JP4237839B2 - 1,2,4-Triazole group-containing vinyl derivative, polymer thereof and organic EL device using the same - Google Patents
1,2,4-Triazole group-containing vinyl derivative, polymer thereof and organic EL device using the same Download PDFInfo
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- JP4237839B2 JP4237839B2 JP32217697A JP32217697A JP4237839B2 JP 4237839 B2 JP4237839 B2 JP 4237839B2 JP 32217697 A JP32217697 A JP 32217697A JP 32217697 A JP32217697 A JP 32217697A JP 4237839 B2 JP4237839 B2 JP 4237839B2
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- 229920000642 polymer Polymers 0.000 title claims description 61
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 title claims description 14
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 7
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 description 50
- 238000006243 chemical reaction Methods 0.000 description 44
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 30
- 239000013078 crystal Substances 0.000 description 27
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 24
- 238000003786 synthesis reaction Methods 0.000 description 24
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 239000010410 layer Substances 0.000 description 16
- 239000012046 mixed solvent Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- -1 diphenylamino group Chemical group 0.000 description 15
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 12
- 238000002189 fluorescence spectrum Methods 0.000 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 238000006116 polymerization reaction Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 8
- 239000000178 monomer Substances 0.000 description 8
- 239000012299 nitrogen atmosphere Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000005406 washing Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- HRXZRAXKKNUKRF-UHFFFAOYSA-N 4-ethylaniline Chemical compound CCC1=CC=C(N)C=C1 HRXZRAXKKNUKRF-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- VBVAVBCYMYWNOU-UHFFFAOYSA-N coumarin 6 Chemical compound C1=CC=C2SC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 VBVAVBCYMYWNOU-UHFFFAOYSA-N 0.000 description 5
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- 229920002554 vinyl polymer Polymers 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000012044 organic layer Substances 0.000 description 4
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- QIYUZQOXXHXTLO-UHFFFAOYSA-N C(#N)C1=CC=C(C=C1)C1=NN=C(N1C1=CC=C(C=C1)C=C)C1=CC=C(C=C1)C#N Chemical compound C(#N)C1=CC=C(C=C1)C1=NN=C(N1C1=CC=C(C=C1)C=C)C1=CC=C(C=C1)C#N QIYUZQOXXHXTLO-UHFFFAOYSA-N 0.000 description 3
- VDFBMBNYQJZKFN-UHFFFAOYSA-N C=CC1=CC=C(C=C1)C2=NN=C(N2C3=CC=CC=C3)C4=CC=C(C=C4)C#N Chemical compound C=CC1=CC=C(C=C1)C2=NN=C(N2C3=CC=CC=C3)C4=CC=C(C=C4)C#N VDFBMBNYQJZKFN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 2
- QKXWHAPEUSZKFM-UHFFFAOYSA-N 1-n,1-n'-bis(3-methylphenyl)-4-phenylcyclohexa-2,4-diene-1,1-diamine Chemical compound CC1=CC=CC(NC2(C=CC(=CC2)C=2C=CC=CC=2)NC=2C=C(C)C=CC=2)=C1 QKXWHAPEUSZKFM-UHFFFAOYSA-N 0.000 description 2
- LNETULKMXZVUST-UHFFFAOYSA-N 1-naphthoic acid Chemical compound C1=CC=C2C(C(=O)O)=CC=CC2=C1 LNETULKMXZVUST-UHFFFAOYSA-N 0.000 description 2
- 125000004801 4-cyanophenyl group Chemical group [H]C1=C([H])C(C#N)=C([H])C([H])=C1* 0.000 description 2
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical class C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- OFFQNKIPGAJMOU-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)C1=NN=C(N1C1=CC=C(C=C1)C=C)C1=CC=CC2=CC=CC=C12 Chemical compound C1(=CC=CC2=CC=CC=C12)C1=NN=C(N1C1=CC=C(C=C1)C=C)C1=CC=CC2=CC=CC=C12 OFFQNKIPGAJMOU-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000004663 dialkyl amino group Chemical group 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N hydrazine Substances NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 2
- 235000019341 magnesium sulphate Nutrition 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- MHAKZZONPKXZMU-UHFFFAOYSA-N n'-(4-phenylbenzoyl)naphthalene-1-carbohydrazide Chemical compound C=1C=CC2=CC=CC=C2C=1C(=O)NNC(=O)C(C=C1)=CC=C1C1=CC=CC=C1 MHAKZZONPKXZMU-UHFFFAOYSA-N 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000001226 reprecipitation Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000003852 triazoles Chemical group 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- WPFVBOQKRVRMJB-VIFPVBQESA-N (3s)-7-hydroxy-3,7-dimethyloctanal Chemical compound O=CC[C@@H](C)CCCC(C)(C)O WPFVBOQKRVRMJB-VIFPVBQESA-N 0.000 description 1
- FKASFBLJDCHBNZ-UHFFFAOYSA-N 1,3,4-oxadiazole Chemical compound C1=NN=CO1 FKASFBLJDCHBNZ-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- 125000006083 1-bromoethyl group Chemical group 0.000 description 1
- 125000001637 1-naphthyl group Chemical group [H]C1=C([H])C([H])=C2C(*)=C([H])C([H])=C([H])C2=C1[H] 0.000 description 1
- SNTWKPAKVQFCCF-UHFFFAOYSA-N 2,3-dihydro-1h-triazole Chemical compound N1NC=CN1 SNTWKPAKVQFCCF-UHFFFAOYSA-N 0.000 description 1
- IUBBZPXRBPEIKQ-UHFFFAOYSA-N 4-cyano-N'-(4-cyanobenzoyl)benzohydrazide Chemical compound C(#N)C1=CC=C(C(=O)NNC(C2=CC=C(C=C2)C#N)=O)C=C1 IUBBZPXRBPEIKQ-UHFFFAOYSA-N 0.000 description 1
- 125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 description 1
- JPVUWCPKMYXOKW-UHFFFAOYSA-N 4-phenylbenzoyl chloride Chemical compound C1=CC(C(=O)Cl)=CC=C1C1=CC=CC=C1 JPVUWCPKMYXOKW-UHFFFAOYSA-N 0.000 description 1
- 101100481033 Arabidopsis thaliana TGA7 gene Proteins 0.000 description 1
- IBSHUFNQPMWCSZ-UHFFFAOYSA-N C1(=CC=CC2=CC=CC=C12)C1=NN=C(N1C1=CC=C(C=C1)CC)C1=CC=CC2=CC=CC=C12 Chemical compound C1(=CC=CC2=CC=CC=C12)C1=NN=C(N1C1=CC=C(C=C1)CC)C1=CC=CC2=CC=CC=C12 IBSHUFNQPMWCSZ-UHFFFAOYSA-N 0.000 description 1
- 0 CC(*)C=NN=C(C)C Chemical compound CC(*)C=NN=C(C)C 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 238000012662 bulk polymerization Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000012690 ionic polymerization Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- CALCWQPEUTXALN-UHFFFAOYSA-N n'-(4-cyanobenzoyl)-4-ethylbenzohydrazide Chemical compound C1=CC(CC)=CC=C1C(=O)NNC(=O)C1=CC=C(C#N)C=C1 CALCWQPEUTXALN-UHFFFAOYSA-N 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- VMFUMDXVTKTZQY-UHFFFAOYSA-N naphthalene-1-carbohydrazide Chemical compound C1=CC=C2C(C(=O)NN)=CC=CC2=C1 VMFUMDXVTKTZQY-UHFFFAOYSA-N 0.000 description 1
- NSNPSJGHTQIXDO-UHFFFAOYSA-N naphthalene-1-carbonyl chloride Chemical compound C1=CC=C2C(C(=O)Cl)=CC=CC2=C1 NSNPSJGHTQIXDO-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000011368 organic material Substances 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
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010557 suspension polymerization reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
Images
Description
【０００１】
【発明の属する技術分野】
本発明は、新規な１，２，４−トリアゾール基含有ビニル誘導体、その高分子、およびそれを用いた有機ＥＬ素子に関する。
【０００２】
【従来技術】
有機ＥＬ素子の発光は、陽極や陰極のそれぞれから注入されたホールと電子が有機層内を移動し、再結合した際に得られる励起エネルギーを発光エネルギーに変換することによって得られる。しかし、低分子有機材料を用いたＥＬ素子においては、電流注入にともない発生する熱や時間経過等による有機層の結晶化、凝集が素子劣化を引き起こすため、素子の耐久性つまり素子寿命に多大なる影響を与えている。
【０００３】
この影響を抑えるため、低分子有機層の利用から結晶性が低く、耐熱性の高い高分子有機層の利用の方向への転換が提案されており、今までにキャリア輸送性基を高分子中に取り込んだ有機ＥＬ素子が報告されている。本出願人は、先にホール輸送性基である芳香族ジアミンを含有するポリマーを提案しており、耐熱性が高いうえ、ホール輸送層として機能する優れたポリマーであることを報告している（特願平８−３１００４９号、特願平７−９４２９４号、特願平６−２１０５４４号）、また、電子輸送性ポリマーに関しても、１，３，４−オキサジアゾールを含有する主鎖型および側鎖型ポリマーを開発している。（特願平８−９４８１８号など）
【０００４】
１，２，４−トリアゾール誘導体に関しても、本出願人は種々の低分子１，２，４−トリアゾール誘導体を合成し、それらの蒸着膜が有機ＥＬ素子において、キャリア輸送層や発光層として極めて優れた特性を有することを示した。
【０００５】
【発明が解決しようとする課題】
しかし、低分子膜を素子に用いるには真空蒸着法により、成膜する必要があり、素子作製に時間がかかる。さらに、蒸着膜の結晶化により高温における素子耐久性に乏しい欠点を有している。
【０００６】
そこで、本発明の目的は、１，２，４−トリアゾール基を側鎖に含有するビニル誘導体、その重合物である耐熱性に優れた新規な１，２，４−トリアゾール基含有高分子およびそれを用いた有機ＥＬ素子を提供する点にある。
【０００７】
【課題を解決するための手段】
本発明の第一は、下記一般式〔１〕
【化４】
で示される１，２，４−トリアゾール基含有ビニル誘導体に関する。
【０００８】
本発明の第二は、下記一般式〔２〕
【化５】
で示される繰り返し単位を有する数平均分子量１，０００〜１，０００，０００の１，２，４−トリアゾール基含有高分子に関する。
【０００９】
本発明の第三は、下記一般式〔３〕
【化６】
で示される繰り返し単位を有する数平均分子量１，０００〜１，０００，０００の１，２，４−トリアゾール基含有高分子に関する。
【００１０】
本発明の第四は、請求項２および／または請求項３記載の１，２，４−トリアゾール基含有高分子をキャリア輸送層および／または発光層に使用することを特徴とする有機エレクトロルミネッセント素子に関する。
【００１１】
前記置換基としては、アルキル基、アルコキシ基、アミノ基、ジアルキルアミノ基、ジフェニルアミノ基、シアノ基、ハロゲンなどを挙げることができ、前記アルキル基、アルコキシ基、ジアルキルアミノ基などにおける炭素数は前記ビニル単量体の重合にさいして立体障害にならない大きさであれば、格別の制限はない。
【００１２】
本発明のモノマー合成法の一例を示す。
【化７】
前記式中、ＮＢＳは、Ｎ−ブロモこはく酸イミド、ＡＩＢＮは、アゾイソブチロニトリル、ＣＣｌ4は、四塩化炭素、ｔ−ＢｕＯＫは、カリウムの第三ブチルアルコラート、ＴＨＦは、テトラヒドロフランである。
【００１４】
本発明のビニル化合物は、通常のビニル化合物と同様に重合または共重合することができる。重合方法としてはバルク重合、溶液重合、乳化重合、懸濁重合のいずれの方法も採用することができる。実施例はラジカル重合の系を示しているが、本発明のモノマーはイオン重合とくにアニオン重合によっても高分子化が可能である
【００１５】
本発明のポリマーを重合条件を調製することによりワックス状のものから固体状のものに至るまで任意の分子量のものをうることができるが、通常１，０００〜１，０００，０００の分子量のものがポリマーの種々の用途に用いるために有用である。
【００１６】
本発明の新規ポリマーは電子輸送性を有するので、単なるポリマーの用途に加えて、この特性を生かした種々の用途に用いることができ、とくにＥＬ素子への利用が考えられる。すなわち、本発明の１，２，４−トリアゾール基含有高分子は、キャリア輸送性で知られる１，２，４−トリアゾール基を側鎖に含有することで、電子や正孔などのキャリアを輸送する特性を示すため、有機ＥＬ素子のキャリア輸送層或いは発光層として用いることができる。また、溶液からの塗布により簡便に成膜することができるので、素子製造の際にコストを低減することが可能となる。
【００１７】
【実施例】
以下に、実施例を挙げて本発明を具体的に説明するが、本発明はこれにより何ら限定されるものではない。
【００１８】
実施例１（モノマーの合成例１）
実施例１の合成プロセスを反応式で示すと下記のとおりである。
【００１９】
【化８】
（１）１−ナフトエ酸メチルエステル〔前記反応式中（Ａ）の化合物〕の合成
１−ナフトエ酸６．０３ｇ（３５ｍｍｏｌ）をメタノール（１５０ｍｌ）に溶解し、濃硫酸（７ｍｌ）を触媒として加え、９０℃で６時間還流した。反応終了後エステルをジエチルエーテルで抽出した。エタノールと濃硫酸を水洗により取り除き、ジエチルエーテルを乾燥後留去し、褐色の液状エステル（Ａ）を得た。
Ｃ12Ｈ10Ｏ2（１８６．２１）
収量 ５．６３ｇ
収率 ８６．５％
ＩＲ（ＫＢｒ）ν−ＣＯＣＨ3１７１７ｃｍ-1
【００２１】
（２）１−ナフトヒドラジド〔前記反応式中（Ｂ）の化合物〕の合成
ヒドラジン−水和物１５ｇ（３００ｍｍｏｌ）をエタノール（１００ｍｌ）に溶解させ窒素置換後、この溶液中に前記化合物（Ａ）５．５９ｇ（３０ｍｍｏｌ）を滴下させ、滴下終了後８５℃で４８時間還流させた。反応終了後溶媒を除去し、析出した結晶を冷メタノールにて吸引濾過し生成物（Ｂ）を得た。
Ｃ11Ｈ10Ｎ2Ｏ（１８６．２２）
収量 ３．３５ｇ
収率 ６６．９％
ＩＲ（ＫＢｒ）ν−ＮＨ2３４００ｃｍ-1，ν−ＣＯＮＨ−１７１７ｃｍ-1
【００２２】
（３）Ｎ−（１−ナフトイル）−Ｎ′−（４−フェニルベンゾイル）ヒドラジン〔前記反応式中（Ｃ）の化合物〕の合成
前記化合物（Ｂ）２．７０ｇ（１３．０ｍｍｏｌ）をピリジン（５０ｍｌ）に溶解させ窒素置換後、この溶液中に４−フェニルベンゾイルクロリド２．４２ｇ（１３．０ｍｍｏｌ）を滴下させ、滴下終了後室温で１９時間還流させた。反応終了後、溶液を蒸留水中へ注ぎ入れ白沈した反応生成物を水洗した。水洗後反応物を吸引濾過し、化合物（Ｃ）を得た。
Ｃ24Ｈ18Ｎ2Ｏ2（３６６．４２）
収量 ３．７８ｇ
収率 ７９．４％
ＩＲ（ＫＢｒ）ν−ＣＯＮＨ−３１９５ｃｍ-1
【００２３】
（４）３−（１−ナフチル）−４−（４−エチルフェニル）−５−（４−フェニルベンゾイル）−１，２，４−トリアゾール〔前記反応式中（Ｄ）の化合物〕の合成
ｏ−ジクロロベンゼン（９０ｍｌ）中にｐ−エチルアニリン７．３４ｇ（６０．６ｍｍｏｌ）を溶解させてから三塩化リン１．５３ｇ（１１．１ｍｍｏｌ）を加え、約一時間反応させ、反応後Ｎ−（１−ナフトイル）−Ｎ′−（４−フェニルベンゾイル）ヒドラジン〔前記化合物（Ｃ）〕３．７０ｇ（１０．１ｍｍｏｌ）を加え、窒素雰囲気下２００℃で４８時間還流させた。反応終了後溶液を０．５Ｎの塩酸水溶液、蒸留水の順で洗浄し、洗浄後ｏ−ジクロロベンゼンを減圧蒸留（８０℃／３ｍｍＨｇ）で除去し、粗結晶を得た。得られた粗結晶は混合比１：４の酢酸エチル、クロロホルムの混合溶媒にてカラム精製し、化合物（Ｄ）を得た。
（５）３−（１−ナフチル）−４−〔４−（１−ブロモエチルフェニル）〕−５−（４−フェニルベンゾイル）−１，２，４−トリアゾール〔前記反応式中（Ｅ）の化合物〕の合成
四塩化炭素（５０ｍｌ）にＮ−ブロモこはく酸イミド０．２８ｇ（１．５６ｍｍｏｌ）とアゾイソブチロニトリル（ＡＩＢＮ）０．０２６ｇ（０．１６ｍｍｏｌ）を溶解し、３−（１−ナフチル）−４−（４−エチルフェニル）−５−（４−フェニルベンゾイル）−１，２，４−トリアゾール〔前記化合物（Ｄ）〕０．７０ｇ（１．５６ｍｍｏｌ）を加え、窒素雰囲気下９５℃で２４時間還流させた。反応終了後２時間放置して未反応物を析出させてから濾過し、濾液の溶媒を除去して粗結晶を得た。得られた粗結晶を酢酸エチル、クロロホルムの混合溶媒でカラム精製し、さらに粗結晶を混合比１：２のベンゼン、ｎ−ヘキサンの混合溶媒で再結晶を行い前記化合物（Ｅ）を得た。
（６）３−（１−ナフチル）−４−（４−ビニルフェニル）−５−（４−フェニルベンゾイル）−１，２，４−トリアゾール〔前記反応式中（Ｆ）の化合物〕の合成
乾燥テトラヒドロフラン（ＴＨＦ）４０ｍｌにカリウム−ｔ−ブトキシド０．３７ｇ（３．２８ｍｍｏｌ）を溶解し０℃で撹拌し、この溶液中に乾燥ＴＨＦ１０ｍｌに溶解した３−（１−ナフチル）−４−〔４−（１−ブロモエチルフェニル）〕−５−（４−フェニルベンゾイル）−１，２，４−トリアゾール〔前記化合物（Ｅ）〕０．５８ｇ（１．０９ｍｍｏｌ）を滴下させ、滴下終了後室温で２４時間反応させた。反応終了後溶媒を除去し、残査にクロロホルムを加え、０．０１Ｎの水酸化ナトリウム、蒸留水の順で洗浄し、硫酸マグネシウムで乾燥させた後、溶媒を除去して粗結晶を得た。得られた粗結晶を混合比２：３のベンゼン、ｎ−ヘキサンの混合溶媒で再結晶を行い前記化合物（Ｆ）を得た。
実施例２（モノマーの合成例２）
実施例２の合成プロセスを反応式に示すと下記のとおりである。
【００２７】
【化９】
（１）Ｎ，Ｎ′−（１−ジナフトイル）−ヒドラジン〔前記反応式中（Ｃ′）の化合物〕の合成
実施例１の（２）で得られた１−ナフトヒドラジン〔前記（Ｂ）の化合物〕
３．３０ｇ（１７．７ｍｍｏｌ）をピリジン（６０ｍｌ）に溶解させ窒素置換後、この溶液中に１−ナフタレンカルボン酸クロリド３．３８ｇ（１７．７ｍｍｏｌ）を滴下させ、滴下終了後室温で１９時間還流させた。反応終了後、溶液を蒸留水中へ注ぎ入れ白沈した反応生成物を水洗した。水洗後反応物を吸引濾過し、生成物（Ｃ′）を得た。
Ｃ22Ｈ16Ｎ2Ｏ2（３４０．３９）
収量 ５．２５ｇ
収率 ８７．１％
ＩＲ（ＫＢｒ）ν−ＣＯＮＨ−３１８７ｃｍ-1
【００２９】
（２）３，５−ジナフチル−４−（４−エチルフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｄ′）の化合物〕の合成
ｏ−ジクロロベンゼン（９０ｍｌ）中にｐ−エチルアニリン１１．３ｇ（９３．４ｍｍｏｌ）を溶解させてから三塩化リン２．３５ｇ（１７．１ｍｍｏｌ）を加え、約一時間反応させ、反応後Ｎ，Ｎ′−（１−ジナフトイル）−ヒドラジン〔前記化合物（Ｃ′）〕５．２０ｇ（１５．５ｍｍｏｌ）を加え、窒素雰囲気下２００℃で４８時間還流させた。反応終了後溶液を０．５Ｎの塩酸水溶液、蒸留水の順で洗浄し、洗浄後ｏ−ジクロロベンゼンを減圧蒸留（８０℃／３ｍｍＨｇ）で除去し、粗結晶を得た。得られた粗結晶は混合比１：４の酢酸エチル、ジクロロメタンの混合溶媒でカラム精製し、化合物（Ｄ′）を得た。
（３）３，５−ジナフチル−４−〔４−（１−ブロモエチルフェニル）〕−１，２，４−トリアゾール〔前記反応式中（Ｅ′）の化合物〕の合成
四塩化炭素（１８０ｍｌ）にＮ−ブロモこはく酸イミド０．８４ｇ（４．７０ｍｍｏｌ）とＡＩＢＮ０．０８ｇ（０．４７ｍｍｏｌ）を溶解し、３，５−ジナフチル−４−（４−エチルフェニル）−１，２，４−トリアゾール〔前記化合物（Ｄ′）〕２．００ｇ（４．７０ｍｍｏｌ）を加え窒素雰囲気下９５℃で２４時間還流させた。反応終了後２時間放置して未反応物を析出させてから濾過し、濾液の溶媒を除去して粗結晶を得た。得られた粗結晶を酢酸エチル、クロロホルムの混合溶媒でカラム精製し、さらに粗結晶を混合比１：２のベンゼン、ｎ−ヘキサンの混合溶媒で再結晶を行い前記化合物（Ｅ′）を得た。
（４）３，５−ジナフチル−４−（４−ビニルフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｆ′）の化合物〕の合成
乾燥ＴＨＦ４０ｍｌにカリウム−ｔ−ブトキシド０．８７ｇ（７．７３ｍｍｏｌ）を溶解し０℃で撹拌し、この溶液中に乾燥ＴＨＦ１０ｍｌに溶解した３，５−ジナフチル−４−〔４−（１−ブロモエチルフェニル）〕−１，２，４−トリアゾール〔前記化合物（Ｅ′）〕１．３０ｇ（２．５８ｍｍｏｌ）を滴下させ、滴下終了後室温で２４時間反応させた。反応終了後溶媒を除去し、残査にクロロホルムを加え、０．０１Ｎの水酸化ナトリウム、蒸留水の順で洗浄し、硫酸マグネシウムで乾燥させた後、溶媒を除去して粗結晶を得た。得られた粗結晶を混合比２：３のベンゼン、ｎ−ヘキサンの混合溶媒で再結晶を行い前記化合物（Ｆ′）を得た。
実施例３（モノマーの合成例３）
下記の反応式により３，５−ジ（４−シアノフェニル）−４−（４−ビニルフェニル）−１，２，４−トリアゾールを合成した。
【００３３】
【化１０】
（１）３，５−ジ（４−シアノフェニル）−４−（４−エチルフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｈ）の化合物〕の合成
ｏ−ジクロロベンゼン中１２０ｍｌにｐ−エチルアニリン９．２４ｇを溶解させてから三塩化リン１．９２ｇを加え、約一時間反応させた。反応後Ｎ，Ｎ′−ジ（４−シアノベンゾイル）−ヒドラジン〔前記反応式中（Ｇ）の化合物〕３．７ｇを加え、窒素雰囲気下、２４時間還流させた。反応終了後溶液を０．５Ｎの塩酸水溶液、蒸留水の順で洗浄し、洗浄後ｏ−ジクロロベンゼンを減圧蒸留にて除去し、真空乾燥させて粗結晶を得た。これを酢酸エチル：クロロホルム＝１：４の混合溶媒でカラム精製し、アセトン：ｎ−ヘキサン＝１：８で再結晶し、化合物（Ｈ）針状結晶１．４６ｇを得た。
収率３１．２％，ｍ．ｐ．：２３７〜２３９℃，ＩＲ（ＫＢｒ）：１６０８ｃｍ-1（−Ｃ＝Ｎ−），２９６６ｃｍ-1（−ＣＨ3），1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3）：δ（ｐｐｍ）１．３（ｔ，３Ｈ，−ＣＨ3），２．８（ｑ，２Ｈ，−ＣＨ2−），７．１〜７．７（ｍ，１２Ｈ，Ａｒ），ＡＮＡＬ．Ｃａｌｃｄ ｆｏｒ Ｃ24Ｈ17Ｎ5；Ｃ，７６．７８％；Ｈ，４．５６％；Ｎ，１８．６５％．Ｆｏｕｎｄ；Ｃ，７６．８５％；Ｈ，４．６５％；Ｎ，１８．３２％．
【００３５】
（２）３，５−ジ（４−シアノフェニル）−４−〔４−（１−ブロモエチルフェニル）〕−１，２，４−トリアゾール〔前記反応式中（Ｉ）の化合物〕の合成
四塩化炭素中に３，５−ジ（４−シアノフェニル）−４−（４−エチルフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｈ）の化合物〕（１．４３ｍｍｏｌ）、ＮＢＳ（４．２９ｍｍｏｌ）、ＡＩＢＮ（０．１４３ｍｍｏｌ）を入れ、窒素雰囲気下２４時間還流させた。反応終了後四塩化炭素を除去し粗結晶を得た。これを酢酸エチル：クロロホルム １：２の混合溶媒でカラム精製し、更にアセトン：ｎ−ヘキサン １：８で再結晶し、化合物（Ｉ）の結晶を得た。
収率４６．２％，ｍ．ｐ．：１７４〜１７６℃，ＩＲ（ＫＢｒ）：１６０８ｃｍ-1（−Ｃ＝Ｎ−），２９６６ｃｍ-1（−ＣＨ3），1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3）：δ（ｐｐｍ）２．０（ｄ，３Ｈ，−ＣＨ3），５．２（ｑ，１Ｈ，−ＣＨＢｒ−），７．１〜７．６（ｍ，１２Ｈ，Ａｒ−Ｈ），ＡＮＡＬ．Ｃａｌｃｄ ｆｏｒ Ｃ24Ｈ17Ｎ5Ｂｒ1；Ｃ，６３．３１％；Ｈ，４．５７％；Ｎ，１５．３８％．Ｆｏｕｎｄ；Ｃ，６３．０２％；Ｈ，３．９８％；Ｎ，１５．５６％．
【００３６】
（３）３，５−ジ（４−シアノフェニル）−４−（４−ビニルフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｊ）の化合物〕の合成
三口フラスコ中の乾燥させたＴＨＦ７０ｍｌ中にカリウム−ｔ−ブトキシド３．３０ｍｍｏｌを溶解し氷水で三口フラスコを冷却し、窒素置換後ＴＨＦ３０ｍｌに溶解させた３，５−ジ（４−シアノフェニル）−４−〔４−（１−ブロモエチルフェニル）〕−１，２，４−トリアゾール〔前記化合物（Ｉ）〕１３．２ｍｍｏｌを滴下させた。滴下終了後２４時間室温で反応させた。反応終了後ＴＨＦを除去し、粗結晶を得、これをジクロロエタン：酢酸エチル＝４：１の混合溶媒でカラム精製した。更に、アセトン：ｎ−ヘキサン＝１：１０の混合溶媒で再結晶し、化合物（Ｊ）の針状結晶０．２０ｇを得た。
収率２５．８％，ｍ．ｐ．：２０９〜２１０℃，ＩＲ（ＫＢｒ）：１６０８ｃｍ-1（−Ｃ＝Ｎ−），９２４ｃｍ-1（＝ＣＨ2），1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3）：δ（ｐｐｍ）５．５，５．９（ｄ，２Ｈ，＝ＣＨ2），６．８（ｑ，１Ｈ，−ＣＨ＝），７．１〜７．７（ｍ，１２Ｈ，Ａｒ−Ｈ），ＡＮＡＬ．Ｃａｌｃｄ ｆｏｒ Ｃ24Ｈ15Ｎ5；Ｃ，７７．２％；Ｈ，４．０５％；Ｎ，１８．７５％．Ｆｏｕｎｄ；Ｃ，７６．８７％；Ｈ，４．２９％；Ｎ，１８．３３％．
蛍光スペクトル（励起波長２８４ｎｍ）：最大値３９４ｎｍ
【００３７】
実施例４（モノマーの合成例４）
下記の反応式により３−（４−ビニルフェニル）−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾールを合成した。
【００３８】
【化１１】
（１）３−（４−エチルフェニル）−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｈ′）の化合物〕の合成
ジクロロベンゼン中１５０ｍｌにアニリン１８．２９ｇを溶解させてから三塩化リン５．３９ｇを加え、約一時間反応させた。反応後Ｎ−（４−シアノフェニルカルボニル）−Ｎ′−（４−エチルフェニルカルボニル）−ヒドラジン〔前記式中（Ｇ′）の化合物〕９．６ｇを加え、窒素雰囲気下で還流温度まで上昇させた。ここで、前駆体が溶解していないので、滴下ロートよりゆっくりとピリジンを滴下させた。５ｍｌほど滴下させた後、前駆体全てが溶解したところで滴下を終了し、１２時間、１９０℃で反応させた。反応終了後溶液を０．５Ｎの塩酸水溶液、蒸留水の順で洗浄し、洗浄後ｏ−ジクロロベンゼンを減圧蒸留にて除去し、真空乾燥させて粗結晶を得た。これを酢酸エチル：クロロホルム＝１：４の混合溶媒でカラム精製し生成物（４．３９ｇ）を得た。また、アセトン：ｎ−ヘキサンにて再結晶を行い化合物（Ｈ′）の針状結晶を得た。
収率３８．３％，ｍ．ｐ．：１９０〜１９２℃，ＩＲ（ＫＢｒ）：１６０８ｃｍ-1（−Ｃ＝Ｎ−），２９６６ｃｍ-1（−ＣＨ3），1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3）：δ（ｐｐｍ）１．３（ｔ，３Ｈ，−ＣＨ3），２．７（ｑ，２Ｈ，−ＣＨ2−），７．２〜７．７（ｍ，１３Ｈ，Ａｒ），ＡＮＡＬ．Ｃａｌｃｄ ｆｏｒ Ｃ24Ｈ17Ｎ5；Ｃ，７６．８３％；Ｈ，５．１８％；Ｎ，１５．９９％．Ｆｏｕｎｄ；Ｃ，７９．０３％；Ｈ，５．２９％；Ｎ，１５．５６％．
【００４０】
（２）３−〔４−（１−ブロモエチルフェニル）〕−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｉ′）の化合物〕の合成
四塩化炭素中に３−（４−エチルフェニル）−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾール〔化合物（Ｈ′）〕（１．４３ｍｍｏｌ）、Ｎ−ブロモこはく酸イミド（ＮＢＳ）２．１５ｍｍｏｌ、ＡＩＢＮ（０．１４３ｍｍｏｌ）を入れ、窒素雰囲気下で２４時間還流させた。反応終了後四塩化炭素を除去し粗結晶を得た。これを酢酸エチル：クロロホルム＝１：２の混合溶媒でカラム精製し、更にアセトン：ｎ−ヘキサン＝１：８で再結晶し、化合物（Ｉ′）の結晶を得た。
収率５８．６％，ｍ．ｐ．：１２２〜１２３℃，ＩＲ（ＫＢｒ）：１６０８ｃｍ-1（−Ｃ＝Ｎ−），２９６６ｃｍ-1（−ＣＨ3），1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3）：δ（ｐｐｍ）２．１（ｄ，３Ｈ，−ＣＨ3），５．２（ｑ，１Ｈ，−ＣＨＢｒ−），７．１〜７．９（ｍ，１３Ｈ，Ａｒ−Ｈ），ＡＮＡＬ．Ｃａｌｃｄ ｆｏｒ Ｃ23Ｈ17Ｎ4Ｂｒ1；Ｃ，６４．３５％；Ｈ，３．９９％；Ｎ，１３．０５％．Ｆｏｕｎｄ；Ｃ，６５．０１％；Ｈ，４．３５％；Ｎ，１２．８８％。
【００４１】
（３）３−（４−ビニルフェニル）−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾール〔前記反応式中（Ｊ′）の化合物〕の合成
三口フラスコ中の乾燥させたＴＨＦ３０ｍｌ中にカリウム−ｔ−ブトキシド２．２４ｍｍｏｌを溶解し氷水で三口フラスコを冷却し、窒素置換後ＴＨＦ１０ｍｌに溶解させた３−〔４−（１−ブロモエチルフェニル）〕−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾール〔前記化合物（Ｉ′）〕０．７４５ｍｍｏｌを滴下させた。滴下終了後２４時間室温で反応させた。反応終了後ＴＨＦを除去し、粗結晶を得、これをジクロロエタン：酢酸エチル＝４：１の混合溶媒でカラム精製した。更に、アセトン：ｎ−ヘキサン＝１：１０の混合溶媒で再結晶し、化合物（Ｊ′）の針状結晶０．１５ｇを得た。
収率６１．１％，ｍ．ｐ．：２２１〜２２３℃，ＩＲ（ＫＢｒ）：１６０８ｃｍ-1（−Ｃ＝Ｎ−），９２４ｃｍ-1（＝ＣＨ2），1Ｈ−ＮＭＲ（２７０ＭＨｚ，ＣＤＣｌ3）：δ（ｐｐｍ）５．５，５．９（ｄ，２Ｈ，＝ＣＨ2），６．８（ｑ，１Ｈ，−ＣＨ＝），７．１〜７．７（ｍ，１３Ｈ，Ａｒ−Ｈ），ＡＮＡＬ．Ｃａｌｃｄ ｆｏｒ Ｃ23Ｈ16Ｎ4；Ｃ，７９．３％；Ｈ，４．６３％；Ｎ，１６．１％．Ｆｏｕｎｄ；Ｃ，７９．０％；Ｈ，４．５２％；Ｎ，１６．０％．
蛍光スペクトル（励起波長３０９ｎｍ）：最大値３８８ｎｍ
【００４２】
実施例５（実施例１のポリマーの合成）
重合管にジメチルホルムアミド（ＤＭＦ）０．２ｍｌに溶解させた３−（１−ナフチル）−４−（４−ビニルフェニル）−５−（４−フェニルベンゾイル）−１，２，４−トリアゾール〔前記化合物（Ｆ）〕０．０５ｇ（０．１１１ｍｍｏｌ）、ＡＩＢＮ０．００２ｇ（０．０１１ｍｏｌ）を入れ凍結脱気窒素置換後、恒温槽で６０℃において１２時間反応させた。反応終了後メタノールに再沈させてポリマーを得た。このポリマーを３回再沈精製を繰り返し精製した。このポリマーは下記の繰り返し単位を有する。また、その物性は表１〜表３および図１に示した。
実施例６（実施例２のポリマーの合成）
重合管にＤＭＦ０．２ｍｌに溶解させた３，５−ジナフチル−４−（４−ビニルフェニル）−１，２，４−トリアゾール〔前記化合物（Ｆ′）〕０．０５ｇ（０．１１８ｍｍｏｌ）、開始剤としてＡＩＢＮ０．００２ｇ（０．０１１ｍｏｌ）を入れ凍結脱気窒素置換後、恒温槽で６０℃において１２時間反応させた。反応終了後メタノールに再沈させてポリマーを得た。このポリマーを３回再沈精製を繰り返し精製した。このポリマーは下記の繰り返し単位を有する。また、その物性は表１〜表３および図２に示した。
実施例７（実施例３のポリマーの合成）
５ｍｌの重合管に３，５−ジ（４−シアノフェニル）−４−（４−ビニルフェニル）−１，２，４−トリアゾール〔化合物（Ｊ）〕０．３ｇ、開始剤としてＡＩＢＮ０．０１３ｇを入れＤＭＦ３ｍｌを溶媒とし、凍結乾燥後２４時間６０℃で重合させ、下記の繰り返し単位を有するポリマーを得た。また、その物性は表１〜表３および図３に示した。
収量 ０．１２ｇ
収率 ３９％
Ｍｎ＝２３，０００
Ｍｗ／Ｍｎ＝１．２
【化１４】
実施例８（実施例４のポリマーの合成）
５ｍｌの重合管に３−（４−ビニルフェニル）−４−フェニル−５−（４−シアノフェニル）−１，２，４−トリアゾール〔化合物（Ｊ′）〕０．１ｇ、開始剤としてＡＩＢＮ５．０×１０-4ｇを入れＤＭＦ１ｍｌを溶媒とし、凍結乾燥後２４時間６０℃で重合させ、下記の繰り返し単位を有するポリマーを得た。また、その物性は表１〜表３および図４に示した。とくに表１から明らかなように、実施例５〜７のトリアゾールの４位の位置がビニル芳香族で置換されたポリマーに較べて、本実施例のトリアゾールの３位の位置がビニル芳香族基で置換されたポリマーは有機溶剤に対する溶解性が大きい。
収量 ０．０４０ｇ，収率 ４０％，Ｍｎ＝６７，０００，Ｍｗ／Ｍｎ＝１．４
【化１５】
【表１】
【表２】
【００４８】
【表３】
【００４９】
実施例９（実施例８のポリマーを用いたＥＬ素子）
図５に示す単層型有機ＥＬ素子において、電子輸送性ポリマー層として、実施例８のポリマーを用いて有機ＥＬ素子を製造した。このＥＬ素子の電流密度−電圧特性は図６に示すとおりであった。なお図５における陽極はガラス基板上に形成されたＩＴＯ層であり、そのシート抵抗は１５Ω／□であり、陰極はＭｇ：Ａｇ積層層である。
【００５０】
実施例１０（実施例８のポリマーにＴＰＤを配合）
図５に示す単層型有機ＥＬ素子において、電子輸送性ポリマー層として、実施例８のポリマーに下記式
【化１６】
【００５１】
実施例１１（実施例８のポリマーにＴＰＤをドープ）
図５に示す単層型有機ＥＬ素子において、電子輸送性ポリマー層として、実施例８のポリマーにＴＰＤをドーピングした層を用いた。このＥＬ素子の輝度と波長の関係を図９に示した。ポリマーのみの蛍光スペクトルのピークは３８８ｎｍにあり、ＴＰＤのみの蛍光スペクトルのピークは４１０ｎｍにあるのに較べて、ポリマーにＴＰＤをドープしたものの発光スペクトルのピークは５１２ｎｍであり、ポリマーとＴＰＤの相互作用によりそれぞれ単独の場合に較べて発光スペクトルが長波長側にシフトし、緑色発光を示している。
【００５２】
実施例１２（実施例８のポリマーにＴＰＤとクマリン６を併用）
図５に示す単層型有機ＥＬ素子において、電子輸送性ポリマー層として、ポリマーにＴＰＤを１０ｗｔ％、下記式
【化１７】
で示されるクマリン６を１ｗｔ％配合した場合のＥＬ素子が示す電流密度−電圧特性および発光強度−電圧特性を図１０と図１１に示す。クマリン６の併用により発光強度が向上することが分かる。
【００５３】
【効果】
本発明により、新規モノマー、新規ポリマーおよびそれを用いた有機ＥＬ素子を提供できた。
【図面の簡単な説明】
【図１】実施例５のポリマーの蛍光スペクトル図である。
【図２】実施例６のポリマーの蛍光スペクトル図である。
【図３】実施例７のポリマーの蛍光スペクトル図である。
【図４】実施例８のポリマーの蛍光スペクトル図である。
【図５】単層型有機ＥＬ素子の積層構造を示す。
【図６】実施例８のポリマーのみを電子輸送性ポリマー層として用いた図５に示すＥＬ素子の電流密度−電圧特性を示す。
【図７】実施例８のポリマーにＴＰＤを種々の割合で配合したものを電子輸送性ポリマー層として用いた場合の図５に示すＥＬ素子（実施例１０の素子）の電流密度−電圧特性を示す。
【図８】実施例１０の各ＥＬ素子の発光強度−電圧特性を示す。
【図９】実施例８のポリマーにＴＰＤをドーピングした実施例１１のＥＬ素子の発光スペクトルをポリマー自体の蛍光スペクトル、ＴＰＤ自体の蛍光スペクトルと対比して示す。
【図１０】実施例８のポリマーにＴＰＤとクマリン６を併用した実施例１２のＥＬ素子の電流密度−電圧特性を示す。
【図１１】実施例８のポリマーにＴＰＤとクマリン６を併用した実施例１２のＥＬ素子の発光強度−電圧特性を示す。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a
[0002]
[Prior art]
Light emission of the organic EL element can be obtained by converting excitation energy obtained when holes and electrons injected from each of the anode and the cathode move in the organic layer and recombine to light emission energy. However, in an EL device using a low-molecular organic material, the crystallization and aggregation of the organic layer due to heat generated with current injection and the passage of time cause deterioration of the device, which increases the durability of the device, that is, the device life. It has an influence.
[0003]
In order to suppress this effect, the use of a low molecular weight organic layer has been proposed to shift to the use of a polymer organic layer with low crystallinity and high heat resistance. An organic EL device incorporated in is reported. The present applicant has previously proposed a polymer containing an aromatic diamine that is a hole-transporting group, and reports that it is an excellent polymer that has high heat resistance and functions as a hole-transporting layer ( Japanese Patent Application No. 8-310049, Japanese Patent Application No. 7-94294, Japanese Patent Application No. 6-210544), and the electron-transporting polymer also includes a main chain type containing 1,3,4-oxadiazole and We are developing side chain polymers. (Japanese Patent Application No. 8-94818, etc.)
[0004]
As for 1,2,4-triazole derivatives, the present applicants synthesized various low-molecular 1,2,4-triazole derivatives, and their deposited films are extremely excellent as carrier transport layers and light emitting layers in organic EL devices. It has shown that it has the characteristic.
[0005]
[Problems to be solved by the invention]
However, in order to use a low molecular film for an element, it is necessary to form a film by a vacuum deposition method, and it takes time to manufacture the element. Furthermore, it has a defect of poor element durability at high temperatures due to crystallization of the deposited film.
[0006]
Accordingly, an object of the present invention is to provide a vinyl derivative containing a 1,2,4-triazole group in the side chain, a
[0007]
[Means for Solving the Problems]
The first of the present invention is the following general formula [1]
[Formula 4]
The 1,2,4-triazole group containing vinyl derivative shown by these.
[0008]
The second of the present invention is the following general formula [2]
[Chemical formula 5]
And a 1,2,4-triazole group-containing polymer having a number average molecular weight of 1,000 to 1,000,000 having a repeating unit represented by
[0009]
The third of the present invention is the following general formula [3]
[Chemical 6]
And a 1,2,4-triazole group-containing polymer having a number average molecular weight of 1,000 to 1,000,000 having a repeating unit represented by
[0010]
A fourth aspect of the present invention is an organic electroluminescence characterized in that the 1,2,4-triazole group-containing polymer according to claim 2 and / or claim 3 is used for a carrier transport layer and / or a light emitting layer. The cent element.
[0011]
Examples of the substituent include an alkyl group, an alkoxy group, an amino group, a dialkylamino group, a diphenylamino group, a cyano group, and a halogen. The number of carbon atoms in the alkyl group, the alkoxy group, the dialkylamino group, etc. There is no particular limitation as long as it does not cause steric hindrance during polymerization of the vinyl monomer.
[0012]
An example of the monomer synthesis method of the present invention is shown.
[Chemical 7]
In the above formula, NBS is N-bromosuccinimide, AIBN is azoisobutyronitrile, CClFourIs carbon tetrachloride, t-BuOK is tert-butyl alcoholate of potassium, and THF is tetrahydrofuran.
[0014]
The vinyl compound of the present invention can be polymerized or copolymerized in the same manner as a normal vinyl compound. As the polymerization method, any of bulk polymerization, solution polymerization, emulsion polymerization, and suspension polymerization can be employed. Although the examples show radical polymerization systems, the monomers of the present invention can also be polymerized by ionic polymerization, particularly anionic polymerization.
[0015]
The polymer of the present invention can be obtained with any molecular weight from waxy to solid by adjusting the polymerization conditions, but usually has a molecular weight of 1,000 to 1,000,000. Are useful for various applications of polymers.
[0016]
Since the novel polymer of the present invention has an electron transporting property, it can be used for various applications utilizing this characteristic in addition to the use of a simple polymer. In particular, it can be used for EL devices. That is, the 1,2,4-triazole group-containing polymer of the present invention contains a 1,2,4-triazole group, known for carrier transportability, in the side chain, thereby transporting carriers such as electrons and holes. Therefore, it can be used as a carrier transport layer or a light emitting layer of an organic EL element. In addition, since it is possible to easily form a film by application from a solution, it is possible to reduce the cost when manufacturing the element.
[0017]
【Example】
Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.
[0018]
Example 1 (Monomer Synthesis Example 1)
The synthesis process of Example 1 is shown as a reaction formula as follows.
[0019]
[Chemical 8]
(1) Synthesis of 1-naphthoic acid methyl ester [compound of (A) in the above reaction formula]
6.03 g (35 mmol) of 1-naphthoic acid was dissolved in methanol (150 ml), concentrated sulfuric acid (7 ml) was added as a catalyst, and the mixture was refluxed at 90 ° C. for 6 hours. After completion of the reaction, the ester was extracted with diethyl ether. Ethanol and concentrated sulfuric acid were removed by washing with water, and diethyl ether was distilled off after drying to obtain a brown liquid ester (A).
C12HTenO2(186.21)
Yield 5.63g
Yield 86.5%
IR (KBr) ν-COCHThree1717cm-1
[0021]
(2) Synthesis of 1-naphthhydrazide [compound of (B) in the above reaction formula]
After 15 g (300 mmol) of hydrazine-hydrate was dissolved in ethanol (100 ml) and purged with nitrogen, 5.59 g (30 mmol) of the compound (A) was added dropwise to this solution, and after completion of the addition, the mixture was refluxed at 85 ° C. for 48 hours. It was. After completion of the reaction, the solvent was removed, and the precipitated crystals were subjected to suction filtration with cold methanol to obtain a product (B).
C11HTenN2O (186.22)
Yield 3.35g
Yield 66.9%
IR (KBr) ν-NH23400cm-1, Ν-CONH-1717cm-1
[0022]
(3) Synthesis of N- (1-naphthoyl) -N ′-(4-phenylbenzoyl) hydrazine [compound of (C) in the above reaction formula]
After 2.70 g (13.0 mmol) of the compound (B) was dissolved in pyridine (50 ml) and purged with nitrogen, 2.42 g (13.0 mmol) of 4-phenylbenzoyl chloride was added dropwise to this solution, and after completion of the addition, room temperature. At reflux for 19 hours. After completion of the reaction, the solution was poured into distilled water, and the reaction product which had been white-washed was washed with water. After washing with water, the reaction product was suction filtered to obtain compound (C).
Ctwenty fourH18N2O2(366.42)
Yield 3.78g
Yield 79.4%
IR (KBr) ν-CONH-3195cm-1
[0023]
(4) Synthesis of 3- (1-naphthyl) -4- (4-ethylphenyl) -5- (4-phenylbenzoyl) -1,2,4-triazole [compound of (D) in the above reaction formula]
After dissolving 7.34 g (60.6 mmol) of p-ethylaniline in o-dichlorobenzene (90 ml), 1.53 g (11.1 mmol) of phosphorus trichloride was added and reacted for about one hour. 3.70 g (10.1 mmol) of (1-naphthoyl) -N ′-(4-phenylbenzoyl) hydrazine [the compound (C)] was added, and the mixture was refluxed at 200 ° C. for 48 hours under a nitrogen atmosphere. After completion of the reaction, the solution was washed with a 0.5N aqueous hydrochloric acid solution and distilled water in this order. After washing, o-dichlorobenzene was removed by distillation under reduced pressure (80 ° C./3 mmHg) to obtain crude crystals. The resulting crude crystals were column purified with a mixed solvent of ethyl acetate and chloroform having a mixing ratio of 1: 4 to obtain compound (D).
(5) 3- (1-Naphtyl) -4- [4- (1-bromoethylphenyl)]-5- (4-phenylbenzoyl) -1,2,4-triazole [in the above reaction formula, Compound]
In carbon tetrachloride (50 ml), 0.28 g (1.56 mmol) of N-bromosuccinimide and 0.026 g (0.16 mmol) of azoisobutyronitrile (AIBN) were dissolved, and 3- (1-naphthyl)- 4- (4-Ethylphenyl) -5- (4-phenylbenzoyl) -1,2,4-triazole [the aforementioned compound (D)] (0.70 g, 1.56 mmol) was added, and the mixture was added at 95 ° C. under a nitrogen atmosphere at 24 ° C. Reflux for hours. After the reaction was completed, the mixture was allowed to stand for 2 hours to precipitate unreacted substances, followed by filtration. The filtrate was freed from the solvent to obtain crude crystals. The resulting crude crystals were column purified with a mixed solvent of ethyl acetate and chloroform, and the crude crystals were recrystallized with a mixed solvent of benzene and n-hexane having a mixing ratio of 1: 2, to obtain the compound (E).
(6) Synthesis of 3- (1-naphthyl) -4- (4-vinylphenyl) -5- (4-phenylbenzoyl) -1,2,4-triazole [compound of (F) in the above reaction formula]
In 40 ml of dry tetrahydrofuran (THF), 0.37 g (3.28 mmol) of potassium tert-butoxide was dissolved and stirred at 0 ° C. 3- (1-naphthyl) -4- [4 dissolved in 10 ml of dry THF in this solution. -(1-Bromoethylphenyl)]-5- (4-phenylbenzoyl) -1,2,4-triazole [the compound (E)] (0.58 g, 1.09 mmol) was added dropwise, and after completion of the addition, at room temperature. The reaction was performed for 24 hours. After completion of the reaction, the solvent was removed, chloroform was added to the residue, washed with 0.01N sodium hydroxide and distilled water in that order, dried over magnesium sulfate, and then the solvent was removed to obtain crude crystals. The obtained crude crystals were recrystallized with a mixed solvent of benzene and n-hexane having a mixing ratio of 2: 3 to obtain the compound (F).
Example 2 (Monomer Synthesis Example 2)
The synthesis process of Example 2 is shown in the reaction formula as follows.
[0027]
[Chemical 9]
(1) Synthesis of N, N ′-(1-dinaphthoyl) -hydrazine [compound of the above reaction formula (C ′)]
1-Naphthhydrazine obtained in (2) of Example 1 [Compound of (B) above]
After 3.30 g (17.7 mmol) was dissolved in pyridine (60 ml) and purged with nitrogen, 3.38 g (17.7 mmol) of 1-naphthalenecarboxylic acid chloride was added dropwise to this solution, and refluxed at room temperature for 19 hours after completion of the addition. I let you. After completion of the reaction, the solution was poured into distilled water, and the reaction product which had been white-washed was washed with water. After washing with water, the reaction product was subjected to suction filtration to obtain a product (C ′).
Ctwenty twoH16N2O2(340.39)
Yield 5.25g
Yield 87.1%
IR (KBr) ν-CONH-3187cm-1
[0029]
(2) Synthesis of 3,5-dinaphthyl-4- (4-ethylphenyl) -1,2,4-triazole [compound of (D ′) in the above reaction formula]
After dissolving 11.3 g (93.4 mmol) of p-ethylaniline in o-dichlorobenzene (90 ml), 2.35 g (17.1 mmol) of phosphorus trichloride was added and reacted for about one hour. N ′-(1-Dinaphthoyl) -hydrazine [the compound (C ′)] (5.20 g, 15.5 mmol) was added, and the mixture was refluxed at 200 ° C. for 48 hours in a nitrogen atmosphere. After completion of the reaction, the solution was washed with a 0.5N aqueous hydrochloric acid solution and distilled water in this order. After washing, o-dichlorobenzene was removed by distillation under reduced pressure (80 ° C./3 mmHg) to obtain crude crystals. The resulting crude crystals were column purified with a mixed solvent of ethyl acetate and dichloromethane in a mixing ratio of 1: 4 to obtain compound (D ′).
(3) Synthesis of 3,5-dinaphthyl-4- [4- (1-bromoethylphenyl)]-1,2,4-triazole [compound of the above reaction formula (E ′)]
In carbon tetrachloride (180 ml), N-bromosuccinimide 0.84 g (4.70 mmol) and AIBN 0.08 g (0.47 mmol) were dissolved, and 3,5-dinaphthyl-4- (4-ethylphenyl) -1 2,4-triazole [the compound (D ′)] 2.00 g (4.70 mmol) was added, and the mixture was refluxed at 95 ° C. for 24 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was allowed to stand for 2 hours to precipitate unreacted substances, followed by filtration. The filtrate was freed from the solvent to obtain crude crystals. The obtained crude crystals were column purified with a mixed solvent of ethyl acetate and chloroform, and the crude crystals were recrystallized with a mixed solvent of benzene and n-hexane in a mixing ratio of 1: 2 to obtain the compound (E ′). .
(4) Synthesis of 3,5-dinaphthyl-4- (4-vinylphenyl) -1,2,4-triazole [compound of (F ′) in the above reaction formula]
0.87 g (7.73 mmol) of potassium tert-butoxide was dissolved in 40 ml of dry THF and stirred at 0 ° C., and 3,5-dinaphthyl-4- [4- (1-bromoethyl) dissolved in 10 ml of dry THF was dissolved in this solution. Phenyl)]-1,2,4-triazole [said compound (E ′)] 1.30 g (2.58 mmol) was added dropwise, and the mixture was reacted at room temperature for 24 hours. After completion of the reaction, the solvent was removed, chloroform was added to the residue, washed with 0.01N sodium hydroxide and distilled water in that order, dried over magnesium sulfate, and then the solvent was removed to obtain crude crystals. The obtained crude crystals were recrystallized with a mixed solvent of benzene and n-hexane having a mixing ratio of 2: 3 to obtain the compound (F ′).
Example 3 (Monomer Synthesis Example 3)
3,5-di (4-cyanophenyl) -4- (4-vinylphenyl) -1,2,4-triazole was synthesized according to the following reaction formula.
[0033]
[Chemical Formula 10]
(1) Synthesis of 3,5-di (4-cyanophenyl) -4- (4-ethylphenyl) -1,2,4-triazole [compound of (H) in the above reaction formula]
After dissolving 9.24 g of p-ethylaniline in 120 ml of o-dichlorobenzene, 1.92 g of phosphorus trichloride was added and allowed to react for about 1 hour. After the reaction, 3.7 g of N, N′-di (4-cyanobenzoyl) -hydrazine [compound of (G) in the above reaction formula] was added and refluxed for 24 hours in a nitrogen atmosphere. After completion of the reaction, the solution was washed with a 0.5N aqueous hydrochloric acid solution and distilled water in this order, and after washing, o-dichlorobenzene was removed by distillation under reduced pressure and vacuum dried to obtain crude crystals. This was column purified with a mixed solvent of ethyl acetate: chloroform = 1: 4 and recrystallized with acetone: n-hexane = 1: 8 to obtain 1.46 g of compound (H) needle crystals.
Yield 31.2%, m.p. p. : 237 to 239 ° C., IR (KBr): 1608 cm-1(-C = N-), 2966 cm-1(-CHThree),1H-NMR (270 MHz, CDClThree): Δ (ppm) 1.3 (t, 3H, —CHThree), 2.8 (q, 2H, -CH2-), 7.1-7.7 (m, 12H, Ar), ANAL. Calcd for Ctwenty fourH17NFiveC, 76.78%; H, 4.56%; N, 18.65%. Found; C, 76.85%; H, 4.65%; N, 18.32%.
[0035]
(2) Synthesis of 3,5-di (4-cyanophenyl) -4- [4- (1-bromoethylphenyl)]-1,2,4-triazole [compound of (I) in the above reaction formula]
3,5-di (4-cyanophenyl) -4- (4-ethylphenyl) -1,2,4-triazole [compound of (H) in the above reaction formula] (1.43 mmol) in carbon tetrachloride NBS (4.29 mmol) and AIBN (0.143 mmol) were added and refluxed for 24 hours under a nitrogen atmosphere. After completion of the reaction, carbon tetrachloride was removed to obtain crude crystals. This was purified by column purification with a mixed solvent of ethyl acetate: chloroform 1: 2, and recrystallized with acetone: n-hexane 1: 8 to obtain crystals of compound (I).
Yield 46.2%, m.p. p. : 174 to 176 ° C., IR (KBr): 1608 cm-1(-C = N-), 2966 cm-1(-CHThree),1H-NMR (270 MHz, CDClThree): Δ (ppm) 2.0 (d, 3H, —CHThree), 5.2 (q, 1H, —CHBr—), 7.1 to 7.6 (m, 12H, Ar—H), ANAL. Calcd for Ctwenty fourH17NFiveBr1C, 63.31%; H, 4.57%; N, 15.38%. Found; C, 63.02%; H, 3.98%; N, 15.56%.
[0036]
(3) Synthesis of 3,5-di (4-cyanophenyl) -4- (4-vinylphenyl) -1,2,4-triazole [compound of (J) in the above reaction formula]
3,5-di (4-cyanophenyl) -4 dissolved in 3.30 mmol of potassium tert-butoxide in 70 ml of dried THF in a three-necked flask, cooled in ice water with ice water, purged with nitrogen and dissolved in 30 ml of THF. -[4- (1-Bromoethylphenyl)]-1,2,4-triazole [said compound (I)] 13.2 mmol was added dropwise. It was made to react at room temperature for 24 hours after completion | finish of dripping. After completion of the reaction, THF was removed to obtain crude crystals, which were purified by column using a mixed solvent of dichloroethane: ethyl acetate = 4: 1. Furthermore, recrystallization was performed with a mixed solvent of acetone: n-hexane = 1: 10 to obtain 0.20 g of needle crystals of the compound (J).
Yield 25.8%, m.p. p. : 209-210 ° C, IR (KBr): 1608 cm-1(-C = N-), 924cm-1(= CH2),1H-NMR (270 MHz, CDClThree): Δ (ppm) 5.5, 5.9 (d, 2H, ═CH2), 6.8 (q, 1H, -CH =), 7.1-7.7 (m, 12H, Ar-H), ANAL. Calcd for Ctwenty fourH15NFiveC, 77.2%; H, 4.05%; N, 18.75%. Found; C, 76.87%; H, 4.29%; N, 18.33%.
Fluorescence spectrum (excitation wavelength 284 nm): maximum value 394 nm
[0037]
Example 4 (Monomer Synthesis Example 4)
3- (4-Vinylphenyl) -4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole was synthesized according to the following reaction formula.
[0038]
Embedded image
(1) Synthesis of 3- (4-ethylphenyl) -4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole [compound of (H ′) in the above reaction formula]
After dissolving 18.29 g of aniline in 150 ml of dichlorobenzene, 5.39 g of phosphorus trichloride was added and reacted for about one hour. After the reaction, 9.6 g of N- (4-cyanophenylcarbonyl) -N ′-(4-ethylphenylcarbonyl) -hydrazine [compound of the above formula (G ′)] is added, and the temperature is raised to the reflux temperature in a nitrogen atmosphere. It was. Here, since the precursor was not dissolved, pyridine was dropped slowly from the dropping funnel. After about 5 ml was dropped, the dropping was terminated when all the precursors were dissolved, and the mixture was reacted at 190 ° C. for 12 hours. After completion of the reaction, the solution was washed with a 0.5N aqueous hydrochloric acid solution and distilled water in this order, and after washing, o-dichlorobenzene was removed by distillation under reduced pressure and vacuum dried to obtain crude crystals. This was column purified with a mixed solvent of ethyl acetate: chloroform = 1: 4 to obtain a product (4.39 g). Further, recrystallization was performed with acetone: n-hexane to obtain needle crystals of the compound (H ′).
Yield 38.3%, m.p. p. : 190-192 ° C, IR (KBr): 1608 cm-1(-C = N-), 2966 cm-1(-CHThree),1H-NMR (270 MHz, CDClThree): Δ (ppm) 1.3 (t, 3H, —CHThree), 2.7 (q, 2H, -CH2-), 7.2-7.7 (m, 13H, Ar), ANAL. Calcd for Ctwenty fourH17NFiveC, 76.83%; H, 5.18%; N, 15.99%. Found; C, 79.03%; H, 5.29%; N, 15.56%.
[0040]
(2) 3- [4- (1-Bromoethylphenyl)]-4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole [compound of (I ′) in the above reaction formula] Composition
3- (4-Ethylphenyl) -4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole [compound (H ′)] (1.43 mmol), N-bromo in carbon tetrachloride Succinimide (NBS) 2.15 mmol and AIBN (0.143 mmol) were added and refluxed for 24 hours under a nitrogen atmosphere. After completion of the reaction, carbon tetrachloride was removed to obtain crude crystals. This was purified by column purification with a mixed solvent of ethyl acetate: chloroform = 1: 2, and recrystallized with acetone: n-hexane = 1: 8 to obtain a crystal of compound (I ′).
Yield 58.6%, m.p. p. : 122-123 ° C, IR (KBr): 1608 cm-1(-C = N-), 2966 cm-1(-CHThree),1H-NMR (270 MHz, CDClThree): Δ (ppm) 2.1 (d, 3H, —CHThree), 5.2 (q, 1H, —CHBr—), 7.1 to 7.9 (m, 13H, Ar—H), ANAL. Calcd for Ctwenty threeH17NFourBr1C, 64.35%; H, 3.99%; N, 13.05%. Found; C, 65.01%; H, 4.35%; N, 12.88%.
[0041]
(3) Synthesis of 3- (4-vinylphenyl) -4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole [compound of (J ′) in the above reaction formula]
3- [4- (1-Bromoethylphenyl)] dissolved in 30 ml of dry THF in a three-necked flask was dissolved in 2.24 mmol of potassium tert-butoxide, cooled in ice water with nitrogen, purged with nitrogen, and dissolved in 10 ml of THF. 0.745 mmol of -4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole [the compound (I ′)] was added dropwise. It was made to react at room temperature for 24 hours after completion | finish of dripping. After completion of the reaction, THF was removed to obtain crude crystals, which were purified by column using a mixed solvent of dichloroethane: ethyl acetate = 4: 1. Furthermore, recrystallization was performed with a mixed solvent of acetone: n-hexane = 1: 10 to obtain 0.15 g of needle-like crystals of the compound (J ′).
Yield 61.1%, m.p. p. : 221 to 223 ° C., IR (KBr): 1608 cm-1(-C = N-), 924cm-1(= CH2),1H-NMR (270 MHz, CDClThree): Δ (ppm) 5.5, 5.9 (d, 2H, ═CH2), 6.8 (q, 1H, -CH =), 7.1-7.7 (m, 13H, Ar-H), ANAL. Calcd for Ctwenty threeH16NFourC, 79.3%; H, 4.63%; N, 16.1%. Found; C, 79.0%; H, 4.52%; N, 16.0%.
Fluorescence spectrum (excitation wavelength 309 nm): maximum value 388 nm
[0042]
Example 5 (Synthesis of polymer of Example 1)
3- (1-Naphthyl) -4- (4-vinylphenyl) -5- (4-phenylbenzoyl) -1,2,4-triazole dissolved in 0.2 ml of dimethylformamide (DMF) in a polymerization tube Compound (F)] 0.05 g (0.111 mmol) and AIBN 0.002 g (0.011 mol) were added, and after substitution by freeze degassing nitrogen, the mixture was reacted at 60 ° C. for 12 hours in a thermostatic bath. After completion of the reaction, it was reprecipitated in methanol to obtain a polymer. This polymer was purified by repeating reprecipitation purification three times. This polymer has the following repeating units. The physical properties are shown in Tables 1 to 3 and FIG.
Example 6 (Synthesis of polymer of Example 2)
0.05 g (0.118 mmol) of 3,5-dinaphthyl-4- (4-vinylphenyl) -1,2,4-triazole [the compound (F ′)] dissolved in 0.2 ml of DMF in a polymerization tube, start AIBN 0.002 g (0.011 mol) was added as an agent, and after substitution by freeze deaeration and nitrogen, the reaction was carried out at 60 ° C. for 12 hours in a thermostatic bath. After completion of the reaction, it was reprecipitated in methanol to obtain a polymer. This polymer was purified by repeating reprecipitation purification three times. This polymer has the following repeating units. The physical properties are shown in Tables 1 to 3 and FIG.
Example 7 (Synthesis of polymer of Example 3)
In a 5 ml polymerization tube, 0.3 g of 3,5-di (4-cyanophenyl) -4- (4-vinylphenyl) -1,2,4-triazole [compound (J)] and 0.013 g of AIBN as an initiator were added. Into 3 ml of DMF as a solvent, polymerization was performed at 60 ° C. for 24 hours after lyophilization to obtain a polymer having the following repeating units. The physical properties are shown in Tables 1 to 3 and FIG.
Yield 0.12g
Yield 39%
Mn = 23,000
Mw / Mn = 1.2
Embedded image
Example 8 (Synthesis of polymer of Example 4)
Into a 5 ml polymerization tube, 0.1 g of 3- (4-vinylphenyl) -4-phenyl-5- (4-cyanophenyl) -1,2,4-triazole [compound (J ′)], AIBN5. 0x10-Fourg was added and 1 ml of DMF was used as a solvent, and after lyophilization, polymerization was carried out at 60 ° C. for 24 hours to obtain a polymer having the following repeating units. The physical properties are shown in Tables 1 to 3 and FIG. In particular, as is clear from Table 1, the triazole position of this example is a vinyl aromatic group as compared to the polymer substituted at position 4 of the triazole of Examples 5 to 7 with vinyl aromatic. The substituted polymer is highly soluble in organic solvents.
Yield 0.040 g, Yield 40%, Mn = 67,000, Mw / Mn = 1.4
Embedded image
[Table 1]
[Table 2]
[0048]
[Table 3]
[0049]
Example 9 (EL device using the polymer of Example 8)
In the single-layer organic EL element shown in FIG. 5, an organic EL element was produced using the polymer of Example 8 as the electron transporting polymer layer. The current density-voltage characteristics of this EL element were as shown in FIG. The anode in FIG. 5 is an ITO layer formed on a glass substrate, the sheet resistance is 15Ω / □, and the cathode is a Mg: Ag multilayer.
[0050]
Example 10 (compounding TPD with the polymer of Example 8)
In the single-layer organic EL device shown in FIG. 5, the polymer of Example 8 has the following formula as an electron transporting polymer layer.
Embedded image
[0051]
Example 11 (The polymer of Example 8 is doped with TPD)
In the single-layer organic EL device shown in FIG. 5, a layer obtained by doping the polymer of Example 8 with TPD was used as the electron transporting polymer layer. The relationship between the luminance and wavelength of this EL element is shown in FIG. The peak of the fluorescence spectrum of the polymer alone is at 388 nm, and the peak of the emission spectrum of the polymer doped with TPD is 512 nm compared to the peak of the fluorescence spectrum of TPD only at 410 nm, and the interaction between the polymer and TPD As a result, the emission spectrum is shifted to the longer wavelength side as compared with the case of each of them, indicating green light emission.
[0052]
Example 12 (combined use of TPD and coumarin 6 in the polymer of Example 8)
In the single-layer organic EL device shown in FIG. 5, as an electron transporting polymer layer, TPD is 10 wt% in the polymer, and the following formula
Embedded image
10 and 11 show current density-voltage characteristics and light emission intensity-voltage characteristics exhibited by the EL element when 1 wt% of coumarin 6 represented by formula (1) is blended. It can be seen that the combined use of coumarin 6 improves the emission intensity.
[0053]
【effect】
According to the present invention, a novel monomer, a novel polymer, and an organic EL device using the same can be provided.
[Brief description of the drawings]
1 is a fluorescence spectrum diagram of the polymer of Example 5. FIG.
2 is a fluorescence spectrum diagram of the polymer of Example 6. FIG.
3 is a fluorescence spectrum diagram of the polymer of Example 7. FIG.
4 is a fluorescence spectrum diagram of the polymer of Example 8. FIG.
FIG. 5 shows a laminated structure of a single layer type organic EL element.
6 shows the current density-voltage characteristics of the EL device shown in FIG. 5 in which only the polymer of Example 8 was used as the electron transporting polymer layer.
7 shows the current density-voltage characteristics of the EL device shown in FIG. 5 (device of Example 10) when the polymer of Example 8 blended with TPD in various proportions is used as the electron transporting polymer layer. Show.
8 shows the light emission intensity-voltage characteristics of each EL element of Example 10. FIG.
9 shows the emission spectrum of the EL device of Example 11 in which the polymer of Example 8 is doped with TPD in comparison with the fluorescence spectrum of the polymer itself and the fluorescence spectrum of TPD itself. FIG.
10 shows current density-voltage characteristics of an EL device of Example 12 in which TPD and coumarin 6 are used in combination with the polymer of Example 8. FIG.
11 shows the luminescence intensity-voltage characteristics of the EL device of Example 12 in which TPD and coumarin 6 are used in combination with the polymer of Example 8. FIG.
Claims (4)
で示される１，２，４−トリアゾール基含有ビニル誘導体。The following general formula [1]
The 1,2,4-triazole group containing vinyl derivative shown by these.
で示される繰り返し単位を有する数平均分子量１，０００〜１，０００，０００の１，２，４−トリアゾール基含有高分子。The following general formula [2]
A 1,2,4-triazole group-containing polymer having a number average molecular weight of 1,000 to 1,000,000 having a repeating unit represented by
で示される繰り返し単位を有する数平均分子量１，０００〜１，０００，０００の１，２，４−トリアゾール基含有高分子。The following general formula [3]
A 1,2,4-triazole group-containing polymer having a number average molecular weight of 1,000 to 1,000,000 having a repeating unit represented by
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| EXPY | Cancellation because of completion of term |