JP2004284971A - Triazine compound and organic electroluminescent element using the same - Google Patents
Triazine compound and organic electroluminescent element using the same Download PDFInfo
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- JP2004284971A JP2004284971A JP2003077388A JP2003077388A JP2004284971A JP 2004284971 A JP2004284971 A JP 2004284971A JP 2003077388 A JP2003077388 A JP 2003077388A JP 2003077388 A JP2003077388 A JP 2003077388A JP 2004284971 A JP2004284971 A JP 2004284971A
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- compound
- triazine compound
- triazine
- compound according
- general formula
- Prior art date
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- Granted
Links
- -1 Triazine compound Chemical class 0.000 title claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- BABQOLWRWSQINM-UHFFFAOYSA-N 2,4,6-tris(5-methylpyridin-3-yl)-1,3,5-triazine Chemical compound CC1=CN=CC(C=2N=C(N=C(N=2)C=2C=C(C)C=NC=2)C=2C=C(C)C=NC=2)=C1 BABQOLWRWSQINM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000002894 organic compounds Chemical class 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 125000004306 triazinyl group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Chemical group 0.000 claims description 3
- 239000004480 active ingredient Substances 0.000 claims description 2
- 229910000102 alkali metal hydride Inorganic materials 0.000 claims description 2
- 150000008046 alkali metal hydrides Chemical class 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000000470 constituent Substances 0.000 claims 1
- 238000002425 crystallisation Methods 0.000 abstract description 11
- 230000008025 crystallization Effects 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 54
- 239000007787 solid Substances 0.000 description 26
- 239000000203 mixture Substances 0.000 description 18
- 238000001914 filtration Methods 0.000 description 17
- 239000011521 glass Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000005684 electric field Effects 0.000 description 13
- 239000000725 suspension Substances 0.000 description 13
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 9
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000005525 hole transport Effects 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000012141 concentrate Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000000921 elemental analysis Methods 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229940125782 compound 2 Drugs 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- KMVWNDHKTPHDMT-UHFFFAOYSA-N 2,4,6-tripyridin-2-yl-1,3,5-triazine Chemical compound N1=CC=CC=C1C1=NC(C=2N=CC=CC=2)=NC(C=2N=CC=CC=2)=N1 KMVWNDHKTPHDMT-UHFFFAOYSA-N 0.000 description 2
- QRXBTPFMCTXCRD-UHFFFAOYSA-N 2-chloropyridine-4-carbonitrile Chemical compound ClC1=CC(C#N)=CC=N1 QRXBTPFMCTXCRD-UHFFFAOYSA-N 0.000 description 2
- YONYPNNXOHWPBZ-UHFFFAOYSA-N 2-methyl-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(C)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 YONYPNNXOHWPBZ-UHFFFAOYSA-N 0.000 description 2
- GQPYONBHVVYRKV-UHFFFAOYSA-N 4,6-diphenyl-1,3,5-triazine-2-carbaldehyde Chemical compound N=1C(C=O)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 GQPYONBHVVYRKV-UHFFFAOYSA-N 0.000 description 2
- MUDSDYNRBDKLGK-UHFFFAOYSA-N 4-methylquinoline Chemical compound C1=CC=C2C(C)=CC=NC2=C1 MUDSDYNRBDKLGK-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 235000019270 ammonium chloride Nutrition 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229940125773 compound 10 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- ZLVXBBHTMQJRSX-VMGNSXQWSA-N jdtic Chemical compound C1([C@]2(C)CCN(C[C@@H]2C)C[C@H](C(C)C)NC(=O)[C@@H]2NCC3=CC(O)=CC=C3C2)=CC=CC(O)=C1 ZLVXBBHTMQJRSX-VMGNSXQWSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 2
- IBHBKWKFFTZAHE-UHFFFAOYSA-N n-[4-[4-(n-naphthalen-1-ylanilino)phenyl]phenyl]-n-phenylnaphthalen-1-amine Chemical compound C1=CC=CC=C1N(C=1C2=CC=CC=C2C=CC=1)C1=CC=C(C=2C=CC(=CC=2)N(C=2C=CC=CC=2)C=2C3=CC=CC=C3C=CC=2)C=C1 IBHBKWKFFTZAHE-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 2
- GYBMSOFSBPZKCX-UHFFFAOYSA-N sodium;ethanol;ethanolate Chemical compound [Na+].CCO.CC[O-] GYBMSOFSBPZKCX-UHFFFAOYSA-N 0.000 description 2
- SUBJHSREKVAVAR-UHFFFAOYSA-N sodium;methanol;methanolate Chemical compound [Na+].OC.[O-]C SUBJHSREKVAVAR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- CSTSYSPTBAXGEG-UHFFFAOYSA-N 2,4,6-tris(6-methylpyridin-3-yl)-1,3,5-triazine Chemical compound C1=NC(C)=CC=C1C1=NC(C=2C=NC(C)=CC=2)=NC(C=2C=NC(C)=CC=2)=N1 CSTSYSPTBAXGEG-UHFFFAOYSA-N 0.000 description 1
- QQIGHOIUDIEFEC-UHFFFAOYSA-N 2,4,6-tris[2-[(2-methylpropan-2-yl)oxy]pyridin-4-yl]-1,3,5-triazine Chemical compound C1=NC(OC(C)(C)C)=CC(C=2N=C(N=C(N=2)C=2C=C(OC(C)(C)C)N=CC=2)C=2C=C(OC(C)(C)C)N=CC=2)=C1 QQIGHOIUDIEFEC-UHFFFAOYSA-N 0.000 description 1
- STTGYIUESPWXOW-UHFFFAOYSA-N 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline Chemical compound C=12C=CC3=C(C=4C=CC=CC=4)C=C(C)N=C3C2=NC(C)=CC=1C1=CC=CC=C1 STTGYIUESPWXOW-UHFFFAOYSA-N 0.000 description 1
- IKAJOXJNEIOYIP-UHFFFAOYSA-N 2-[2-(4,6-diphenyl-1,3,5-triazin-2-yl)ethyl]-4,6-diphenyl-1,3,5-triazine Chemical compound N=1C(C=2C=CC=CC=2)=NC(C=2C=CC=CC=2)=NC=1CCC(N=1)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 IKAJOXJNEIOYIP-UHFFFAOYSA-N 0.000 description 1
- GCUCYKMDPCZMSH-UHFFFAOYSA-N 2-[4,6-di(quinolin-2-yl)-1,3,5-triazin-2-yl]quinoline Chemical compound C1=CC=CC2=NC(C=3N=C(N=C(N=3)C=3N=C4C=CC=CC4=CC=3)C3=NC4=CC=CC=C4C=C3)=CC=C21 GCUCYKMDPCZMSH-UHFFFAOYSA-N 0.000 description 1
- FFNVQNRYTPFDDP-UHFFFAOYSA-N 2-cyanopyridine Chemical compound N#CC1=CC=CC=N1 FFNVQNRYTPFDDP-UHFFFAOYSA-N 0.000 description 1
- NZAZWLSRKMDRNS-UHFFFAOYSA-N 2-methoxypyridine-4-carbonitrile Chemical compound COC1=CC(C#N)=CC=N1 NZAZWLSRKMDRNS-UHFFFAOYSA-N 0.000 description 1
- VDWQWOXVBXURMT-UHFFFAOYSA-N 5-methylpyridine-3-carbonitrile Chemical compound CC1=CN=CC(C#N)=C1 VDWQWOXVBXURMT-UHFFFAOYSA-N 0.000 description 1
- PBLOYQAQGYUPCM-UHFFFAOYSA-N 6-methylpyridine-3-carbonitrile Chemical compound CC1=CC=C(C#N)C=N1 PBLOYQAQGYUPCM-UHFFFAOYSA-N 0.000 description 1
- GLOZCEDUHQCECL-AOWAJDGISA-N C(c1ccc(/C=C/c2nc(-c3ccccc3)nc(-c3ccccc3)n2)cc1)=C/c1nc(-c2ccccc2)nc(-c2ccccc2)n1 Chemical compound C(c1ccc(/C=C/c2nc(-c3ccccc3)nc(-c3ccccc3)n2)cc1)=C/c1nc(-c2ccccc2)nc(-c2ccccc2)n1 GLOZCEDUHQCECL-AOWAJDGISA-N 0.000 description 1
- BXMFMETUNZQMPC-UHFFFAOYSA-N C1(=CC=CC=C1)C1=NC=NC(=N1)C1=CC=CC=C1.C1(=CC=CC=C1)C1=NC=NC(=N1)C1=CC=CC=C1.C1(=CC=C(C=C1)C#C)C#C Chemical compound C1(=CC=CC=C1)C1=NC=NC(=N1)C1=CC=CC=C1.C1(=CC=CC=C1)C1=NC=NC(=N1)C1=CC=CC=C1.C1(=CC=C(C=C1)C#C)C#C BXMFMETUNZQMPC-UHFFFAOYSA-N 0.000 description 1
- AGLRIRWGOBMAMG-UHFFFAOYSA-N C1=NC(OC)=CC(C=2N=C(N=C(N=2)C=2C=C(OC)N=CC=2)C=2C=C(OC)N=CC=2)=C1 Chemical compound C1=NC(OC)=CC(C=2N=C(N=C(N=2)C=2C=C(OC)N=CC=2)C=2C=C(OC)N=CC=2)=C1 AGLRIRWGOBMAMG-UHFFFAOYSA-N 0.000 description 1
- WINOMXCOPUSDIV-UHFFFAOYSA-N C1=NC(OCC)=CC(C=2N=C(N=C(N=2)C=2C=C(OCC)N=CC=2)C=2C=C(OCC)N=CC=2)=C1 Chemical compound C1=NC(OCC)=CC(C=2N=C(N=C(N=2)C=2C=C(OCC)N=CC=2)C=2C=C(OCC)N=CC=2)=C1 WINOMXCOPUSDIV-UHFFFAOYSA-N 0.000 description 1
- GINQYRIEBJEDMI-UHFFFAOYSA-N C=1C=NC2=CC=CC=C2C=1C=CC(N=1)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 Chemical compound C=1C=NC2=CC=CC=C2C=1C=CC(N=1)=NC(C=2C=CC=CC=2)=NC=1C1=CC=CC=C1 GINQYRIEBJEDMI-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000003506 n-propoxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- RPDAUEIUDPHABB-UHFFFAOYSA-N potassium ethoxide Chemical compound [K+].CC[O-] RPDAUEIUDPHABB-UHFFFAOYSA-N 0.000 description 1
- 229910000105 potassium hydride Inorganic materials 0.000 description 1
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 description 1
- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- WDXARTMCIRVMAE-UHFFFAOYSA-N quinoline-2-carbonitrile Chemical compound C1=CC=CC2=NC(C#N)=CC=C21 WDXARTMCIRVMAE-UHFFFAOYSA-N 0.000 description 1
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- SYXYWTXQFUUWLP-UHFFFAOYSA-N sodium;butan-1-olate Chemical compound [Na+].CCCC[O-] SYXYWTXQFUUWLP-UHFFFAOYSA-N 0.000 description 1
- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000001771 vacuum deposition Methods 0.000 description 1
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- Plural Heterocyclic Compounds (AREA)
Abstract
Description
【０００１】
【発明の属する技術分野】
本発明は新規なトリアジン化合物、その製造方法および該化合物を電子注入化合物とする有機発光素子に関する。
【０００２】
【従来の技術】
近年、情報機器の多様化に伴って、Ｃａｔｈｏｄｅ Ｒａｙ Ｔｕｂｅ（いわゆるＣＲＴ）よりも低消費電力で空間占有面積の小さい平面型表示素子に関するニーズが高くなり、特に自発光型で表示が鮮明、かつエネルギー変換効率の高い有機ＥＬ素子に対する注目が集まり、様々な材料並びに有機発光素子の提案がなされてきた。
【０００３】
有機発光素子、特に有機電界素子（有機ＥＬ素子）は、通常、ガラスやプラスチックなどの透明基板上に陽極を設け、その上に正孔輸送、発光、電子輸送（電子注入）のための各種の有機薄膜層が積層され、更にその上に陰極が設けられた構造となっている。
かかる有機電界素子の両電極間に電圧を印加すると、正孔輸送、発光、電子輸送の各層に電流が流れ、発光層において正孔と電子の再結合により発光現象が生じ、発生した光のうち透明電極及び透明基板を厚さ方向に透過した光が外部に照射されて、１０Ｖ前後の電圧の印加により１００〜１００００カンデラ／ｍ２といった極めて高輝度の発光が得られることから、次世代ディスプレイ素子の有力候補として注目されている。
【０００４】
このような有機電界発光素子において、従来型の殆どの有機ＥＬ素子においては発生した光の一部のみが透明な陽極側より照射されるが、その割合は、素子内の屈折率ｎに対し理論的には１／（２ｎ２）であり、例えば屈折率ｎが１．５の場合、外部照射の割合はわずか２２％程度であって、残りの７８％近くは有機積層内やガラス基板を導波して金属面で吸収されるか、基板の端から放出され、極めて発光効率の悪いものである。
【０００５】
かかる発光効率を向上させるために、陽極、陰極ともにＩｎｄｉｕｍ−Ｔｉｎ−Ｏｘｉｄｅ（以下「ＩＴＯ」と略記する。）からなる透明電極を用いた例も報告され、更には、ＩＴＯ電極を陽極とし、ビス−（α−ナフチルフェニルアミノ）ビフェニル（ＮＰＤ）を正孔輸送層、トリス（８−キノリノラト）アルミニウム錯体（いわゆるＡｌｑ３）を電子輸送性発光層とし、その上に陰極としてＩＴＯ電極を製膜した透明有機電界素子も報告されている。
【０００６】
しかし、かかる素子においてはまだ発光効率の改善が十分でなく、更なる発光効率向上のために、上記の素子において、Ａｌｑ３を発光層とし、該Ａｌｑ３発光層とＩＴＯ電極との間に下記式で示される
【０００７】
【特許文献１】
特開２００２−３３２５６７号公報
【０００８】
しかしながら、陽極および陰極の両電極を光透過度の高い透明ＩＴＯ電極とし、Ａｌｑ３を電子輸送性発光層とすることにより素子内で発生した光を効率よく素子外部に取り出し、さらにはＢＣＰを電子輸送層として設けた場合には、発光効率をより向上させることはできるが、ＢＣＰは結晶化し易いために素子としての透明性が失われたリ、結晶化により電流が流れにくくなるため、結果として素子寿命が短くなるという問題があり、その改善が求められていた。
【０００９】
【発明が解決しようとする課題】
このようなことから、本発明者らは、透過率を損なうことなく発光を取り出すことが可能な透明な陽極および陰極、とりわけ両電極を光透過度の高いＩＴＯ電極として用いた有機ＥＬ素子において、上記のＡｌｑ３を電子輸送性発光層とする場合およびＢＣＰを電子輸送層として使用する場合のそれぞれの問題点を同時に解決し、発光効率としてはＡｌｑ３を発光層とする場合よりも高くなり、しかも、電子輸送層における電子注入材料として使用してもＢＣＰのように結晶化を生じることもなく、素子寿命に対する影響も少なく、電子輸送層として良好な製膜性を有する化合物を開発するとともに、該化合物を電子輸送層における電子注入化合物として用いた有機電界素子を開発すべく検討を行い、本発明に至った。
【００１０】
【課題を解決するための手段】
本発明の第１は、下記一般式（１）
【化１】
で表されるトリアジン化合物を、本発明の第２はその製造方法を、本発明の第３は該トリアジン化合物を有効成分とする有機発光素子を提供するものである。
【００１１】
【発明の実施の形態】
前記一般式（１）で示される本発明のトリアジン化合物において、環Ａとしてはフェニル環、ピリジン環、シクロペンタジエン環が、アルキル基としてはメチル、エチル、ｎ−またはｉｓｏ−プロピル、ｎ−、ｓｅｃ−またはｔ−ブチルなどが、アルコキシル基としてはメトキシ、エトキシ、ｎ−またはｉｓｏ−プロポキシ、ｎ−、ｓｅｃ−またはｔ−ブトキシなどがそれぞれ例示される。
また、隣接して結合しているＲ４およびＲ５の末端同士が結合して、環Ａを構成する２個の炭素原子を共有する５員環または６員環を形成している場合の例としては環Ａをあわせた全体としてキノリン環が挙げられる。
このような本発明のトリアジン化合物として、具体的には以下に示す化合物が例示される。
【００１２】
（化合物１）
（化合物２）
（化合物３）
（化合物４）
（化合物５）
（化合物６）
（化合物７）
（化合物８）
（化合物９）
（化合物１０）
本発明の上記一般式（１）で示されるトリアジン化合物は、例えば一般式（４）
【００２３】
ここで、塩基としては水素化ナトリウム、水素化カリウムなどのアルカリ金属水素化物や、ナトリウムメトキシド、ナトリウムエトキシド、ナトリウムブトキシド、カリウムメトキシド、カリウムエトキシド、カリウム−ｔ−ブトキシドなどのアルカリ金属アルコキシド、塩化アンモニウムなどのハロゲン化アンモニウムなどが好適に使用される。
【００２４】
塩基の使用量は反応条件によっても異なるが、一般には原料シアノ化合物に対して０．０１〜２モル倍の範囲であり、反応温度は原料化合物や溶媒を使用する場合にはその溶媒の種類などによっても異なり、それぞれの条件に応じて最適の温度が設定される。
【００２５】
尚、アルカリ金属アルコキシド特に、ナトリウムメトキシド、ナトリウムエトキシドなどを使用する場合には対応するアルコール溶液として使用される。
その他、反応溶媒として反応に不活性な有機溶媒を適宜用いてもよい。
【００２６】
尚、前記一般式（１）において、ｎ＝１であるトリアジン化合物を製造する場合には、例えば、２−メチル−４−Ｒ１−６−Ｒ２−ｓ−トリアジン化合物と、置換基Ｒ３に対応するアルデヒド化合物とを、例えば濃硫酸、酢酸などの存在下に脱水反応させることにより製造することができる。
【００２７】
かかる一般式（１）で示されるトリアジン化合物は有機発光素子、特に有機電界素子として有用である。
次に、本発明のトリアジン化合物を用いた有機電界素子について説明するが、本発明の有機電界素子の構造それ自体は特に限定されず、本発明のトリアジン化合物を電子注入材料として使用する限りにおいて、従来より公知の各種の有機電界素子に適用される。
【００２８】
図１は、本発明の有機電界素子の一実施形態を示す概念図である。
この例で示す有機電界素子は、透明基板（１）上に、透明な陽極（２ａ）、有機化合物からなる正孔輸送層（３）、有機化合物からなる発光層（４）、有機化合物からなる電子輸送層（５）および透明な陰極（２ｂ）が順次積層された構造からなっている。
【００２９】
ここで、透明基板としては通常ガラス、透明プラスチックなどが使用される。
また、この例においては、陽極（２ａ）としては厚さ１１０ｎｍ程度に積層された導電性材料であるＩＴＯが、正孔輸送層（３）として５０ｎｍ程度の厚さに成膜したα―ＮＰＤを含む有機化合物層が、発光層（４）として５０ｎｍ程度の厚さに成膜したＡｌｑ３を含む有機化合物層が、電子輸送層（５）として１０ｎｍ程度の厚さに成膜した本発明の一般式（１）で示されるトリアジン化合物を含む有機化合物層がそれぞれ形成され、陰極（２ｂ）として１０ｎｍ程度の厚さに成膜したＩＴＯが積層されている。
【００３０】
尚、正孔輸送層および発光層として使用される化合物は前記例示化合物に限られず、従来から当該分野において使用されている各種の化合物が適宜使用され、また、各層にはそれぞれの目的に照らして当該化合物以外の他の有機化合物が含まれていてもよい。
同様に、上記各層の厚みについても、上記に限定されず、適宜最適の厚みとなるように設定される。
【００３１】
【発明の効果】
本願発明に特定する前記一般式（１）で示されるトリアジン化合物を、陽極および陰極の両電極が導電性材料である透明ＩＴＯ電極からなり、電子輸送層を構成する電子注入材料（電子注入化合物）として用いた有機電界素子は、発光効率としてはＡｌｑ３を発光層とする場合よりも高くなり、しかも、電子輸送層における電子注入材料として使用してもＢＣＰのように結晶化を生じることもなく、素子寿命に対する影響も少ないなどの優れた効果を奏する。
【００３２】
【実施例】
以下、本発明を実施例によりさらに詳細に説明するが、本発明がこれらに限定されるものでないことはいうまでもない。
【００３３】
尚、以下の実施例において、発光能の測定にはアジレント・テクノロジー・インク社製のＡｇｉｌｅｎｔ ４１５５Ｃ ｓｅｍｉｃｏｎｄｕｃｔｏｒ ｐａｒａｍｅｔｅｒ ａｎａｌｙｚｅｒおよびニューポート社製のＭｕｌｔｉ−ｆｕｎｃｔｉｏｎ ｏｐｔｉｃａｌ ｍｅｔｅｒを使用した。
【００３４】
実施例１
２，４，６−トリ（５−メチル−３−ピリジル）−ｓ−トリアジン（Ｔ５Ｍ３ＰｙＴＺ）（化合物１）の合成
温度計を備えたガラス製フラスコに、３−シアノ−５−メチルピリジン２３．７ｇ（０．２ｍｏｌ）と水素化ナトリウム０．４８ｇ（０．０２ｍｏｌ）を仕込み、窒素気流下に撹拌しながら１３０℃に昇温した。６時間撹拌した後、８０℃に冷却し、撹拌下にメタノール１０ｇを加えた。この懸濁液を４０℃に冷却し、撹拌下に水１０ｇを加えて未反応の水素化ナトリウムを分解した。この懸濁液を濾過して得た固体に、水１００ｇとメタノール４０ｇを加え、室温で１時間撹拌した。この懸濁液を濾過し、得られた固体をエバポレーターを用いて乾燥し、Ｔ５Ｍ３ＰｙＴＺの淡黄色固体を２．８７ｇ（収率１２．０％）得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：２．５１（ｓ，９Ｈ）、８．６７（ｓ，３Ｈ）、８．６７（ｓ，３Ｈ），８．６８（ｓ，３Ｈ）、９．６７（ｓ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１８．５、１３０．６、１３３．２、１３６．４、１４７．９、１５４．０、１７０．６
ＬＣＭＳ（ＥＳＩ）ｍ／ｚ：３５４［Ｍ＋］
λｍａｘ（ＣＨＣｌ３）：２５６ｎｍ、２８９ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：２７６℃
【００３５】
実施例２
２，４，６−トリ（６−メチル−３−ピリジル）−ｓ−トリアジン（Ｔ６Ｍ３ＰｙＴＺ）（化合物２）の合成
１ｌガラス製反応器に、２−メチル−５−シアノピリジン１１８．１４ｇ、メタノール２９５．４ｇを仕込み、２８％ナトリウムメトキシドメタノール溶液２８９．４６ｇを４〜１２℃の間にて１．２５時間かけ滴下したのち、７７時間加熱還流させた。反応液の濃縮物に、水１０５０ｇを加え、室温で１時間撹拌した。濾過後、濾残にトルエン６４ｇを加え、室温で１時間撹拌した。濾過後、濾残をトルエンで洗浄し減圧乾燥することにより、Ｔ６Ｍ３ＰｙＴＺ５．２４ｇ（収率４．４％）を得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：２．７１（ｓ，９Ｈ）、７．３８（ｄ，Ｊ＝７．９Ｈｚ，３Ｈ）、８．８３（ｄ，Ｊ＝７．８Ｈｚ，３Ｈ）、９．７８（ｓ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：２４．８、１２３．２、１２８．５、１３６．５、１５０．１、１６３．０、１７０．５
ＤＩＭＳ（ＥＩ）ｍ／ｚ：３５４［Ｍ＋］
λｍａｘ（ＣＨＣｌ３）：２８７ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：２８１−２８３℃
【００３６】
実施例３
２，４，６−トリ（２−ピリジル）−ｓ−トリアジン（Ｔ２ＰｙＴＺ）（化合物３）の合成
温度計を備えたガラス製フラスコに、２−シアノピリジン２６．０ｇ（０．２５ｍｏｌ）と塩化アンモニウム１．３４ｇ（０．０２５ｍｏｌ）とエチレングリコール２６ｇを仕込み、１５５℃から１６５℃で１２時間撹拌した。
この懸濁液を室温に冷却した後、濾過して得た固体に、１０７ｇの１０％硫酸水溶液と活性炭１８ｇを加えて室温で１時間撹拌した。これを濾過して活性炭を除いた後、アルカリで中和して析出した結晶を濾過してエバポレーターを用いて乾燥し、目的とするＴ２ＰｙＴＺの淡黄色固体を１７．１３ｇ（収率６５．４％）得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：７．５７（ｍ，３Ｈ）、７．９９（ｍ，３Ｈ）、８．８８（ｄ，Ｊ＝７．９Ｈｚ，３Ｈ）、８．９７（ｄ，Ｊ＝４．４Ｈｚ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１２５．２、１２６．７、１３７．３、１５０．４、１５２．９、１７２．０
ＤＩＭＳ（ＥＩ）ｍ／ｚ：３１２［Ｍ＋］
λｍａｘ（ＣＨＣｌ３）：２４９、２８２ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：２４６℃
【００３７】
実施例４
２，４，６−トリ（２−メトキシ−４−ピリジル）−ｓ−トリアジン（ＴＭＰｙＴＺ）（化合物４）の合成
５０ｍｌガラス製反応器に、２−メトキシ−４−シアノピリジン４．０２ｇ、メタノール１０．１ｇを仕込み、２８％ナトリウムメトキシドメタノール溶液８．８７ｇを室温にて１．５時間かけ滴下したのち、１７時間加熱還流させた。濾過後、濾残をメタノールで洗浄した。得られた固体に、水１３．０ｇ、メタノール３．４ｇを加え、室温で１時間撹拌した。濾過後、濾残を水で洗浄し乾燥することで、固体１．０２ｇを得た。この固体に、メタノール１２．０ｇを加え、室温で１時間撹拌した。濾過後、濾残を減圧乾燥することにより、目的とするＴＭＰｙＴＺ０．４１ｇ（収率１０．２％）を得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：４．０６（ｓ，９Ｈ）、７．９９（ｓ，３Ｈ）、８．０７（ｍ，３Ｈ）、８．４１（ｄ，Ｊ＝５．３Ｈｚ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：５３．９、１１０．５、１１５．２、１４５．３、１４８．０、１６５．２、１７１．０
ＤＩＭＳ（ＥＩ）ｍ／ｚ：４０２［Ｍ＋］
元素分析 計算値：Ｃ，６２．７；Ｈ，４．５１；Ｎ，２０．９
測定値：Ｃ，６２．９；Ｈ，４．２９；Ｎ，２１．１
λｍａｘ（ＣＨＣｌ３）：２４９ｎｍ、３２６ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：２５９℃
【００３８】
実施例５
２，４，６−トリ（２−エトキシ−４−ピリジル）−ｓ−トリアジン（ＴＥＰｙＴＺ）（化合物５）の合成
２００ｍｌガラス製反応器に、２−クロロ−４−シアノピリジン１０．３９ｇ、エタノール４１．０ｇを仕込み、２０％ナトリウムエトキシドエタノール溶液４３．４６ｇを室温にて１時間かけ滴下した。６時間加熱還流したのち、２０％ナトリウムエトキシドエタノール溶液１５．４３ｇを追加し、４時間加熱還流した。反応液を濾過し、濾残をエタノールで洗浄した。得られた固体に、水５０ｇを加え室温で３０分撹拌したのち、濾過を行い、濾残を水で洗浄した。この操作を２度行った。得られた固体をクロロホルム１３０ｇに溶かし、水２０ｇを加え撹拌した。分液後下層を濃縮することにより、ＴＥＰｙＴＺ１．１６ｇ（収率１０．４％）を得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１．４８（ｔ，Ｊ＝７．１Ｈｚ，９Ｈ）、４．４７（ｑ，Ｊ＝７．１Ｈｚ，６Ｈ）、７．９９（ｓ，３Ｈ）、８．０６（ｍ，３Ｈ）、８．３９（ｄ，Ｊ＝５．３Ｈｚ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１４．７、６２．２、１１０．７、１１５．１、１４５．３、１４８．０、１６５．０、１７１．０ＤＩＭＳ（ＥＩ）ｍ／ｚ：４４４［Ｍ＋］
λｍａｘ（ＣＨＣｌ３）：３２７ｎｍ、２４９ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：１８２−１８４℃
【００３９】
実施例６
２，４，６−トリ（２−ｔｅｒｔ−ブトキシ−４−ピリジル）−ｓ−トリアジン（ＴＢＰｙＴＺ）（化合物６）の合成
３００ｍｌガラス製反応器に、カリウムｔｅｒｔ−ブトキシド２８．０５ｇ、テトラヒドロフラン１１０．９ｇを仕込み、撹拌しながら２−クロロ−４−シアノピリジン１３．８５ｇを室温にて加え、１８時間加熱還流した。反応液の濃縮物に、水２６３ｇを加え、室温で２時間撹拌し、濾過後、濾残を水で洗浄した。得られた固体にメタノール１７８ｇを加え、室温で２時間撹拌し、濾過後、濾残をメタノールで洗浄した。得られた固体を減圧乾燥することにより、ＴＢＰｙＴＺ０．７９ｇ（収率４．５％）を得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１．６７（ｓ，２７Ｈ）、７．９２（ｓ，３Ｈ）、８．０３（ｍ，３Ｈ）、８．３７（ｄ，Ｊ＝５．３Ｈｚ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：２８．７、８０．３、１１２．７、１１４．６、１４５．１、１４７．５、１６５．０、１７１．２ＤＩＭＳ（ＥＩ）ｍ／ｚ：５２８［Ｍ＋］
λｍａｘ（ＣＨＣｌ３）：３２９ｎｍ、２５０ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：１９１℃
【００４０】
実施例７
２，４，６−トリ（２−キノリル）−ｓ−トリアジン（ＴＱＴＺ）（化合物７）の合成
３０ｍｌガラス製反応器に、２−キノリンカルボニトリル２．００ｇ、メタノール５．０ｇおよび２８％ナトリウムメトキシドメタノール溶液３．７６ｇを仕込み、窒素雰囲気下１９時間加熱還流させた。反応液の濃縮物に、ノルマルヘキサン５２ｇを加え、室温で４０分間撹拌した。濾過後、濾液にメタノールを加え撹拌したのち分液した。更に、下層にノルマルヘキサン１５ｇを加え、抽出、分液を行った。ノルマルヘキサン層を集め濃縮し、固体０．７５ｇを得た。得られた固体に、メタノール１０ｇ、無水酢酸０．５ｇを加え、室温で２日間撹拌した。反応液の濃縮物に水を加えたのち、４８％水酸化ナトリウム水溶液を滴下しｐＨ８．８とした。濾過後、濾残を水で洗浄し、得られた固体をメタノール１０ｇに溶解させた。しばらくして析出した結晶を濾過した。濾液から再度析出した結晶とを合わせ乾燥することにより、目的とするＴＱＴＺを０．１５ｇ（収率７．５％）得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：７．７０（ｍ，３Ｈ）、７．８６（ｍ，３Ｈ）、７．９７（ｄ，Ｊ＝８．０Ｈｚ，３Ｈ）、８．５０（ｄ，Ｊ＝８．６Ｈｚ，３Ｈ）、８．５３（ｄ，Ｊ＝８．５Ｈｚ，３Ｈ）、９．０６（ｄ，Ｊ＝８．５Ｈｚ，３Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１２１．５、１２７．６、１２８．５、１２９．５、１３０．２、１３１．２、１３７．４、１４８．４、１５２．９、１７２．５
ＤＩＭＳ（ＥＩ）ｍ／ｚ：４６２［Ｍ＋］
元素分析 計算値：Ｃ，７７．９；Ｈ，３．９２；Ｎ，１８．２
測定値：Ｃ，７７．１；Ｈ，３．８；Ｎ，１７．９
λｍａｘ（ＣＨＣｌ３）：２６５ｎｍ、３１９ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：２７８−２８１℃
【００４１】
実施例８
２，２’−（ｐ−フェニレンジビニレン）ビス（４，６−ジフェニル−ｓ−トリアジン）（ＰＶＢＤＰＴＺ）（化合物８）の合成
温度計を備えたガラス製フラスコに、２−メチル−４，６−ジフェニル−ｓ−トリアジン６．０ｇ（２４．２５ｍｍｏｌ）、テレフタルアルデヒド１．６３ｇ（１２．１５ｍｍｏｌ）および濃硫酸６０ｇを仕込み、６０℃で４．５日間撹拌した。その後反応液を水４８０ｇ中に加え、懸濁液を濾過して得た固体に、１８０ｇのメタノールを加え、室温で１時間撹拌した。この懸濁液を濾過して得た固体に、１８０ｇのクロロホルムを加え、室温で１時間撹拌した。この懸濁液を濾過し、得られた固体をエバポレーターを用いて乾燥した後、３５５℃、２０〜４８ＭＰａで昇華精製し、目的とするＰＶＢＤＰＴＺの黄色固体を５．７６ｇ（収率８０．０％）得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＦ３ＣＯＯＤ，ＣＤＣｌ３，ｐｐｍ）δ：７．５８（ｄ，Ｊ＝１５．４，２Ｈ）、７．７５（ｄｄ，Ｊ＝７．７，４Ｈ）、７．９０（ｄｄ，Ｊ＝７．５，８Ｈ）、７．９８（ｓ，４Ｈ）、８．６８（ｄ，Ｊ＝７．３，８Ｈ）、８．９３（ｄ，Ｊ＝１５．４，２Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＦ３ＣＯＯＤ，ＣＤＣｌ３，ｐｐｍ）δ：１１１．０、１１３．８、１１６．６、１１８．６、１１９．５、１３０．８、１３１．５、１３１．７、１３８．２、１５２．０、１６５．３、１７０．６
ＤＩＭＳ（ＥＩ）ｍ／ｚ：５９２［Ｍ＋］
元素分析 計算値：Ｃ，８１．１；Ｈ，４．７３；Ｎ，１４．２
測定値：Ｃ，８０．８；Ｈ，４．７４；Ｎ，１４．２
λｍａｘ（ＣＨＣｌ３）：２７０ｎｍ、３６８ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：３００℃以上
【００４２】
実施例９
２，２’−（１，２−エチレン）ビス（４，６−ジフェニル−ｓ−トリアジン）（ＥＢＤＰＴＺ）（化合物９）の合成
温度計を備えたガラス製フラスコに、４，６−ジフェニル−ｓ−トリアジン ２−アルデヒド３．１４ｇ（１２．０ｍｍｏｌ）、２−メチル−４，６−ジフェニル−ｓ−トリアジン３．５６ｇ（１４．４ｍｍｏｌ）および酢酸１４．４ｇを仕込み、環流下４時間撹拌した。これに水２０ｇを加え、この懸濁液を濾過して得た固体に、５０ｇのメタノールを加え、室温で１時間撹拌した。この懸濁液を濾過して得た固体に３０ｇのクロロホルムを加え、室温で１時間撹拌した。この懸濁液を濾過して得た固体に再び３０ｇのクロロホルムを加え、室温で１時間撹拌した。この懸濁液を濾過し、得られた固体をエバポレーターを用いて乾燥し、目的とするＥＢＤＰＴＺの白色固体を３．３６ｇ（収率５７．０％）得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＦ３ＣＯＯＤ，ＣＤＣｌ３，ｐｐｍ）δ：７．８０（ｄｄ，Ｊ＝７．９，８Ｈ）、７．９７（ｄｄ，Ｊ＝７．５，４Ｈ）、８．７４（ｄ，Ｊ＝７．５，８Ｈ）、８．９４（ｓ，２Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＦ３ＣＯＯＤ，ＣＤＣｌ３，ｐｐｍ）δ：１２３．０、１３０．７、１３１．５、１３６．３、１３８．７、１６３．３、１７１．３
ＤＩＭＳ（ＥＩ）ｍ／ｚ：４９０［Ｍ＋］
元素分析 計算値：Ｃ，７８．４；Ｈ，４．４９；Ｎ，１７．１
測定値：Ｃ，７８．３；Ｈ，４．７５；Ｎ，１７．１
λｍａｘ（ＣＨＣｌ３）：２７７ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：３００℃以上
【００４３】
実施例１０
２−［２−（４−キノリル）ビニル］−４，６−ジフェニル−ｓ−トリアジン（４ＱＤＰＴＺ）（化合物１０）の合成
温度計を備えたガラス製フラスコに、４，６−ジフェニル−ｓ−トリアジン ２−アルデヒド５．２３ｇ（２０．０ｍｍｏｌ）、４−メチルキノリン３．４４ｇ（２４．０ｍｍｏｌ）および酢酸２４．０ｇを仕込み、１３５℃で２０時間撹拌した。これにメタノール４０ｇを加え、この懸濁液を濾過して得た固体に、６０ｇのメタノールを加え、室温で１時間撹拌した。この懸濁液を濾過し、得られた固体をエバポレーターを用いて乾燥し、目的とする４ＱＤＰＴＺの淡黄色固体を１．１８ｇ（収率１５．０％）得た。
１Ｈ−ＮＭＲ（４００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：７．４２（ｄ，Ｊ＝１５．７Ｈｚ，１Ｈ）、７．５−７．６（ｍ，６Ｈ）、７．６５（ｄｄ，Ｊ＝８．１Ｈｚ，１Ｈ）、７．６７（ｄ，Ｊ＝４．５Ｈｚ，１Ｈ）、７．７７（ｄｄ，Ｊ＝８．１Ｈｚ，１Ｈ）、８．１７（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ）、８．３１（ｄ，Ｊ＝８．１Ｈｚ，１Ｈ）、８．７０（ｄ，Ｊ＝６．８Ｈｚ，４Ｈ）、８．９５（ｄ，Ｊ＝４．５Ｈｚ，１Ｈ）、９．０５（ｄ，Ｊ＝１５．７Ｈｚ，１Ｈ）
１３Ｃ−ＮＭＲ（１００ＭＨｚ，ＣＤＣｌ３，ｐｐｍ）δ：１１８．１、１２３．５、１２６．２、１２７．１、１２８．６、１２８．９、１２９．６、１３０．２、１３２．６、１３２．８、１３５．５、１３５．８、１４０．９、１４８．８、１５０．２、１７１．０、１７１．６
ＬＣＭＳ（ＥＳＩ）ｍ／ｚ：３８６［Ｍ＋］
λｍａｘ（ＣＨＣｌ３）：２７３ｎｍ、３２６ｎｍ
Ｍｅｌｔｉｎｇ Ｐｏｉｎｔ：１７６℃
【００４４】
実施例１１
ＩＴＯ薄膜がコートされているガラス基板（三容真空工業株式会社製）の上に、真空蒸着法によりα−ＮＰＤを厚さ５０ｎｍになるように積層した。さらに、その上に発光層材料として厚さ５０ｎｍのＡｌｑ３層を形成し、その上に電子輸送層として実施例１で得たＴ５Ｍ３ＰｙＴＺ（化合物１）を１０ｎｍ蒸着し、最後に陰極としてＩＴＯ層を１００ｎｍ蒸着して素子を完成させた。
このデバイスに電圧を印加したところ良好な発光特性が得られ、最大外部量子効率０．４％が観測された。
また、この素子を２週間室内に放置しても、Ｔ５Ｍ３ＰｙＴＺ層の結晶化による濁りは見られず、素子の透明性に変化は見られなかった。
【００４５】
実施例１２
実施例１１において、Ｔ５Ｍ３ＰｙＴＺ（化合物１）の代わりに、Ｔ６Ｍ３ＰｙＴＺ（化合物２）を用いる以外は、実施例１１と同様にして素子を得た。
このデバイスに電圧を印加したところ良好な発光特性が得られ、最大外部量子効率０．３６％が観測された。
また、この素子を２週間室内に放置しても、Ｔ６Ｍ３ＰｙＴＺ層の結晶化による濁りは見られず、素子の透明性に変化は見られなかった。
【００４６】
実施例１３
実施例１１において、Ｔ５Ｍ３ＰｙＴＺ（化合物１）の代わりに、ＴＭＰｙＴＺ（化合物４）を用いる以外は、実施例１１と同様にして素子を得た。
このデバイスに電圧を印加したところ良好な発光特性が得られ、最大外部量子効率０．３４％が観測された。
また、この素子を２週間室内に放置しても、ＴＭＰｙＴＺ層の結晶化による濁りは見られず、素子の透明性に変化は見られなかった。
【００４７】
実施例１４
実施例１１において、Ｔ５Ｍ３ＰｙＴＺ（化合物１）の代わりに、ＴＥＰｙＴＺ（化合物５）を用いる以外は、実施例１１と同様にして素子を得た。
このデバイスに電圧を印加したところ良好な発光特性が得られ、最大外部量子効率０．２５％が観測された。
また、この素子を２週間室内に放置しても、ＴＥＰｙＴＺ層の結晶化による濁りは見られず、素子の透明性に変化は見られなかった。
【００４８】
実施例１５
実施例１１において、Ｔ５Ｍ３ＰｙＴＺ（化合物１）の代わりに、ＴＢＰｙＴＺ（化合物６）を用いる以外は、実施例１１と同様にして素子を得た。
このデバイスに電圧を印加したところ良好な発光特性が得られ、最大外部量子効率０．３６％が観測された。
また、この素子を２週間室内に放置しても、ＴＢＰｙＴＺ層の結晶化による濁りは見られず、素子の透明性に変化は見られなかった。
【００４９】
実施例１６
実施例１１において、Ｔ５Ｍ３ＰｙＴＺ（化合物１）の代わりに、ＰＶＢＤＰＴＺ（化合物８）を用いる以外は、実施例１１と同様にして素子を得た。
このデバイスに電圧を印加したところ良好な発光特性が得られ、最大外部量子効率０．０６％が観測された。
また、この素子を２週間室内に放置しても、ＰＶＢＤＰＴＺ層の結晶化による濁りは見られず、素子の透明性に変化は見られなかった。
【００５０】
比較例１
Ｔ５Ｍ３ＰｙＴＺ層を電子輸送層として使用しない以外は実施例１１と同様にして素子を得た。
この素子を２週間室内に放置しても、素子の透明性に変化は見られなかったが、このデバイスに電圧を印加したところ、最大外部量子効率は０．０３％であった。
【００５１】
比較例２
実施例１１において、Ｔ５Ｍ３ＰｙＴＺ（化合物１）の代わりに、ＢＣＰを用いる以外は、実施例１１と同様にして素子を得た。
このデバイスに電圧を印加したところ、最大外部量子効率は０．３０％であったが、この素子を室内に放置したところ、２日後にはＢＣＰの結晶化による濁りが見られ、素子の透明性および発光能が損なわれていた。
【図面の簡単な説明】
【図１】本発明の有機電界素子の一実施態様を示す概念図である。
【符号の説明】
１：透明基板
２ａ：陽極
３：正孔輸送層
４：発光層
５：電子輸送層
２ｂ：陰極[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel triazine compound, a method for producing the same, and an organic light emitting device using the compound as an electron injection compound.
[0002]
[Prior art]
2. Description of the Related Art In recent years, with the diversification of information devices, there has been an increasing need for a flat display element that consumes less power and has a smaller space occupation area than a Cathode Ray Tube (so-called CRT). Attention has been focused on organic EL elements having high conversion efficiency, and various materials and organic light-emitting elements have been proposed.
[0003]
2. Description of the Related Art An organic light-emitting element, particularly an organic electric field element (organic EL element) is generally provided with an anode on a transparent substrate such as glass or plastic, on which various types of holes, light emission, and electron transport (electron injection) are provided. The structure is such that an organic thin film layer is laminated and a cathode is further provided thereon.
When a voltage is applied between both electrodes of such an organic electric field element, a current flows through each layer of hole transport, light emission, and electron transport, and a light-emitting phenomenon occurs due to recombination of holes and electrons in the light-emitting layer. Light that has passed through the transparent electrode and the transparent substrate in the thickness direction is radiated to the outside, and 100 to 10,000 candela / m by applying a voltage of about 10 V. 2 Because it can emit light with extremely high brightness, it is attracting attention as a promising candidate for next-generation display elements.
[0004]
In such an organic electroluminescent device, in most of the conventional organic EL devices, only a part of the generated light is irradiated from the transparent anode side, but the ratio is theoretically relative to the refractive index n in the device. Typically 1 / (2n 2 For example, when the refractive index n is 1.5, the ratio of the external irradiation is only about 22%, and the remaining 78% is absorbed by the metal surface in the organic laminate or through the glass substrate. Or it is emitted from the edge of the substrate and has extremely poor luminous efficiency.
[0005]
In order to improve the luminous efficiency, an example in which a transparent electrode made of Indium-Tin-Oxide (hereinafter abbreviated as “ITO”) is used for both the anode and the cathode has been reported. -(Α-naphthylphenylamino) biphenyl (NPD) is converted to a hole transport layer, a tris (8-quinolinolato) aluminum complex (so-called Alq 3 ) Is used as an electron-transporting light-emitting layer, and a transparent organic electric field device in which an ITO electrode is formed as a cathode thereon has been reported.
[0006]
However, the luminous efficiency has not yet been sufficiently improved in such a device, and in order to further improve the luminous efficiency, Alq. 3 Is a light emitting layer, and the Alq 3 It is represented by the following formula between the light emitting layer and the ITO electrode.
[0007]
[Patent Document 1]
JP-A-2002-332567
[0008]
However, both the anode and the cathode are transparent ITO electrodes having high light transmittance, and Alq 3 Is used as an electron-transporting light-emitting layer to efficiently extract light generated in the device to the outside of the device. Further, when BCP is provided as an electron-transporting layer, the luminous efficiency can be further improved. However, there is a problem that the crystal is easily crystallized, so that the transparency of the element is lost, and the current becomes difficult to flow due to the crystallization. As a result, there is a problem that the life of the element is shortened.
[0009]
[Problems to be solved by the invention]
From such a fact, the present inventors, in a transparent anode and a cathode capable of extracting light emission without impairing the transmittance, particularly in an organic EL element using both electrodes as ITO electrodes having high light transmittance, Alq above 3 Are simultaneously solved when the film is used as an electron transporting light emitting layer and when BCP is used as an electron transporting layer. 3 Is higher than in the case where the light-emitting layer is used as a light-emitting layer, and even when used as an electron-injecting material in the electron-transporting layer, crystallization does not occur unlike BCP, and there is little influence on the device life, and the electron-transporting layer is good. In addition to developing a compound having film forming properties, the present inventors have conducted studies to develop an organic electric field device using the compound as an electron injecting compound in the electron transport layer, and have reached the present invention.
[0010]
[Means for Solving the Problems]
A first aspect of the present invention is the following general formula (1)
Embedded image
A second aspect of the present invention provides a triazine compound represented by the formula (1), and a third aspect of the present invention provides an organic light-emitting device containing the triazine compound as an active ingredient.
[0011]
BEST MODE FOR CARRYING OUT THE INVENTION
In the triazine compound of the present invention represented by the general formula (1), the ring A is a phenyl ring, a pyridine ring, or a cyclopentadiene ring, and the alkyl group is methyl, ethyl, n- or iso-propyl, n-, sec. And methoxy, ethoxy, n- or iso-propoxy, n-, sec- or t-butoxy, and the like.
In addition, adjacently bonded R 4 And R 5 Are bonded to form a 5- or 6-membered ring that shares two carbon atoms constituting ring A, a quinoline ring as a whole of ring A is included. .
Specific examples of the triazine compound of the present invention include the following compounds.
[0012]
(Compound 1)
(Compound 2)
(Compound 3)
(Compound 4)
(Compound 5)
(Compound 6)
(Compound 7)
(Compound 8)
(Compound 9)
(Compound 10)
The triazine compound represented by the above general formula (1) of the present invention is, for example, a compound represented by the general formula (4)
[0023]
Here, examples of the base include alkali metal hydrides such as sodium hydride and potassium hydride, and alkali metal alkoxides such as sodium methoxide, sodium ethoxide, sodium butoxide, potassium methoxide, potassium ethoxide, and potassium-t-butoxide. And ammonium halides such as ammonium chloride are preferably used.
[0024]
Although the amount of the base used varies depending on the reaction conditions, it is generally in the range of 0.01 to 2 moles per mol of the starting cyano compound, and the reaction temperature is, for example, the kind of the starting compound or the solvent when the solvent is used. The optimum temperature is set according to each condition.
[0025]
When an alkali metal alkoxide, particularly sodium methoxide, sodium ethoxide or the like is used, it is used as a corresponding alcohol solution.
In addition, an organic solvent inert to the reaction may be appropriately used as a reaction solvent.
[0026]
In the case of producing a triazine compound in which n = 1 in the general formula (1), for example, 2-methyl-4-R 1 -6-R 2 -S-triazine compound and a substituent R 3 Can be produced by a dehydration reaction with an aldehyde compound corresponding to, for example, concentrated sulfuric acid, acetic acid or the like.
[0027]
The triazine compound represented by the general formula (1) is useful as an organic light emitting device, particularly, an organic electric field device.
Next, an organic electric field device using the triazine compound of the present invention will be described, but the structure itself of the organic electric field device of the present invention is not particularly limited, as long as the triazine compound of the present invention is used as an electron injection material. The present invention is applied to various conventionally known organic electric field elements.
[0028]
FIG. 1 is a conceptual diagram showing one embodiment of the organic electric field device of the present invention.
The organic electric field element shown in this example comprises a transparent substrate (1), a transparent anode (2a), a hole transport layer (3) made of an organic compound, a light emitting layer (4) made of an organic compound, and an organic compound. It has a structure in which an electron transport layer (5) and a transparent cathode (2b) are sequentially laminated.
[0029]
Here, glass, transparent plastic or the like is usually used as the transparent substrate.
In this example, as the anode (2a), ITO, which is a conductive material laminated to a thickness of about 110 nm, was used. As the hole transport layer (3), α-NPD formed to a thickness of about 50 nm was used. An organic compound layer containing Alq formed as a light emitting layer (4) to a thickness of about 50 nm. 3 The organic compound layer containing the triazine compound represented by the general formula (1) of the present invention is formed as the electron transport layer (5) to a thickness of about 10 nm, and the cathode (2b) An ITO film having a thickness of about 10 nm is laminated.
[0030]
The compounds used as the hole transport layer and the light-emitting layer are not limited to the above-described compounds, and various compounds conventionally used in the art are appropriately used. An organic compound other than the compound may be included.
Similarly, the thickness of each of the above layers is not limited to the above, and is appropriately set to an optimum thickness.
[0031]
【The invention's effect】
An electron injecting material (electron injecting compound) comprising the triazine compound represented by the general formula (1) specified in the invention of the present application, comprising a transparent ITO electrode in which both an anode and a cathode are made of a conductive material and constituting an electron transporting layer. The organic electric field element used as the luminous efficiency is Alq 3 Is higher than in the case where is used as a light emitting layer, and even when used as an electron injecting material in an electron transporting layer, crystallization does not occur unlike BCP, and excellent effects such as little influence on device life are exhibited. .
[0032]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples, but it goes without saying that the present invention is not limited to these.
[0033]
In the following Examples, the measurement of the luminous ability was performed using an Agilent 4155C semiconductor parameter analyzer and a Multi-function optical meter manufactured by Newport.
[0034]
Example 1
Synthesis of 2,4,6-tri (5-methyl-3-pyridyl) -s-triazine (T5M3PyTZ) (Compound 1)
A glass flask equipped with a thermometer was charged with 23.7 g (0.2 mol) of 3-cyano-5-methylpyridine and 0.48 g (0.02 mol) of sodium hydride, and stirred at 130 ° C. under a nitrogen stream. The temperature rose. After stirring for 6 hours, the mixture was cooled to 80 ° C., and 10 g of methanol was added with stirring. The suspension was cooled to 40 ° C., and 10 g of water was added with stirring to decompose unreacted sodium hydride. 100 g of water and 40 g of methanol were added to the solid obtained by filtering this suspension, and the mixture was stirred at room temperature for 1 hour. This suspension was filtered, and the obtained solid was dried using an evaporator to obtain 2.87 g (yield 12.0%) of a pale yellow solid of T5M3PyTZ.
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 2.51 (s, 9H), 8.67 (s, 3H), 8.67 (s, 3H), 8.68 (s, 3H), 9.67 (s, 3H).
Thirteen C-NMR (100 MHz, CDCl 3 , 18.5, 130.6, 133.2, 136.4, 147.9, 154.0, 170.6
LCMS (ESI) m / z: 354 [M +]
λ max (CHCl 3 ): 256 nm, 289 nm
Melting Point: 276 ° C
[0035]
Example 2
Synthesis of 2,4,6-tri (6-methyl-3-pyridyl) -s-triazine (T6M3PyTZ) (Compound 2)
A 1-liter glass reactor was charged with 118.14 g of 2-methyl-5-cyanopyridine and 295.4 g of methanol, and 289.46 g of a 28% methanol solution of sodium methoxide was placed at 4 to 12 ° C. for 1.25 hours. After the dropwise addition, the mixture was heated under reflux for 77 hours. 1050 g of water was added to the concentrate of the reaction solution, and the mixture was stirred at room temperature for 1 hour. After filtration, 64 g of toluene was added to the residue, and the mixture was stirred at room temperature for 1 hour. After filtration, the residue was washed with toluene and dried under reduced pressure to obtain 5.24 g of T6M3PyTZ (4.4% yield).
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 2.71 (s, 9H), 7.38 (d, J = 7.9 Hz, 3H), 8.83 (d, J = 7.8 Hz, 3H), 9.78 (s, 9H) 3H)
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) δ: 24.8, 123.2, 128.5, 136.5, 150.1, 163.0, 170.5
DIMS (EI) m / z: 354 [M +]
λ max (CHCl 3 ): 287 nm
Melting Point: 281-283 ° C
[0036]
Example 3
Synthesis of 2,4,6-tri (2-pyridyl) -s-triazine (T2PyTZ) (Compound 3)
A glass flask equipped with a thermometer was charged with 26.0 g (0.25 mol) of 2-cyanopyridine, 1.34 g (0.025 mol) of ammonium chloride, and 26 g of ethylene glycol, and stirred at 155 ° C to 165 ° C for 12 hours. .
After the suspension was cooled to room temperature, 107 g of a 10% aqueous sulfuric acid solution and 18 g of activated carbon were added to the solid obtained by filtration, and the mixture was stirred at room temperature for 1 hour. This was filtered to remove activated carbon, then neutralized with an alkali, and the precipitated crystals were filtered and dried using an evaporator. )Obtained.
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 7.57 (m, 3H), 7.99 (m, 3H), 8.88 (d, J = 7.9 Hz, 3H), 8.97 (d, J = 4.4 Hz, 3H)
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) δ: 125.2, 126.7, 137.3, 150.4, 152.9, 172.0
DIMS (EI) m / z: 312 [M +]
λ max (CHCl 3 ): 249, 282 nm
Melting Point: 246 ° C
[0037]
Example 4
Synthesis of 2,4,6-tri (2-methoxy-4-pyridyl) -s-triazine (TMPyTZ) (Compound 4)
A 50 ml glass reactor was charged with 4.02 g of 2-methoxy-4-cyanopyridine and 10.1 g of methanol, and 8.87 g of a 28% sodium methoxide methanol solution was added dropwise at room temperature over 1.5 hours. Heated to reflux for hours. After filtration, the residue was washed with methanol. 13.0 g of water and 3.4 g of methanol were added to the obtained solid, followed by stirring at room temperature for 1 hour. After filtration, the residue was washed with water and dried to obtain 1.02 g of a solid. 12.0 g of methanol was added to this solid, and the mixture was stirred at room temperature for 1 hour. After filtration, the residue was dried under reduced pressure to obtain 0.41 g (yield 10.2%) of target TMPyTZ.
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 4.06 (s, 9H), 7.99 (s, 3H), 8.07 (m, 3H), 8.41 (d, J = 5.3 Hz, 3H).
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) 53.9, 110.5, 115.2, 145.3, 148.0, 165.2, 171.0
DIMS (EI) m / z: 402 [M +]
Elemental analysis Calculated: C, 62.7; H, 4.51; N, 20.9
Found: C, 62.9; H, 4.29; N, 21.1.
λ max (CHCl 3 ): 249 nm, 326 nm
Melting Point: 259 ° C
[0038]
Example 5
Synthesis of 2,4,6-tri (2-ethoxy-4-pyridyl) -s-triazine (TEPyTZ) (compound 5)
In a 200 ml glass reactor, 10.39 g of 2-chloro-4-cyanopyridine and 41.0 g of ethanol were charged, and 43.46 g of a 20% sodium ethoxide ethanol solution was added dropwise at room temperature over 1 hour. After heating under reflux for 6 hours, 15.43 g of a 20% sodium ethoxide ethanol solution was added, and the mixture was heated under reflux for 4 hours. The reaction solution was filtered, and the residue was washed with ethanol. After adding 50 g of water to the obtained solid and stirring at room temperature for 30 minutes, the mixture was filtered, and the residue was washed with water. This operation was performed twice. The obtained solid was dissolved in 130 g of chloroform, 20 g of water was added, and the mixture was stirred. After liquid separation, the lower layer was concentrated to obtain 1.16 g of TEPyTZ (yield 10.4%).
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 1.48 (t, J = 7.1 Hz, 9H), 4.47 (q, J = 7.1 Hz, 6H), 7.99 (s, 3H), 8.06 (m, 3H), 8.39 (d, J = 5.3 Hz, 3H)
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) δ: 14.7, 62.2, 110.7, 115.1, 145.3, 148.0, 165.0, 171.0 DIMS (EI) m / z: 444 [M +]
λ max (CHCl 3 ): 327 nm, 249 nm
Melting Point: 182-184 ° C
[0039]
Example 6
Synthesis of 2,4,6-tri (2-tert-butoxy-4-pyridyl) -s-triazine (TBPyTZ) (Compound 6)
28.05 g of potassium tert-butoxide and 110.9 g of tetrahydrofuran were charged into a 300 ml glass reactor, and 13.85 g of 2-chloro-4-cyanopyridine was added at room temperature with stirring, followed by heating under reflux for 18 hours. 263 g of water was added to the concentrate of the reaction solution, and the mixture was stirred at room temperature for 2 hours. After filtration, the residue was washed with water. 178 g of methanol was added to the obtained solid, and the mixture was stirred at room temperature for 2 hours. After filtration, the residue was washed with methanol. The obtained solid was dried under reduced pressure to obtain 0.79 g (4.5% yield) of TBPyTZ.
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 1.67 (s, 27H), 7.92 (s, 3H), 8.03 (m, 3H), 8.37 (d, J = 5.3 Hz, 3H)
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) δ: 28.7, 80.3, 112.7, 114.6, 145.1, 147.5, 165.0, 171.2 DIMS (EI) m / z: 528 [M +]
λ max (CHCl 3 ): 329 nm, 250 nm
Melting Point: 191 ° C
[0040]
Example 7
Synthesis of 2,4,6-tri (2-quinolyl) -s-triazine (TQTZ) (Compound 7)
Into a 30 ml glass reactor were charged 2.00 g of 2-quinolinecarbonitrile, 5.0 g of methanol and 3.76 g of a 28% sodium methoxide methanol solution, and the mixture was refluxed under a nitrogen atmosphere for 19 hours. 52 g of normal hexane was added to the concentrate of the reaction solution, followed by stirring at room temperature for 40 minutes. After filtration, methanol was added to the filtrate, and the mixture was stirred and then separated. Further, 15 g of normal hexane was added to the lower layer, and extraction and liquid separation were performed. The normal hexane layer was collected and concentrated to obtain 0.75 g of a solid. 10 g of methanol and 0.5 g of acetic anhydride were added to the obtained solid, and the mixture was stirred at room temperature for 2 days. After water was added to the concentrate of the reaction solution, a 48% aqueous sodium hydroxide solution was added dropwise to adjust the pH to 8.8. After filtration, the residue was washed with water, and the obtained solid was dissolved in 10 g of methanol. After a while the crystals precipitated were filtered. By combining and drying the crystals precipitated again from the filtrate, 0.15 g (7.5% yield) of the desired TQTZ was obtained.
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 7.70 (m, 3H), 7.86 (m, 3H), 7.97 (d, J = 8.0 Hz, 3H), 8.50 (d, J = 8.6 Hz, 3H), 8.53 (d, J = 8.5 Hz, 3H), 9.06 (d, J = 8.5 Hz, 3H)
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) δ: 121.5, 127.6, 128.5, 129.5, 130.2, 131.2, 137.4, 148.4, 152.9, 172.5
DIMS (EI) m / z: 462 [M +]
Elemental analysis Calculated: C, 77.9; H, 3.92; N, 18.2.
Found: C, 77.1; H, 3.8; N, 17.9.
λ max (CHCl 3 ): 265 nm, 319 nm
Melting Point: 278-281 ° C
[0041]
Example 8
Synthesis of 2,2 ′-(p-phenylenedivinylene) bis (4,6-diphenyl-s-triazine) (PVBDPTZ) (Compound 8)
A glass flask equipped with a thermometer was charged with 6.0 g (24.25 mmol) of 2-methyl-4,6-diphenyl-s-triazine, 1.63 g (12.15 mmol) of terephthalaldehyde and 60 g of concentrated sulfuric acid. Stirred at C for 4.5 days. Thereafter, the reaction solution was added to 480 g of water, and 180 g of methanol was added to a solid obtained by filtering the suspension, followed by stirring at room temperature for 1 hour. 180 g of chloroform was added to the solid obtained by filtering this suspension, and the mixture was stirred at room temperature for 1 hour. This suspension was filtered, the obtained solid was dried using an evaporator, and then purified by sublimation at 355 ° C. and 20 to 48 MPa to obtain 5.76 g (yield: 80.0%) of a yellow solid of the target PVBDPTZ. )Obtained.
1 H-NMR (400 MHz, CF 3 COOD, CDCl 3 , Ppm) δ: 7.58 (d, J = 15.4, 2H), 7.75 (dd, J = 7.7, 4H), 7.90 (dd, J = 7.5, 8H), 7.98 (s, 4H), 8.68 (d, J = 7.3, 8H), 8.93 (d, J = 15.4, 2H)
Thirteen C-NMR (100 MHz, CF 3 COOD, CDCl 3 , Ppm) δ: 111.0, 113.8, 116.6, 118.6, 119.5, 130.8, 131.5, 131.7, 138.2, 152.0, 165.3, 170 .6
DIMS (EI) m / z: 592 [M +]
Elemental analysis Calculated: C, 81.1; H, 4.73; N, 14.2.
Found: C, 80.8; H, 4.74; N, 14.2.
λ max (CHCl 3 ): 270 nm, 368 nm
Melting Point: 300 ° C or higher
[0042]
Example 9
Synthesis of 2,2 ′-(1,2-ethylene) bis (4,6-diphenyl-s-triazine) (EBDPTZ) (Compound 9)
In a glass flask equipped with a thermometer, 3.14 g (12.0 mmol) of 4,6-diphenyl-s-triazine 2-aldehyde and 3.56 g (14.14 g) of 2-methyl-4,6-diphenyl-s-triazine were added. 4 mmol) and 14.4 g of acetic acid, and stirred under reflux for 4 hours. 20 g of water was added thereto, and 50 g of methanol was added to a solid obtained by filtering the suspension, followed by stirring at room temperature for 1 hour. 30 g of chloroform was added to the solid obtained by filtering this suspension, and the mixture was stirred at room temperature for 1 hour. 30 g of chloroform was added again to the solid obtained by filtering this suspension, and the mixture was stirred at room temperature for 1 hour. The suspension was filtered, and the obtained solid was dried using an evaporator to obtain 3.36 g (yield: 57.0%) of a target EBDPTZ white solid.
1 H-NMR (400 MHz, CF 3 COOD, CDCl 3 , Ppm) δ: 7.80 (dd, J = 7.9, 8H), 7.97 (dd, J = 7.5, 4H), 8.74 (d, J = 7.5, 8H), 8.94 (s, 2H)
Thirteen C-NMR (100 MHz, CF 3 COOD, CDCl 3 , Ppm) δ: 123.0, 130.7, 131.5, 136.3, 138.7, 163.3, 171.3.
DIMS (EI) m / z: 490 [M +]
Elemental analysis Calculated: C, 78.4; H, 4.49; N, 17.1
Found: C, 78.3; H, 4.75; N, 17.1
λ max (CHCl 3 ): 277 nm
Melting Point: 300 ° C or higher
[0043]
Example 10
Synthesis of 2- [2- (4-quinolyl) vinyl] -4,6-diphenyl-s-triazine (4QDPTZ) (Compound 10)
A glass flask equipped with a thermometer was charged with 5.23 g (20.0 mmol) of 4,6-diphenyl-s-triazine 2-aldehyde, 3.44 g (24.0 mmol) of 4-methylquinoline, and 24.0 g of acetic acid. And stirred at 135 ° C. for 20 hours. 40 g of methanol was added thereto, and 60 g of methanol was added to a solid obtained by filtering this suspension, followed by stirring at room temperature for 1 hour. This suspension was filtered, and the obtained solid was dried using an evaporator to obtain 1.18 g (yield: 15.0%) of a target pale yellow solid of 4QDPTZ.
1 H-NMR (400 MHz, CDCl 3 , Ppm) δ: 7.42 (d, J = 15.7 Hz, 1H), 7.5-7.6 (m, 6H), 7.65 (dd, J = 8.1 Hz, 1H), 7. 67 (d, J = 4.5 Hz, 1H), 7.77 (dd, J = 8.1 Hz, 1H), 8.17 (d, J = 8.1 Hz, 1H), 8.31 (d, J = 8.1 Hz, 1H), 8.70 (d, J = 6.8 Hz, 4H), 8.95 (d, J = 4.5 Hz, 1H), 9.05 (d, J = 15.7 Hz, 1H)
Thirteen C-NMR (100 MHz, CDCl 3 , Ppm) δ: 118.1, 123.5, 126.2, 127.1, 128.6, 128.9, 129.6, 130.2, 132.6, 132.8, 135.5, 135 .8, 140.9, 148.8, 150.2, 171.0, 171.6
LCMS (ESI) m / z: 386 [M +]
λ max (CHCl 3 ): 273 nm, 326 nm
Melting Point: 176 ° C
[0044]
Example 11
On a glass substrate (manufactured by Sanyo Vacuum Industry Co., Ltd.) coated with an ITO thin film, α-NPD was laminated to a thickness of 50 nm by a vacuum evaporation method. Further, a 50 nm-thick Alq 3 A layer was formed, and the T5M3PyTZ (Compound 1) obtained in Example 1 was deposited thereon as an electron transporting layer to a thickness of 10 nm, and finally an ITO layer was deposited as a cathode to a thickness of 100 nm to complete the device.
When a voltage was applied to this device, good light-emitting characteristics were obtained, and a maximum external quantum efficiency of 0.4% was observed.
Even when the device was left in a room for 2 weeks, no turbidity due to crystallization of the T5M3PyTZ layer was observed, and no change was observed in the transparency of the device.
[0045]
Example 12
An element was obtained in the same manner as in Example 11, except that T6M3PyTZ (Compound 2) was used instead of T5M3PyTZ (Compound 1).
When a voltage was applied to this device, good light-emitting characteristics were obtained, and a maximum external quantum efficiency of 0.36% was observed.
Even when this device was left in a room for 2 weeks, no turbidity due to crystallization of the T6M3PyTZ layer was observed, and no change was observed in the transparency of the device.
[0046]
Example 13
An element was obtained in the same manner as in Example 11, except that TMPyTZ (Compound 4) was used instead of T5M3PyTZ (Compound 1).
When a voltage was applied to this device, good light-emitting characteristics were obtained, and a maximum external quantum efficiency of 0.34% was observed.
Even when the device was left in a room for 2 weeks, no turbidity due to crystallization of the TMPyTZ layer was observed, and no change was observed in the transparency of the device.
[0047]
Example 14
An element was obtained in the same manner as in Example 11, except that TEPyTZ (Compound 5) was used instead of T5M3PyTZ (Compound 1).
When a voltage was applied to this device, good light-emitting characteristics were obtained, and a maximum external quantum efficiency of 0.25% was observed.
Even when this device was left in a room for 2 weeks, no turbidity due to crystallization of the TEPyTZ layer was observed, and no change was observed in the transparency of the device.
[0048]
Example 15
An element was obtained in the same manner as in Example 11, except that TBPyTZ (Compound 6) was used instead of T5M3PyTZ (Compound 1).
When a voltage was applied to this device, good light-emitting characteristics were obtained, and a maximum external quantum efficiency of 0.36% was observed.
Further, even when this device was left in a room for 2 weeks, no turbidity due to crystallization of the TBPyTZ layer was observed, and no change was observed in the transparency of the device.
[0049]
Example 16
A device was obtained in the same manner as in Example 11 except that PVBDPTZ (Compound 8) was used instead of T5M3PyTZ (Compound 1).
When a voltage was applied to this device, good light-emitting characteristics were obtained, and a maximum external quantum efficiency of 0.06% was observed.
Even when the device was left in a room for 2 weeks, no turbidity due to crystallization of the PVBDPTZ layer was observed, and no change was observed in the transparency of the device.
[0050]
Comparative Example 1
An element was obtained in the same manner as in Example 11, except that the T5M3PyTZ layer was not used as an electron transport layer.
When the device was left in a room for 2 weeks, no change was observed in the transparency of the device. However, when a voltage was applied to the device, the maximum external quantum efficiency was 0.03%.
[0051]
Comparative Example 2
An element was obtained in the same manner as in Example 11 except that BCP was used instead of T5M3PyTZ (Compound 1).
When a voltage was applied to this device, the maximum external quantum efficiency was 0.30%. However, when this device was left indoors, turbidity due to crystallization of BCP was observed two days later, and the transparency of the device was observed. And the luminous ability was impaired.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing one embodiment of the organic electric field device of the present invention.
[Explanation of symbols]
1: Transparent substrate
2a: anode
3: Hole transport layer
4: Light emitting layer
5: electron transport layer
2b: cathode
Claims (11)
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| KR100796988B1 (en) | 2006-09-13 | 2008-01-22 | 연세대학교 산학협력단 | Fluorescent polymer comprising triazine group and preparation method thereof |
| WO2008023628A1 (en) * | 2006-08-21 | 2008-02-28 | Hodogaya Chemical Co., Ltd. | Compound having triazine ring structure substituted with pyridyl group and organic electroluminescent device |
| WO2009107651A1 (en) | 2008-02-26 | 2009-09-03 | 保土谷化学工業株式会社 | Substituted bipyridyl compound and organic electroluminescent element |
| WO2011105373A1 (en) | 2010-02-25 | 2011-09-01 | 保土谷化学工業株式会社 | Substituted pyridyl compound and organic electroluminescent element |
| EP3766875A1 (en) * | 2019-07-15 | 2021-01-20 | Novaled GmbH | Compound and an organic semiconducting layer, an organic electronic device, a display device and a lighting device comprising the same |
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| JPWO2008023628A1 (en) * | 2006-08-21 | 2010-01-07 | 保土谷化学工業株式会社 | Compound having triazine ring structure substituted with pyridyl group and organic electroluminescence device |
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