant material, co-evaporated to a thickness of 40 nm so that the dopant concentration becomes 1 wt%, and the ETL1 was laminated to a thickness of 35 nm as an electron transport material. did. Next, as an electron injection material, lithium was deposited to 0.5 nm and silver was deposited to 150 nm to form a cathode, and a 5 × 5 mm square device was produced. The film thickness referred to here is a display value of a crystal oscillation type film thickness monitor. When an electric current was passed through the light emitting element at 10 mA / cm 2 , the emission spectrum showed red light emission with a peak wavelength of 610 nm and a light emission efficiency of 4.8 cd / A. This device did not reach half the luminance even after 1000 hours.
実施例8〜26、比較例3〜5
正孔注入材料、正孔輸送材料、ホスト材料、ドーパント材料、電子輸送材料、電子注入材料を表2に示した材料を用い、それ以外は実施例7と同様に発光素子の作製を行った。結果を表2、表3に示す。
Examples 8-26, Comparative Examples 3-5
A light emitting device was manufactured in the same manner as in Example 7 except that the materials shown in Table 2 were used as the hole injection material, the hole transport material, the host material, the dopant material, the electron transport material, and the electron injection material. The results are shown in Tables 2 and 3.
実施例27
ホスト材料をHST9、ドーパンド材料を化合物〔24〕とした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が617nm、発光効率は5.2cd/Aの赤色発光が得られた。
Example 27
A light emitting device was fabricated in the same manner as in Example 7 except that the host material was HST9 and the dopant material was compound [24]. When an electric current was passed through the light-emitting element at 10 mA / cm 2 , a red light emission spectrum with a peak wavelength of 617 nm and a light emission efficiency of 5.2 cd / A was obtained.
実施例28
ホスト材料をHST10、ドーパンド材料を化合物〔25〕、電子輸送材料をETL9とした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が614nm、発光効率は5.5cd/Aの赤色発光が得られた。
Example 28
A light emitting device was fabricated in the same manner as in Example 7, except that the host material was HST10, the dopant material was Compound [25], and the electron transport material was ETL9. When an electric current was passed through the light-emitting element at 10 mA / cm 2 , red light emission having a peak wavelength of 614 nm and a light emission efficiency of 5.5 cd / A was obtained.
実施例29
ホスト材料をHST11、ドーパンド材料を化合物〔4〕とした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が616nm、発光効率は4.0cd/Aの赤色発光が得られた。
Example 29
A light emitting device was fabricated in the same manner as in Example 7 except that the host material was HST11 and the dopant material was compound [4]. When an electric current was passed through the light-emitting element at 10 mA / cm 2 , a red light emission spectrum with a peak wavelength of 616 nm and a light emission efficiency of 4.0 cd / A was obtained.
実施例30
正孔輸送材料をHTL3とした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が610nm、発光効率は5.7cd/Aの赤色発光が得られた。
Example 30
A light emitting device was fabricated in the same manner as in Example 7 except that the hole transport material was HTL3. When an electric current was passed through the light-emitting element at 10 mA / cm 2 , red light emission having a peak wavelength of 610 nm and a light emission efficiency of 5.7 cd / A was obtained.
実施例31
正孔輸送材料をHTL4とした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が609nm、発光効率は5.4cd/Aの赤色発光が得られた。
Example 31
A light emitting device was fabricated in the same manner as in Example 7 except that the hole transport material was HTL4. When an electric current was passed through the light emitting element at 10 mA / cm 2 , a red light emission spectrum with a peak wavelength of 609 nm and a light emission efficiency of 5.4 cd / A was obtained.
実施例32
電子輸送材料をETL2、電子注入材料を酸化リチウムとした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が610nm、発光効率は5.5cd/Aの赤色発光が得られた。
Example 32
A light emitting device was manufactured in the same manner as in Example 7 except that the electron transport material was ETL2 and the electron injection material was lithium oxide. When an electric current was passed through the light-emitting element at 10 mA / cm 2 , a red light emission spectrum with a peak wavelength of 610 nm and a light emission efficiency of 5.5 cd / A was obtained.
実施例33
正孔輸送材料を50nm蒸着するまでは実施例7と同様に発光素子作製を行い、次にホスト材料としてHST3、ドーパンド材料として化合物〔24〕を用いて、ドーパント濃度が1wt%になるように40nmの厚さに共蒸着し、電子輸送材料としてHST3を10nmの厚さに蒸着し、さらに、電子輸送材料としてETL4を15nmの厚さに積層した。次に電子注入材料として、リチウムを0.5nm、銀を150nm蒸着して陰極とし、5×5mm角の素子を作製した。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が617nm、発光効率は6.2cd/Aの赤色発光が得られた。
Example 33
The light emitting device was manufactured in the same manner as in Example 7 until the hole transporting material was deposited to 50 nm, and then HST3 was used as the host material and compound [24] was used as the dopant material, so that the dopant concentration was 1 wt%. HST3 was vapor-deposited to a thickness of 10 nm as an electron transport material, and ETL4 was laminated to a thickness of 15 nm as an electron-transport material. Next, as an electron injection material, lithium was deposited to 0.5 nm and silver was deposited to 150 nm to form a cathode, and a 5 × 5 mm square device was produced. When an electric current was passed through the light emitting element at 10 mA / cm 2 , a red light emission spectrum with a peak wavelength of 617 nm and a light emission efficiency of 6.2 cd / A was obtained.
実施例34
ホスト材料を[3]、ドーパント材料を用いないとした以外は、実施例7と同様に発光素子作製を行った。この発光素子に10mA/cm2で電流を流したときの発光スペクトルは、ピーク波長が615nm、発光効率は1.5cd/Aの赤色発光が得られた。
Example 34
A light emitting device was manufactured in the same manner as in Example 7 except that the host material [3] and the dopant material were not used. When an electric current was passed through the light-emitting element at 10 mA / cm 2 , a red light emission spectrum with a peak wavelength of 615 nm and a light emission efficiency of 1.5 cd / A was obtained.
実施例35
正孔輸送材料を50nm蒸着するまでは実施例7と同様に発光素子作製を行い、次にホスト材料としてHST3、ドーパンド材料として化合物〔26〕を用いて、ドーパント濃度が1wt%になるように10nmの厚さに共蒸着し、さらに、ホスト材料として下記に示すHST12、ドーパント材料として下記に示すDPT3を用いて、ドーパント濃度が2wt%になるように15nmの厚さに共蒸着し、電子輸送材料としてETL1を35nmの厚さに積層した。次に電子注入材料として、リチウムを0.5nm、銀を150nm蒸着して陰極とし、5×5mm角の素子を作製した。この発光素子に10mA/cm2で電流を流したときの、発光効率は7.0cd/Aの白色発光が得られた。
Example 35
The light emitting device is manufactured in the same manner as in Example 7 until the hole transport material is deposited to 50 nm, and then HST3 is used as the host material and the compound [26] is used as the dopant material, so that the dopant concentration becomes 1 wt%. Further, using HST12 shown below as a host material and DPT3 shown below as a dopant material, the material is co-evaporated to a thickness of 15 nm so that the dopant concentration is 2 wt%. As a result, ETL1 was laminated to a thickness of 35 nm. Next, as an electron injection material, lithium was deposited to 0.5 nm and silver was deposited to 150 nm to form a cathode, and a 5 × 5 mm square device was produced. When a current was passed through the light emitting element at 10 mA / cm 2 , white light emission with a light emission efficiency of 7.0 cd / A was obtained.
実施例36
化合物〔51〕の合成方法
1,2−ジクロロエタン20ml中に、2−ベンゾイル−3,5−ビス(4−t−ブチルフェニル)ピロール2.0g(0.047モル)、2,4−ビス(4−メトキシフェニル)ピロール2.5g(0.047モル)、オキシ塩化リン0.72gを入れ、加熱環流下12時間反応させた。室温に冷却した後、ジイソプロピルエチルアミン4.8g、三フッ化ホウ素ジエチルエーテル錯体5.3gを加え、6時間撹拌した。20mlの水を加え、ジクロロメタンを投入後、有機層を抽出し、濃縮して、シリカゲルを用いたカラムクロマトグラフィーによる精製をした後、さらに昇華精製を行い、赤色粉末1.9gを得た。得られた粉末の1H−NMR分析結果は次の通りであった。
1H−NMR(CDCl3(d=ppm)):1.19(s,9H),1.35(s,9H),3.66(s,3H),3.85(s,3H),6.36(d,2H),6.44-6.52(dd,4H),6.62-6.68(m,5H),6.80-6.86(m,4H),6.97(d,2H),7.45(d,2H),7.83-7.92(dd,4H)
また、元素分析結果は、組成式C49H47O2BF2N2として以下のとおりであった。なお括弧内は理論値である。C:79.3%(79.0%)、H:6.4%(6.3%)、O:4.4%(4.3%)、B:1.4%(1.5%)、F:4.3%(5.1%)、N:3.9%(3.8%)。
Example 36
Synthesis method of compound [51] In 20 ml of 1,2-dichloroethane, 2.0 g (0.047 mol) of 2-benzoyl-3,5-bis (4-tert-butylphenyl) pyrrole, 2,4-bis ( 4-Methoxyphenyl) pyrrole (2.5 g, 0.047 mol) and phosphorus oxychloride (0.72 g) were added, and the mixture was allowed to react for 12 hours under heating and reflux. After cooling to room temperature, 4.8 g of diisopropylethylamine and 5.3 g of boron trifluoride diethyl ether complex were added and stirred for 6 hours. After adding 20 ml of water and adding dichloromethane, the organic layer was extracted, concentrated, purified by column chromatography using silica gel, and further purified by sublimation to obtain 1.9 g of red powder. The results of 1 H-NMR analysis of the obtained powder were as follows.
1 H-NMR (CDCl 3 (d = ppm)): 1.19 (s, 9H), 1.35 (s, 9H), 3.66 (s, 3H), 3.85 (s, 3H), 6.36 (d, 2H), 6.44 -6.52 (dd, 4H), 6.62-6.68 (m, 5H), 6.80-6.86 (m, 4H), 6.97 (d, 2H), 7.45 (d, 2H), 7.83-7.92 (dd, 4H)
The results of elemental analysis were as follows as the composition formula C 49 H 47 O 2 BF 2 N 2 . The values in parentheses are theoretical values. C: 79.3% (79.0%), H: 6.4% (6.3%), O: 4.4% (4.3%), B: 1.4% (1.5%) ), F: 4.3% (5.1%), N: 3.9% (3.8%).
また、マススペクトルより、目的物の主な分子イオンピークはm/Z=744であった。以上のことから、上記生成物である赤色粉末は、化合物〔51〕であることが確認された。 From the mass spectrum, the main molecular ion peak of the target product was m / Z = 744. From the above, it was confirmed that the red powder as the product was the compound [51].
次に、ドーパント材料に化合物〔51〕を用いた以外は、実施例7と同様に発光素子作製を行った。この発光素子を10mA/cm2で駆動したところ、発光スペクトルのピーク波長が627nm、発光効率が4.2cd/Aの赤色発光が得られた。この素子は、1000時間たっても輝度半減に至らなかった。 Next, a light emitting device was produced in the same manner as in Example 7 except that the compound [51] was used as the dopant material. When this light emitting device was driven at 10 mA / cm 2 , red light emission with a peak wavelength of the emission spectrum of 627 nm and a light emission efficiency of 4.2 cd / A was obtained. This device did not reach half the luminance even after 1000 hours.
また、化合物〔51〕の昇華温度は260℃であり、該昇華温度では分解しなかった。 Compound [51] had a sublimation temperature of 260 ° C. and did not decompose at the sublimation temperature.
比較例6
ITO付きガラス基板を真空蒸着装置内に設置して、装置内の真空度が5×10−5Pa以下になるまで排気するまでは、実施例7と同様に行い、抵抗加熱法によって、まず正孔輸送材料として4,4’−ビス(N−(m−トリル)−N−フェニルアミノ)ビフェニル(m−MTDATA)を50nm蒸着した。次にホスト材料としてHST1、ドーパンド材料として化合物DPT2を用いて、ドーパント濃度が1wt%になるように15nmの厚さに共蒸着し、ホスト材料を35nmの厚さに積層した。次にリチウムを0.5nm、銀を150nm蒸着して陰極とし、5×5mm角の素子を作製した。この発光素子からの発光スペクトルは、ピーク波長が618nm、発光効率は4.2cd/Aの赤色発光が得られた。輝度半減時間は200時間であった。
Comparative Example 6
A glass substrate with ITO is placed in a vacuum deposition apparatus, and the process is performed in the same manner as in Example 7 until the degree of vacuum in the apparatus is reduced to 5 × 10 −5 Pa or less. As a hole transport material, 4,4′-bis (N- (m-tolyl) -N-phenylamino) biphenyl (m-MTDATA) was deposited by 50 nm. Next, HST1 was used as the host material and compound DPT2 was used as the dopant material, so that the host material was co-evaporated to a thickness of 15 nm so that the dopant concentration was 1 wt%, and the host material was laminated to a thickness of 35 nm. Next, lithium was deposited to 0.5 nm and silver was deposited to 150 nm to prepare a cathode having a 5 × 5 mm square. The light emission spectrum from this light emitting element was red light emission with a peak wavelength of 618 nm and a light emission efficiency of 4.2 cd / A. The luminance half time was 200 hours.
表1〜3から、本発明のピロメテン化合物を用いることで、真空蒸着時に分解や重合などの変性が起こらず、従来より高発光効率かつ長寿命の赤色発光素子が得られた。 From Tables 1 to 3, by using the pyromethene compound of the present invention, a red light emitting device with higher luminous efficiency and longer life than before was obtained without any modification such as decomposition or polymerization during vacuum deposition.
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