JP3593719B2 - Novel triphenylamine derivative, its production method and use - Google Patents
Novel triphenylamine derivative, its production method and use Download PDFInfo
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- JP3593719B2 JP3593719B2 JP18320194A JP18320194A JP3593719B2 JP 3593719 B2 JP3593719 B2 JP 3593719B2 JP 18320194 A JP18320194 A JP 18320194A JP 18320194 A JP18320194 A JP 18320194A JP 3593719 B2 JP3593719 B2 JP 3593719B2
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- 125000006617 triphenylamine group Chemical group 0.000 title claims description 14
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000000463 material Substances 0.000 claims description 70
- 230000005525 hole transport Effects 0.000 claims description 33
- -1 triphenylamine compound Chemical group 0.000 claims description 23
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- OILAIQUEIWYQPH-UHFFFAOYSA-N cyclohexane-1,2-dione Chemical compound O=C1CCCCC1=O OILAIQUEIWYQPH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 150000002894 organic compounds Chemical class 0.000 claims description 4
- 125000005259 triarylamine group Chemical group 0.000 claims 1
- 239000010410 layer Substances 0.000 description 97
- 150000001875 compounds Chemical class 0.000 description 39
- 238000002347 injection Methods 0.000 description 23
- 239000007924 injection Substances 0.000 description 23
- 108091008695 photoreceptors Proteins 0.000 description 22
- 239000000758 substrate Substances 0.000 description 19
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000000034 method Methods 0.000 description 18
- 229920005989 resin Polymers 0.000 description 18
- 239000011347 resin Substances 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- 239000010408 film Substances 0.000 description 11
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 8
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- 239000000956 alloy Substances 0.000 description 8
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- 229910052749 magnesium Inorganic materials 0.000 description 7
- 239000011777 magnesium Substances 0.000 description 7
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- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
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- 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 6
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- 229940098779 methanesulfonic acid Drugs 0.000 description 4
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- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical class N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 3
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- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 2
- MEKOFIRRDATTAG-UHFFFAOYSA-N 2,2,5,8-tetramethyl-3,4-dihydrochromen-6-ol Chemical compound C1CC(C)(C)OC2=C1C(C)=C(O)C=C2C MEKOFIRRDATTAG-UHFFFAOYSA-N 0.000 description 2
- OAIASDHEWOTKFL-UHFFFAOYSA-N 3-methyl-n-[4-[4-(n-(4-methylphenyl)anilino)phenyl]phenyl]-n-phenylaniline Chemical compound C1=CC(C)=CC=C1N(C=1C=CC(=CC=1)C=1C=CC(=CC=1)N(C=1C=CC=CC=1)C=1C=C(C)C=CC=1)C1=CC=CC=C1 OAIASDHEWOTKFL-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 description 2
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 2
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
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- 238000004440 column chromatography Methods 0.000 description 2
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- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 230000007123 defense Effects 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
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- 229910044991 metal oxide Inorganic materials 0.000 description 2
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- 238000013365 molecular weight analysis method Methods 0.000 description 2
- LKKPNUDVOYAOBB-UHFFFAOYSA-N naphthalocyanine Chemical class N1C(N=C2C3=CC4=CC=CC=C4C=C3C(N=C3C4=CC5=CC=CC=C5C=C4C(=N4)N3)=N2)=C(C=C2C(C=CC=C2)=C2)C2=C1N=C1C2=CC3=CC=CC=C3C=C2C4=N1 LKKPNUDVOYAOBB-UHFFFAOYSA-N 0.000 description 2
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- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 2
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
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Images
Description
【０００１】
【産業上の利用分野】
本発明は、新規なトリフェニルアミン誘導体、その製造方法及びその用途に関するものであり、本誘導体は感光材料、有機光導電材料等に使用でき、さらに具体的には、平面光源や表示に使用される有機エレクトロルミネッセンス（ＥＬ）素子あるいは電子写真感光体の正孔輸送材料として有用な材料である。
【０００２】
【従来の技術】
感光材料や正孔輸送材料として開発されている有機光導電材料は、低コスト、加工性が多様であり、無公害性などの多くの利点があり、多くの化合物が提案されている。例えば、オキサジアゾール誘導体（米国特許第３，１８９，４４７号）、オキサゾール誘導体（米国特許第３，２５７，２０３号）、ヒドラゾン誘導体（米国特許第３，７１７，４６２号、特開昭５４−５９，１４３号、米国特許第４，１５０，９７８号）、トリアリールピラゾリン誘導体（米国特許第３，８２０，９８９号、特開昭５１−９３，２２４号、特開昭５５−１０８，６６７号）、アリールアミン誘導体（米国特許第３，１８０，７３０号、米国特許第４，２３２，１０３号、特開昭５５−１４４，２５０号、特開昭５６−１１９，１３２号）、スチルベン誘導体（特開昭５８−１９０，９５３号、特開昭５９−１９５，６５８号）などの有機光導電性材料が開示されている。
【０００３】
正孔輸送材料を利用した技術の一つとしては、有機ＥＬ素子が挙げられる。有機物質を使用したＥＬ素子は、固体発光型の安価な大面積フルカラー表示素子としての用途が有望視され、多くの開発が行われている。一般にＥＬは発光層および該層をはさんだ一対の対向電極から構成されている。発光は、両電極間に電界が印加されると、陰極側から電子が注入され、陽極側から正孔が注入される。さらに、この電子が発光層において正孔と再結合し、エネルギー準位が伝導帯から価電子帯に戻る際にエネルギーを光として放出する現象である。
【０００４】
従来の有機ＥＬ素子は、無機ＥＬ素子に比べて駆動電圧が高く、発光輝度や発光効率も低かった。また、特性劣化も著しく実用化には至っていなかった。
近年、１０Ｖ以下の低電圧で発光する高い蛍光量子効率を持った有機化合物を含有した薄膜を積層した有機ＥＬ素子が報告され、関心を集めている（アプライド・フィジクス・レターズ、５１巻、９１３ページ、１９８７年参照）。
この方法は、金属キレート錯体を蛍光体層、アミン系化合物を正孔注入層に使用して、高輝度の緑色発光を得ており、６〜７Ｖの直流電圧で輝度は数１００ｃｄ／ｍ２、最大発光効率は１．５ｌｍ／Ｗを達成して、実用領域に近い性能を持っている。
【０００５】
しかしながら、現在までの有機ＥＬ素子は、構成の改善により発光強度は改良されているが、未だ充分な発光輝度は有していない。また、繰り返し使用時の安定性に劣るという大きな問題を持っている。従って、より大きな発光輝度を持ち、繰り返し使用時での安定性の優れた有機ＥＬ素子の開発のために、優れた正孔輸送能力を有し、耐久性のある正孔輸送材料の開発が望まれている。
【０００６】
さらに、正孔輸送材料を利用した技術としては、電子写真感光体が挙げられる。電子写真方式は、カールソンにより発明された画像形成法の一つである。この方式は、コロナ放電により感光体を帯電した後、光像露光して感光体に静電潜像を得、該静電潜像にトナーを付着させて現像し、得られたトナー像を紙へ転写することからなる。このような電子写真方式における感光体に要求される基本的な特性としては、暗所において適当な電位が保持されること、暗所における電荷の放電が少ないこと、光照射により速やかに電荷を放電することなどが挙げられる。従来までの電子写真感光体は、セレン、セレン合金、酸化亜鉛、硫化カドミウムおよびテルルなどの無機光導電体が使用されてきた。これらの無機光導電体は、耐久性が高く、耐刷枚数が多いなどの利点を有しているが、製造コストが高く、加工性が劣り、毒性を有するなどの問題点が指摘されている。これらの欠点を克服するために有機感光体の開発が行われているが、従来までの有機光導電材料を正孔輸送材料として用いた電子写真感光体は、帯電性、感度および残留電位などの電子写真特性が、必ずしも満足されているものとは言えないのが現状であり、優れた電荷輸送能力を有し、耐久性のある正孔輸送材料の開発が望まれていた。
【０００７】
【発明が解決しようとする課題】
本発明の目的は、耐久性のある正孔輸送材料として有用な、新規トリフェニルアミン誘導体、その製造方法及びその用途を提供することにある。
【０００８】
【課題を解決するための手段】
即ち、第一の発明は、一般式［１］で示されるトリフェニルアミン誘導体である。
一般式［１］
【化４】
一般式［２］
【化５】
【０００９】
第二の発明は、１，２−シクロヘキサジオンと、下記一般式［３］で示されるトリフェニルアミン化合物とを反応させることを特徴とする請求項１記載のトリフェニルアミン誘導体の製造方法である。
一般式［３］
【化６】
【００１０】
第三の発明は、請求項１記載のトリフェニルアミン誘導体からなる正孔輸送材料である。
【００１１】
第四の発明は、一対の電極間に発光層または発光層を含む複数層の有機化合物薄膜を備えた有機エレクトロルミネッセンス素子において、少なくとも一層が請求項３記載の正孔輸送材料を含有する有機エレクトロルミネッセンス素子である。
【００１２】
第五の発明は、導電性支持体上に、電荷発生材料および正孔輸送材料を使用してなる電子写真感光体において、正孔輸送材料が、請求項３記載の正孔輸送材料である電子写真感光体である。
【００１３】
本発明における一般式［１］で示される化合物の、Ａ1は一般式［２］で示されるトリフェニルアミン化合物残基を示し、Ａ2は、それぞれ独立に水素原子もしくは、一般式［２］で示されるトリフェニルアミン化合物残基を示す。
式中、Ｒ1〜Ｒ4は、それぞれ独立に、水素原子、未置換のアルキル基である。
Ｒ1〜Ｒ4の具体例は、未置換のアルキル基としては、メチル基、エチル基、プロピル基、ブチル基、ｓｅｃ−ブチル基、ｔｅｒｔ−ブチル基、ペンチル基、ヘキシル基、ヘプチル基、オクチル基、ステアリル基等がある。
【００１４】
本発明において、一般式［１］で示される化合物は、新規物質であり、例えば以下の方法により製造することができる。
１，２−シクロヘキサジオンに、４〜５倍モルの下記一般式［３］で示される置換基を有するトリフェニルアミン化合物を酢酸溶媒中、メタンスルホン酸等の酸触媒を用いて脱水反応させることにより、一般式［１］で示されるトリフェニルアミン誘導体を製造することができる。また、本発明で用いられる酸触媒としては、メタンスルホン酸の代わりに、トリフルオロ酢酸、ｐ−トルエンスルホン酸の様な有機酸、または、硫酸、塩酸、ルイス酸等も可能である。また、有機溶剤としては、酢酸の他に、１，４−ジオキサン、エーテル、石油エーテル等も可能である。ここで、１，２−シクロヘキサジオン及び一般式［３］の混合比を１：４以下にするとトリフェニルアミン化合物の導入個数が４個より少なくなり、反応時間を２０時間以上にすることにより、トリフェニルアミン誘導体の収率が５０％以上に向上する。
【００１５】
以下に、本発明の化合物の代表例を、表１に具体的に例示するが、本発明は以下の代表例に限定されるものではない。
【００１６】
【表１】
本発明のトリフェニルアミン誘導体は、他の正孔もしくは電子輸送性化合物と混合して使用してもさしつかえない。本発明の化合物は正孔輸送性に優れているので、正孔輸送性材料として極めて有効に使用することができる。
【００２２】
また、請求項２の製造方法は、ジカルボニル化合物と前記一般式［３］で示されるトリフェニルアミン化合物との脱水反応を利用する方法であり、工業的に極めて有用な製造方法である。
【００２３】
まず、一般式［１］で示される化合物を有機ＥＬ素子の正孔輸送材料として用いる場合について説明する。図１〜３に、本発明で使用される有機ＥＬ素子構造の模式図の一例を示した。図中、一般的に電極Ａである２は陽極であり、電極Ｂである６は陰極である。また、（電極Ａ／発光層／電子注入層／電極Ｂ）の層構成で積層した有機ＥＬ素子もあり、一般式［１］の化合物は、どの素子構成においても好適に使用することが出来る。
一般式［１］の化合物は、大きな正孔輸送能力をもっているので、正孔注入層
３もしくは発光層４のいずれの層においても、正孔輸送材料として使用できる。
【００２４】
図１の発光層４には、必要があれば、本発明の一般式［１］の化合物に加えて、発光物質、発光補助材料、キャリア輸送を行う正孔輸送材料や電子輸送材料を使用することもできる。
図２の構造は、発光層４と正孔注入層３を分離している。この構造により、正孔注入層３から発光層４への正孔注入効率が向上して、発光輝度や発光効率を増加させることができる。この場合、発光効率のためには、発光層に使用される発光物質自身が電子輸送性であること、または発光層中に電子輸送輸送材料を添加して発光層を電子輸送性にすることが望ましい。
【００２５】
図３の構造は、正孔注入層３に加えて電子注入層５を有し、発光層４での正孔と電子の再結合の効率を向上させている。このように、有機ＥＬ素子を多層構造にすることにより、クエンチングによる輝度や寿命の低下を防ぐことができる。図２および図３の素子においても、必要があれば、発光物質、発光補助材料、キャリア輸送を行う正孔輸送材料や電子輸送材料を組み合わせて使用することが出来る。また、正孔注入層、発光層、電子注入層は、それぞれ二層以上の層構成により形成されても良い。
【００２６】
有機ＥＬ素子の陽極に使用される導電性物質としては、４ｅＶより大きな仕事関数を持つものが好適であり、炭素、アルミニウム、バナジウム、鉄、コバルト、ニッケル、タングステン、銀、金、白金、パラジウム等およびそれらの合金、ＩＴＯ基板、ＮＥＳＡ基板と称される酸化スズ、酸化インジウム等の酸化金属、さらにはポリチオフェンやポリピロール等の有機導電性樹脂が用いられる。
陰極に使用される導電性物質としては、４ｅＶより小さな仕事関数を持つものが好適であり、マグネシウム、カルシウム、錫、鉛、チタニウム、イットリウム、リチウム、ルテニウム、マンガン等およびそれらの合金が用いられるが、これらに限定されるものではない。陽極および陰極は、必要があれば二層以上の層構成により形成されていても良い。
【００２７】
有機ＥＬ素子では、効率良く発光させるために、２で示される電極Ａまたは６で示される電極Ｂのうち、少なくとも一方は素子の発光波長領域において充分透明にすることが望ましい。また、基板１も透明であることが望ましい。透明電極は、上記した導電性物質を使用して、蒸着やスパッタリング等の方法で所定の透光性が確保するように設定する。発光面の電極は、光透過率が１０％以上であることが望ましい。
【００２８】
基板１は、機械的、熱的強度を有し、透明なものであれば限定されるものではないが、例示すると、ガラス基板、ポリエチレン板、ポリエーテルサルフォン板、ポリプロピレン板等の透明樹脂があげられる。
【００２９】
本発明に係わる有機ＥＬ素子の各層の形成は、真空蒸着、スパッタリング等の乾式成膜法やスピンコーティング、ディッピング等の湿式成膜法のいずれの方法を適用することができる。膜厚は特に限定されるものではないが、各層は適切な膜厚に設定する必要がある。膜厚が厚すぎると、一定の光出力を得るために大きな印加電圧が必要になり効率が悪くなる。膜厚が薄すぎるとピンホール等が発生して、電界を印加しても充分な発光輝度が得られない。通常の膜厚は５ｎｍから１０μｍの範囲が好適であるが、１０ｎｍから０．２μｍの範囲がさらに好ましい。
【００３０】
湿式成膜法の場合、各層を形成する材料を、クロロフォルム、テトラヒドロフラン、ジオキサン等の適切な溶媒に溶解または分散させた薄膜を形成する。また、いずれの薄膜においても、成膜性向上、膜のピンホール防止等のため適切な樹脂や添加剤を使用しても良い。
このような樹脂としては、ポリスチレン、ポリカーボネート、ポリアリレート、ポリエステル、ポリアミド、ポリウレタン、ポリスルフォン、ポリメチルメタクリレート、ポリメチルアクリレート、セルロース等の絶縁性樹脂、ポリ−Ｎ−ビニルカルバゾール、ポリシラン等の光導電性樹脂、ポリチオフェン、ポリピロール等の導電性樹脂を挙げることができる。
【００３１】
本有機ＥＬ素子は、発光層、正孔注入層、電子注入層において、必要があれば、一般式［１］の化合物に加えて、公知の発光物質、発光補助材料、正孔輸送材料、電子輸送材料を使用することもできる。
【００３２】
公知の発光物質または発光物質の補助材料としては、アントラセン、ナフタレン、フェナントレン、ピレン、テトラセン、コロネン、クリセン、フルオレセイン、ペリレン、フタロペリレン、ナフタロペリレン、ペリノン、フタロペリノン、ナフタロペリノン、ジフェニルブタジエン、テトラフェニルブタジエン、クマリン、オキサジアゾール、アルダジン、ビスベンゾキサゾリン、ビススチリル、ピラジン、シクロペンタジエン、オキシン、アミノキノリン、イミン、ジフェニルエチレン、ビニルアントラセン、ジアミノカルバゾール、ピラン、チオピラン、ポリメチン、メロシアニン、イミダゾールキレート化オキシノイド化合物、キナクリドン、ルブレン等およびそれらの誘導体があるが、これらに限定されるものではない。
【００３３】
一般式［１］の正孔輸送材料と併せて使用できる正孔輸送材料としては、正孔を輸送する能力を持ち、発光層または発光物質に対して優れた正孔注入効果を有し、発光層で生成した励起子の電子注入層または電子輸送材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。具体的には、フタロシアニン系化合物、ナフタロシアニン系化合物、ポルフィリン系化合物、オキサジアゾール、トリアゾール、イミダゾール、イミダゾロン、イミダゾールチオン、ピラゾリン、ピラゾロン、テトラヒドロイミダゾール、オキサゾール、オキサジアゾール、ヒドラゾン、アシルヒドラゾン、ポリアリールアルカン、スチルベン、ブタジエン、ベンジジン型トリフェニルアミン、スチリルアミン型トリフェニルアミン、ジアミン型トリフェニルアミン等と、それらの誘導体、およびポリビニルカルバゾール、ポリシラン、導電性高分子等の高分子材料等があるが、これらに限定されるものではない。
【００３４】
電子輸送材料としては、電子を輸送する能力を持ち、発光層または発光物質に対して優れた電子注入効果を有し、発光層で生成した励起子の正孔注入層または正孔輸送材料への移動を防止し、かつ薄膜形成能の優れた化合物が挙げられる。例えば、フルオレノン、アントラキノジメタン、ジフェノキノン、チオピランジオキシド、オキサジアゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等とそれらの誘導体があるが、これらに限定されるものではない。
また、正孔輸送材料に電子受容物質を、電子輸送材料に電子供与性物質を添加することにより増感させることもできる。
【００３５】
図１，２および３に示される有機ＥＬ素子において、本発明の一般式［１］の化合物は、いずれの層に使用することもでき、一般式［１］の化合物の他に、発光物質、発光補助材料、正孔輸送材料および電子輸送材料の少なくとも１種が同一層に含有されてもよい。
また、本発明により得られた有機ＥＬ素子の、温度、湿度、雰囲気等に対する安定性の向上のために、素子の表面に保護層を設けたり、シリコンオイル等を封入して素子全体を保護することも可能である。
以上のように、本発明では有機ＥＬ素子に一般式［１］の化合物を用いたため、発光効率と発光輝度を高くできた。また、この素子は熱や電流に対して非常に安定であり、さらには低い駆動電圧で実用的に使用可能の発光輝度が得られるため、従来まで大きな問題であった劣化も大幅に低下させることができた。
【００３６】
本発明の有機ＥＬ素子は、壁掛けテレビ等のフラットパネルディスプレイや、平面発光体として、複写機やプリンター等の光源、液晶ディスプレイや計器類等
の光源、表示板、標識灯等へ応用が考えられ、その工業的価値は非常に大きい。
【００３７】
次に、本発明の一般式［１］で示される化合物を電子写真感光体として用いる場合について説明する。本発明の一般式［１］で示される化合物は、電子写真感光体の何れの層においても使用できるが、高い正孔輸送特性を有することから正孔輸送材料として使用することが望ましい。該化合物は正孔輸送物質として作用し、光吸収により発生した、もしくは電極より注入した電荷を極めて効率よく輸送できるので、高速応答性に優れた感光体を得ることが可能である。また、該化合物は、耐オゾン性、光安定性に優れているので、耐久性に優れた感光体を得ることができる。
【００３８】
電子写真感光体は、導電性基板上に電荷発生材料と、必要があれば電荷輸送材料を結着樹脂に分散させてなる感光層を設けた単層型感光体、導電性基板上に下引き層、電荷発生層、正孔輸送層の順に積層した、もしくは導電性基板または下引き層上に正孔輸送層、電荷発生層の順に積層した積層型感光体等がある。ここで、下引き層は必要がなければ使用しなくても良い。該感光体は、必要があれば活性ガスからの表面保護およびトナーによるフィルミング防止等の意味でオーバーコート層を設けることも出来る。
【００３９】
電荷発生材料としては、ビスアゾ、キナクリドン、ジケトピロロピロール、インジゴ、ペリレン、ペリノン、多環キノン、スクアリリウム塩、アズレニウム塩、フタロシアニン、ナフタロシアニン等の有機化合物、もしくは、セレン、セレン−テルル合金、硫化カドミウム、酸化亜鉛、アモルファスシリコン等の無機物質が挙げられる。
【００４０】
感光体の各層は蒸着もしくは分散塗工方式により成膜することが出来る。分散塗工は、スピンコーター、アプリケーター、スプレーコーター、浸漬コーター、ローラーコーター、カーテンコーターおよびビードコーター等を用いて行い、乾燥は室温から２００℃、１０分から６時間の範囲で静止または送風条件下で行う。乾燥後の感光層の膜厚は単層型感光体の場合、５ミクロンから５０ミクロン、積層型感光体の場合、電荷発生層は０．０１から５ミクロン、好ましくは０．１から１ミクロンであり、正孔輸送層は５から５０ミクロン、好ましくは１０から２０ミクロンが好適である。
【００４１】
単層型感光体の感光層、積層型感光体の電荷発生層もしくは正孔輸送層を形成する際に使用する樹脂は広範な絶縁性樹脂から選択出来る。また、ポリ−Ｎ−ビニルカルバゾール、ポリビニルアントラセンやポリシラン類などの有機光導電性ポリマーから選択出来る。好ましくは、ポリビニルブチラール、ポリアリレート、ポリカーボネート、ポリエステル、フェノキシ、アクリル、ポリアミド、ウレタン、エポキシ、シリコン、ポリスチレン、ポリ塩化ビニル、塩酢ビ共重合体、フェノールおよびメラミン樹脂等の絶縁性樹脂を挙げることが出来る。電荷発生層もしくは正孔輸送層を形成するために使用される樹脂は、電荷発生材料もしくは正孔輸送材料に対して、１００重量％以下が好ましいがこの限りではない。樹脂は２種類以上組み合わせて使用しても良い。また、必要があれば樹脂を使用しなくてもよい。また、電荷発生層を蒸着、スパッタリング等の物理的成膜法により形成させることも出来る。蒸着、スパッタリング法では、好ましくは１０−５Ｔｏｏｒ以下の真空雰囲気下で成膜することが望ましい。また、窒素、アルゴン、ヘリウム等の不活性ガス中で成膜することも可能である。
【００４２】
電子写真感光体の各層を形成する際に使用する溶剤は、下引き層や他の感光層に影響を与えないものから選択することが好ましい。具体的には、ベンゼン、キシレン等の芳香族炭化水素、アセトン、メチルエチルケトン、シクロヘキサノン等のケトン類、メタノール、エタノール等のアルコール類、酢酸エチル、メチルセロソルブ等のエステル類、四塩化炭素、クロロホルム、ジクロロメタン、ジクロロエタン、トリクロロエチレン等の脂肪族ハロゲン化炭化水素類、クロルベンゼン、ジクロルベンゼン等の芳香族ハロゲン化炭化水素類、テトラヒドロフラン
、ジオキサン等のエーテル類等が用いられるがこれらに限られるものではない。
【００４３】
正孔輸送層は正孔輸送材料のみ、もしくは正孔輸送材料を樹脂に溶解させた塗液を塗布することにより形成される。本感光体に使用される正孔輸送材料は、一般式［１］の化合物に加えて他の正孔輸送材料を組み合わせて使用することもできる。一般式［１］の化合物は、樹脂との相溶性が良く、結晶が析出しにくいので、感度、耐久性の向上のために有利である。
【００４４】
電子写真特性、画像特性等の向上のために、必要があれば基板と有機層の間に下引き層を設けることができ、下引き層としてはポリアミド類、カゼイン、ポリビニルアルコール、ゼラチン、ポリビニルブチラール等の樹脂類、酸化アルミニウム等の金属酸化物などが用いられる。
【００４５】
本発明の材料は、有機ＥＬ素子もしくは電子写真感光体の正孔輸送材料としてのみでなく、光電変換素子、太陽電池、イメージセンサー等の分野においても好適に使用できる。
【００４６】
【実施例】
以下、本発明を実施例に基づきさらに詳細に説明する。
化合物（１）の合成方法
酢酸１８部中に、１，２−シクロヘキサジオン５部、トリフェニルアミン１５部、およびメタンスルホン酸１．５部を入れ、１００℃にて２０時間加熱撹拌した。その後、５００部の水で希釈し、希水酸化ナトリウム水溶液で中和した。この後、酢酸エチルで抽出を行い、濃縮し、シリカゲルを用いたカラムクロマトグラフィーにより精製して白色の蛍光を有する粉末６部を得た。分子量分析の結果、化合物（１）であることを確認した。
以下に生成物の元素分析結果を示す。
元素分析結果
Ｃ７８Ｈ６４Ｎ４として
計算値（％）：Ｃ：８８．６４ Ｈ：６．０６ Ｎ：５．３０
実測値（％）：Ｃ：８８．３９ Ｈ：６．２２ Ｎ：５．３９
この化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図６に示す。
【００４７】
化合物（３）の合成方法
酢酸３０部中に、１，２−シクロヘキサジオン７部、４，４−ジメチルトリフェニルアミン２３部、およびメタンスルホン酸２部を入れ、１０５℃にて３０時間加熱撹拌した。その後、５００部の水で希釈し、希水酸化ナトリウム水溶液で中和した。この後、酢酸エチルで抽出を行い、濃縮し、シリカゲルを用いたカラムクロマトグラフィーにより精製して黄色の蛍光を有する粉末１０部を得た。分子量分析の結果、化合物（３）であることを確認した。
以下に生成物の元素分析結果を示す。
元素分析結果
Ｃ８６Ｈ７６Ｎ４として
計算値（％）：Ｃ：８８．６６ Ｈ：６．５３ Ｎ：４．８１
実測値（％）：Ｃ：８８．４５ Ｈ：６．８１ Ｎ：４．７４
この化合物の赤外吸収スペクトル（ＫＢｒ錠剤法）を図７に示す。
【００４８】
実施例１
洗浄したＩＴＯ電極付きガラス板上に、化合物（２）、トリス（８−ヒドロキシキノリン）アルミニウム錯体、ポリカーボネート樹脂（ＰＣ−Ａ）を３：２：５の比率でテトラヒドロフランに溶解させ、スピンコーティング法により膜厚１００ｎｍの発光層を得た。その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの電極を形成して図１に示す有機ＥＬ素子を得た。この素子は、直流電圧５Ｖで１５０ｃｄ／ｍ２の発光が得られた。
【００４９】
実施例２
洗浄したＩＴＯ電極付きガラス板上に、化合物（３）をテトラヒドロフランに溶解させ、スピンコーティング法により膜厚５０ｎｍの正孔注入層を得た。次いで、トリス（８−ヒドロキシキノリン）アルミニウム錯体を真空蒸着して膜厚３０ｎｍの発光層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して図２に示す有機ＥＬ素子を得た。正孔注入層および発光層は１０−６Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は、直流電圧５Ｖで約２７０ｃｄ／ｍ２の発光が得られた。
【００５０】
実施例３
洗浄したＩＴＯ電極付きガラス板上に、化合物（５）をテトラヒドロフランに溶解させ、スピンコーティング法により膜厚５０ｎｍの正孔注入層を得た。次いで、トリス（８−ヒドロキシキノリン）アルミニウム錯体を真空蒸着して膜厚３０ｎｍの発光層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して図２に示す有機ＥＬ素子を得た。発光層は１０−６Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は、直流電圧５Ｖで約４５０ｃｄ／ｍ２の発光が得られた。
【００５１】
実施例４
洗浄したＩＴＯ電極付きガラス板上に、化合物（６）を真空蒸着して、膜厚２０ｎｍの正孔注入層を得た。さらに、Ｎ，Ｎ’―ジフェニル―Ｎ，Ｎ’―（３―メチルフェニル）―１，１’―ビフェニル―４，４’―ジアミンを真空蒸着して、膜厚３０ｎｍの正孔輸送層を得た。次いで、トリス（８−ヒドロキシキノリン）アルミニウム錯体を真空蒸着して膜厚３０ｎｍの発光層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１００ｎｍの電極を形成して有機ＥＬ素子を得た。正孔注入層および発光層は１０−６Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は、直流電圧５Ｖで約３３０ｃｄ／ｍ２の発光が得られた。
【００５２】
実施例５
洗浄したＩＴＯ電極付きガラス板上に、Ｎ，Ｎ’―ジフェニル―Ｎ，Ｎ’―（３―メチルフェニル）―１，１’―ビフェニル―４，４’―ジアミンを真空蒸着して、膜厚５０ｎｍの正孔注入層を得た。次いで、トリス（８−ヒドロキシキノリン）アルミニウム錯体と化合物（１０）を３：１の割合で真空蒸着して膜厚５０ｎｍの発光層を作成し、その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの膜厚の電極を形成して図２に示す有機ＥＬ素子を得た。正孔注入層および発光層は１０−６Ｔｏｒｒの真空中で、基板温度室温の条件下で蒸着した。この素子は、直流電圧５Ｖで約３７０ｃｄ／ｍ２の発光が得られた。
【００５３】
実施例６
洗浄したＩＴＯ電極付きガラス板上に、化合物（４）をクロロフォルムに溶解させ、スピンコーティング法により膜厚５０ｎｍの正孔注入層を得た。次いで、真空蒸着法によりトリス（８−ヒドロキシキノリン）アルミニウム錯体の膜厚５０ｎｍの発光層を作成し、さらに真空蒸着法により［２−（４−ｔｅｒｔ−ブチルフェニル）−５−（ビフェニル）−１，３，４−オキサジアゾール］の膜厚２０ｎｍの電子注入層を得た。その上に、マグネシウムと銀を１０：１で混合した合金で膜厚１５０ｎｍの電極を形成して図３に示す有機ＥＬ素子を得た。この素子は、直流電圧５Ｖで約５５０ｃｄ／ｍ２の発光が得られた。
【００５４】
本実施例で示された全ての有機ＥＬ素子について、１ｍＡ／ｃｍ２で連続発光させたところ、１０００時間以上安定な発光を観測することができた。
本発明の有機ＥＬ素子は発光効率、発光輝度の向上と長寿命化を達成するものであり、併せて使用される発光物質、発光補助材料、正孔輸送材料、電子輸送材料、増感剤、樹脂、電極材料等および素子作製方法を限定するものではない。
【００５５】
実施例７
ε型銅フタロシアニン４ｇ、化合物（１）２ｇ、ポリエステル樹脂（バイロン２００：東洋防（株）製）１４ｇをテトラヒドロフラン８０ｇと共にボールミルで５時間分散した。この分散液をアルミニウム基板上に塗工、乾燥して、図４に示す膜厚２０ミクロンの単層型電子写真感光体を作製した。
【００５６】
実施例８
ジブロモアントアントロン６ｇ、化合物（３）２ｇ、ポリエステル樹脂（バイロン２００：東洋防（株）製）１２ｇをテトラヒドロフラン８０ｇと共にボールミルで５時間分散した。この分散液をアルミニウム基板上に塗工、乾燥して、図４に示す膜厚２０ミクロンの単層型電子写真感光体を作製した。
【００５７】
実施例９
τ型無金属フタロシアニン２ｇ、ポリビニルブチラール樹脂（ＢＨ−３：積水化学（株）製）２ｇをテトラヒドロフラン９６ｇと共にボールミルで２時間分散した。この分散液をアルミニウム基板上に塗工、乾燥して、膜厚０．３ミクロンの電荷発生層を作製した。次に化合物（４）１０ｇ、ポリカーボネート樹脂（Ｌ−１２５０；帝人化成（株）製）１０ｇをジクロロメタン８０ｇに溶解した。この塗液を電荷発生層上に塗工、乾燥して、膜厚２０ミクロンの電荷輸送層を形成し、図５に示す積層型電子写真感光体を作製した。
【００５８】
実施例１０
Ｎ，Ｎ’−ビス（２，６−ジクロロフェニル）−３，４，９，１０−ペリレンジカルボキシイミド２ｇ、ポリビニルブチラール樹脂（ＢＨ−３：積水化学（株）製）２ｇをテトラヒドロフラン９６ｇと共にボールミルで２時間分散した。この分散液をアルミニウム基板上に塗工、乾燥して、膜厚０．３ミクロンの電荷発生層を作製した。次に化合物（６）１０ｇ、ポリカーボネート樹脂（Ｌ−１２５０；帝人化成（株）製）１０ｇをジクロロメタン８０ｇに溶解した。この塗液を電荷発生層上に塗工、乾燥して、膜厚２０ミクロンの電荷輸送層を形成し、図５に示す積層型電子写真感光体を作製した。
【００５９】
電子写真感光体の電子写真特性は以下の方法で測定した。静電複写紙試験装置（ＥＰＡ−８１００；川口電機製作所（株）製）により、スタティックモード２、コロナ帯電は−５．２（ｋＶ）、５（ｌｕｘ）の白色光を照射して、初期表面電位（Ｖ０）、Ｖ０と２秒間暗所に放置した時の表面電位（Ｖ２）の比（暗減衰率：ＤＤＲ２＝Ｖ２／Ｖ０）、光露光後に帯電量が初期の１／２まで減少する時間から半減露光量感度（Ｅ１／２）および光露光３秒後の表面電位（ＶＲ３）を調べた。実施例７〜１０の電子写真感光体の電子写真特性を表２に示す。
【００６０】
【表２】
１万回以上繰り返して電子写真特性を測定したところ、本実施例で示された全ての電子写真感光体について、安定な表面電位、感度を得ることができた。
【００６２】
【発明の効果】
本発明により、優れた正孔輸送能力を有する化合物を得ることができた。本発明が提供した化合物は、従来に比べて高発光効率、高輝度であり、長寿命の有機ＥＬ素子および感度、正孔輸送特性、初期表面電位、暗減衰率等の初期電子写真特性に優れ、繰り返し使用に対する疲労も少ない電子写真感光体を得ることができた。
【図面の簡単な説明】
【図１】実施例で使用した有機ＥＬ素子の概略構造を表す断面図
【図２】実施例で使用した有機ＥＬ素子の概略構造を表す断面図
【図３】実施例で使用した有機ＥＬ素子の概略構造を表す断面図
【図４】実施例で使用した電子写真感光体の概略構造を表す断面図
【図５】実施例で使用した電子写真感光体の概略構造を表す断面図
【図６】化合物１の赤外吸収スペクトル図
【図７】化合物３の赤外吸収スペクトル図
【符号の説明】
１．基板
２．電極Ａ
３．正孔注入層
４．発光層
５．電子注入層
６．電極Ｂ
７．Ａｌ基板
８．感光層
９．電荷発生層
１０．正孔輸送層[0001]
[Industrial applications]
The present invention relates to a novel triphenylamine derivative, a method for producing the same, and its use. The derivative can be used for a photosensitive material, an organic photoconductive material, and the like, and more specifically, is used for a planar light source or display. This material is useful as a hole transport material for organic electroluminescent (EL) devices or electrophotographic photoreceptors.
[0002]
[Prior art]
Organic photoconductive materials that have been developed as photosensitive materials and hole transport materials have many advantages such as low cost, various processability, and no pollution, and many compounds have been proposed. For example, oxadiazole derivatives (U.S. Pat. No. 3,189,447), oxazole derivatives (U.S. Pat. No. 3,257,203), hydrazone derivatives (U.S. Pat. 59,143, U.S. Pat. No. 4,150,978), triarylpyrazoline derivatives (U.S. Pat. No. 3,820,989, JP-A-51-93,224, JP-A-55-108,667). ), Arylamine derivatives (U.S. Pat. No. 3,180,730, U.S. Pat. No. 4,232,103, JP-A-55-144250, JP-A-56-119,132), stilbene derivatives (Japanese Patent Application Laid-Open Nos. 58-190,953 and 59-195,658) discloses organic photoconductive materials.
[0003]
One of the techniques using a hole transport material is an organic EL device. 2. Description of the Related Art An EL element using an organic substance is expected to be used as a solid-state light-emitting inexpensive large-area full-color display element, and many developments have been made. Generally, an EL is composed of a light emitting layer and a pair of counter electrodes sandwiching the layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side, and holes are injected from the anode side. In addition, the electrons recombine with holes in the light emitting layer, and emit energy as light when the energy level returns from the conduction band to the valence band.
[0004]
The conventional organic EL element has a higher driving voltage and lower light emission luminance and light emission efficiency than the inorganic EL element. In addition, the characteristics deteriorated remarkably, and practical use has not been achieved.
In recent years, an organic EL device formed by laminating a thin film containing an organic compound having a high fluorescence quantum efficiency and emitting light at a low voltage of 10 V or less has been reported and attracted attention (Applied Physics Letters, vol. 51, p. 913). 1987).
This method uses a metal chelate complex for a phosphor layer and an amine compound for a hole injection layer to obtain high-luminance green light emission. The luminance is several hundred cd / m 2 at a DC voltage of 6 to 7 V. The maximum luminous efficiency achieves 1.5 lm / W, which is a performance close to the practical range.
[0005]
However, organic EL devices up to now have improved light emission intensity due to the improved structure, but do not yet have sufficient light emission luminance. In addition, there is a major problem that the stability upon repeated use is poor. Therefore, in order to develop an organic EL device having higher emission luminance and excellent stability in repeated use, it is desired to develop a hole transporting material having excellent hole transporting ability and durability. It is rare.
[0006]
Further, as a technique using a hole transport material, an electrophotographic photoreceptor can be mentioned. The electrophotographic method is one of image forming methods invented by Carlson. In this method, after a photoconductor is charged by corona discharge, an optical image is exposed to obtain an electrostatic latent image on the photoconductor, toner is attached to the electrostatic latent image and developed, and the obtained toner image is printed on paper. Transfer to The basic characteristics required of the photoreceptor in such an electrophotographic method include that an appropriate potential is maintained in a dark place, that the electric charge is less discharged in the dark place, and that the electric charge is quickly discharged by light irradiation. And so on. Conventional electrophotographic photoreceptors have used inorganic photoconductors such as selenium, selenium alloys, zinc oxide, cadmium sulfide, and tellurium. These inorganic photoconductors have advantages such as high durability and a large number of printing presses, but problems such as high production cost, poor workability, and toxicity have been pointed out. . Organic photoreceptors have been developed to overcome these drawbacks.However, conventional electrophotographic photoreceptors using organic photoconductive materials as hole transporting materials have had problems in chargeability, sensitivity and residual potential. At present, it cannot be said that the electrophotographic properties are always satisfactory, and it has been desired to develop a hole transporting material having excellent charge transporting ability and durability.
[0007]
[Problems to be solved by the invention]
An object of the present invention is to provide a novel triphenylamine derivative useful as a durable hole transport material, a method for producing the same, and a use thereof.
[0008]
[Means for Solving the Problems]
That is, the first invention is a triphenylamine derivative represented by the general formula [1].
General formula [1]
Embedded image
General formula [2]
Embedded image
[0009]
The second invention is a method for producing a triphenylamine derivative according to
General formula [3]
Embedded image
[0010]
A third invention is a hole transport material comprising the triphenylamine derivative according to
[0011]
According to a fourth aspect of the present invention, there is provided an organic electroluminescent device comprising a light emitting layer or a plurality of organic compound thin films including a light emitting layer between a pair of electrodes, wherein at least one layer comprises the hole transport material according to claim 3. It is a luminescence element.
[0012]
According to a fifth aspect of the present invention, there is provided an electrophotographic photosensitive member using a charge generating material and a hole transporting material on a conductive support, wherein the hole transporting material is the hole transporting material according to claim 3. It is a photoreceptor.
[0013]
In the compound represented by the general formula [1] in the present invention, A 1 represents a triphenylamine compound residue represented by the general formula [2], and A 2 each independently represents a hydrogen atom or the general formula [2] Represents a triphenylamine compound residue represented by
In the formula, R 1 to R 4 are each independently a hydrogen atom or an unsubstituted alkyl group.
Specific examples of R 1 to R 4 include, as an unsubstituted alkyl group, a methyl group, an ethyl group, a propyl group, a butyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group group, there is a stearyl group, and the like.
[0014]
In the present invention, the compound represented by the general formula [1] is a novel substance and can be produced, for example, by the following method.
The 1,2-cyclohexadione is dehydrated with 4 to 5 times the molar amount of a triphenylamine compound having a substituent represented by the following general formula [3] in an acetic acid solvent using an acid catalyst such as methanesulfonic acid. Thereby, the triphenylamine derivative represented by the general formula [1] can be produced. Further, as the acid catalyst used in the present invention, organic acids such as trifluoroacetic acid and p-toluenesulfonic acid, or sulfuric acid, hydrochloric acid, Lewis acid and the like can be used instead of methanesulfonic acid. Further, as the organic solvent, in addition to acetic acid, 1,4-dioxane, ether, petroleum ether and the like are also possible. Here, when the mixing ratio of 1,2-cyclohexadione and the general formula [3] is 1: 4 or less, the number of triphenylamine compounds introduced becomes less than 4, and the reaction time is increased to 20 hours or more. , The yield of the triphenylamine derivative is improved to 50% or more.
[0015]
Hereinafter, typical examples of the compound of the present invention are specifically illustrated in Table 1, but the present invention is not limited to the following typical examples.
[0016]
[Table 1]
The triphenylamine derivative of the present invention may be used in a mixture with another hole or electron transporting compound. Since the compound of the present invention has excellent hole transporting properties, it can be used very effectively as a hole transporting material.
[0022]
The production method according to
[0023]
First, a case where the compound represented by the general formula [1] is used as a hole transport material of an organic EL device will be described. FIGS. 1 to 3 show an example of a schematic view of an organic EL device structure used in the present invention. In the figure, generally,
Since the compound of the general formula [1] has a large hole transporting ability, it can be used as a hole transporting material in any of the hole injection layer 3 and the
[0024]
In the
In the structure of FIG. 2, the
[0025]
The structure in FIG. 3 has an electron injection layer 5 in addition to the hole injection layer 3, and improves the efficiency of recombination of holes and electrons in the
[0026]
As the conductive substance used for the anode of the organic EL element, those having a work function larger than 4 eV are preferable, and carbon, aluminum, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum, palladium, etc. And alloys thereof, metal oxides such as tin oxide and indium oxide, which are called ITO substrates and NESA substrates, and organic conductive resins such as polythiophene and polypyrrole.
As the conductive material used for the cathode, those having a work function smaller than 4 eV are preferable, and magnesium, calcium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, and the like and alloys thereof are used. However, the present invention is not limited to these. The anode and the cathode may be formed of two or more layers if necessary.
[0027]
In the organic EL device, in order to efficiently emit light, it is desirable that at least one of the electrode A indicated by 2 and the electrode B indicated by 6 be sufficiently transparent in the emission wavelength region of the device. Further, it is desirable that the
[0028]
The
[0029]
Each layer of the organic EL device according to the present invention can be formed by any of dry film forming methods such as vacuum evaporation and sputtering and wet film forming methods such as spin coating and dipping. The thickness is not particularly limited, but each layer needs to be set to an appropriate thickness. When the film thickness is too large, a large applied voltage is required to obtain a constant light output, and the efficiency is deteriorated. If the film thickness is too small, pinholes or the like are generated, and sufficient light emission luminance cannot be obtained even when an electric field is applied. The normal thickness is preferably in the range of 5 nm to 10 μm, but more preferably in the range of 10 nm to 0.2 μm.
[0030]
In the case of a wet film formation method, a thin film is formed by dissolving or dispersing a material forming each layer in an appropriate solvent such as chloroform, tetrahydrofuran, dioxane, or the like. In any of the thin films, a suitable resin or additive may be used to improve film forming properties, prevent pinholes in the film, and the like.
Examples of such a resin include insulating resins such as polystyrene, polycarbonate, polyarylate, polyester, polyamide, polyurethane, polysulfone, polymethyl methacrylate, polymethyl acrylate, and cellulose; and photoconductive materials such as poly-N-vinyl carbazole and polysilane. And conductive resins such as polythiophene and polypyrrole.
[0031]
The present organic EL device may include, if necessary, a known light-emitting substance, a light-emitting auxiliary material, a hole-transporting material, an electron-emitting layer, a hole-injecting layer, and an electron-injecting layer in addition to the compound of the general formula [1]. Transport materials can also be used.
[0032]
Known light-emitting substances or auxiliary materials for light-emitting substances include anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthalopylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, Oxadiazole, aldazine, bisbenzoxazoline, bisstyryl, pyrazine, cyclopentadiene, oxine, aminoquinoline, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compound, quinacridone, Examples include, but are not limited to, rubrene and the like and derivatives thereof.
[0033]
The hole transporting material that can be used in combination with the hole transporting material of the general formula [1] has the ability to transport holes, has an excellent hole injecting effect on a light emitting layer or a light emitting substance, and emits light. Compounds that prevent excitons generated in the layer from migrating to the electron injection layer or the electron transporting material and have excellent thin film forming ability are exemplified. Specifically, phthalocyanine compounds, naphthalocyanine compounds, porphyrin compounds, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, oxazole, oxadiazole, hydrazone, acylhydrazone, poly There are arylalkanes, stilbenes, butadienes, benzidine-type triphenylamines, styrylamine-type triphenylamines, diamine-type triphenylamines, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers. However, the present invention is not limited to these.
[0034]
As an electron transport material, it has the ability to transport electrons, has an excellent electron injection effect on a light emitting layer or a light emitting substance, and transfers excitons generated in the light emitting layer to a hole injection layer or a hole transport material. Compounds that prevent migration and have excellent thin film forming ability can be used. Examples include, but are not limited to, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxadiazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and derivatives thereof. Not something.
In addition, sensitization can be performed by adding an electron accepting substance to the hole transporting material and adding an electron donating substance to the electron transporting material.
[0035]
In the organic EL devices shown in FIGS. 1, 2 and 3, the compound of the general formula [1] of the present invention can be used for any layer, and in addition to the compound of the general formula [1], a luminescent material, At least one of a light emission auxiliary material, a hole transport material, and an electron transport material may be contained in the same layer.
In order to improve the stability of the organic EL device obtained according to the present invention with respect to temperature, humidity, atmosphere, etc., a protective layer is provided on the surface of the device, or silicon oil or the like is sealed to protect the entire device. It is also possible.
As described above, in the present invention, since the compound of the general formula [1] was used for the organic EL device, the luminous efficiency and the luminous brightness could be increased. In addition, this device is extremely stable against heat and current, and furthermore, it can emit light that can be used practically at a low driving voltage, so that the deterioration, which has been a major problem until now, can be significantly reduced. Was completed.
[0036]
The organic EL device of the present invention can be applied to a flat panel display such as a wall-mounted television, a light source such as a copying machine or a printer, a light source such as a liquid crystal display or an instrument, a display board, or a sign lamp as a plane light emitter. , Its industrial value is very large.
[0037]
Next, the case where the compound represented by the general formula [1] of the present invention is used as an electrophotographic photosensitive member will be described. The compound represented by the general formula [1] of the present invention can be used in any layer of an electrophotographic photoreceptor, but is preferably used as a hole transporting material because of having high hole transporting properties. Since the compound acts as a hole transporting substance and can transport the charge generated by light absorption or the charge injected from the electrode very efficiently, it is possible to obtain a photoconductor excellent in high-speed response. Further, since the compound is excellent in ozone resistance and light stability, a photosensitive member having excellent durability can be obtained.
[0038]
An electrophotographic photoreceptor is a single-layer type photoreceptor having a photosensitive layer formed by dispersing a charge generating material on a conductive substrate and, if necessary, a charge transporting material in a binder resin, and subbing on a conductive substrate. There is a laminated photoreceptor in which a layer, a charge generation layer, and a hole transport layer are laminated in this order, or a hole transport layer and a charge generation layer are laminated in this order on a conductive substrate or an undercoat layer. Here, the undercoat layer may not be used if unnecessary. If necessary, the photoreceptor may be provided with an overcoat layer for the purpose of protecting the surface from active gas and preventing filming with toner.
[0039]
As the charge generating material, organic compounds such as bisazo, quinacridone, diketopyrrolopyrrole, indigo, perylene, perinone, polycyclic quinone, squarylium salt, azurenium salt, phthalocyanine, and naphthalocyanine, or selenium, selenium-tellurium alloy, sulfide Examples include inorganic substances such as cadmium, zinc oxide, and amorphous silicon.
[0040]
Each layer of the photoreceptor can be formed by vapor deposition or dispersion coating. The dispersion coating is performed using a spin coater, an applicator, a spray coater, a dipping coater, a roller coater, a curtain coater, a bead coater, etc., and drying is performed at room temperature to 200 ° C. for 10 minutes to 6 hours under static or blowing conditions. Do. The thickness of the photosensitive layer after drying is 5 μm to 50 μm for a single-layer type photoreceptor, and 0.01 to 5 μm, preferably 0.1 to 1 μm for a multi-layer type photoreceptor. Yes, the hole transport layer is suitably 5 to 50 microns, preferably 10 to 20 microns.
[0041]
The resin used for forming the photosensitive layer of the single-layer type photoreceptor or the charge generation layer or the hole transport layer of the laminated type photoreceptor can be selected from a wide range of insulating resins. Further, it can be selected from organic photoconductive polymers such as poly-N-vinylcarbazole, polyvinylanthracene and polysilanes. Preferably, insulating resins such as polyvinyl butyral, polyarylate, polycarbonate, polyester, phenoxy, acrylic, polyamide, urethane, epoxy, silicone, polystyrene, polyvinyl chloride, polyvinyl chloride copolymer, phenol and melamine resin are mentioned. Can be done. The resin used for forming the charge generation layer or the hole transport layer is preferably 100% by weight or less based on the charge generation material or the hole transport material, but is not limited thereto. Two or more resins may be used in combination. Further, if necessary, the resin may not be used. Further, the charge generation layer can be formed by a physical film forming method such as vapor deposition and sputtering. In the evaporation and sputtering methods, it is preferable to form a film in a vacuum atmosphere of preferably 10 −5 Toor or less. It is also possible to form a film in an inert gas such as nitrogen, argon, and helium.
[0042]
The solvent used when forming each layer of the electrophotographic photoreceptor is preferably selected from those which do not affect the undercoat layer or other photosensitive layers. Specifically, aromatic hydrocarbons such as benzene and xylene, ketones such as acetone, methyl ethyl ketone and cyclohexanone, alcohols such as methanol and ethanol, esters such as ethyl acetate and methyl cellosolve, carbon tetrachloride, chloroform and dichloromethane But aliphatic halogenated hydrocarbons such as dichloroethane and trichloroethylene, aromatic halogenated hydrocarbons such as chlorobenzene and dichlorobenzene, and ethers such as tetrahydrofuran and dioxane are used, but are not limited thereto.
[0043]
The hole transport layer is formed by applying only the hole transport material or a coating solution obtained by dissolving the hole transport material in a resin. The hole transport material used in the present photoreceptor can be used in combination with another hole transport material in addition to the compound represented by the general formula [1]. The compound of the general formula [1] is advantageous for improving sensitivity and durability since it has good compatibility with the resin and does not easily precipitate crystals.
[0044]
If necessary, an undercoat layer can be provided between the substrate and the organic layer to improve electrophotographic properties, image properties, and the like. Examples of the undercoat layer include polyamides, casein, polyvinyl alcohol, gelatin, and polyvinyl butyral. And the like, and metal oxides such as aluminum oxide.
[0045]
The material of the present invention can be suitably used not only as a hole transport material of an organic EL device or an electrophotographic photosensitive member, but also in the fields of photoelectric conversion devices, solar cells, image sensors, and the like.
[0046]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples.
Method for synthesizing compound (1) In 18 parts of acetic acid, 5 parts of 1,2-cyclohexadione, 15 parts of triphenylamine and 1.5 parts of methanesulfonic acid were added, and the mixture was heated at 100 ° C for 20 hours. The mixture was heated and stirred. Thereafter, the mixture was diluted with 500 parts of water and neutralized with a dilute aqueous sodium hydroxide solution. Thereafter, extraction was performed with ethyl acetate, concentrated, and purified by column chromatography using silica gel to obtain 6 parts of a powder having white fluorescence. As a result of molecular weight analysis, it was confirmed that the product was Compound (1).
The results of elemental analysis of the product are shown below.
Elemental analysis result: calculated as C 78 H 64 N 4 (%): C: 88.64 H: 6.06 N: 5.30
Obtained value (%): C: 88.39 H: 6.22 N: 5.39
FIG. 6 shows the infrared absorption spectrum (KBr tablet method) of this compound.
[0047]
Synthesis method of compound (3) In 30 parts of acetic acid, 7 parts of 1,2-cyclohexadione, 23 parts of 4,4-dimethyltriphenylamine, and 2 parts of methanesulfonic acid were added, and the mixture was heated to 105 ° C. For 30 hours. Thereafter, the mixture was diluted with 500 parts of water and neutralized with a dilute aqueous sodium hydroxide solution. After that, extraction was performed with ethyl acetate, concentrated, and purified by column chromatography using silica gel to obtain 10 parts of a powder having yellow fluorescence. As a result of molecular weight analysis, it was confirmed to be Compound (3).
The results of elemental analysis of the product are shown below.
Elemental analysis: calculated value as C 86 H 76 N 4 (%): C: 88.66 H: 6.53 N: 4.81
Obtained value (%): C: 88.45 H: 6.81 N: 4.74
FIG. 7 shows the infrared absorption spectrum (KBr tablet method) of this compound.
[0048]
Example 1
Compound (2), tris (8-hydroxyquinoline) aluminum complex, and polycarbonate resin (PC-A) were dissolved in tetrahydrofuran in a ratio of 3: 2: 5 on a washed glass plate with an ITO electrode, and spin-coating was performed. A light emitting layer having a thickness of 100 nm was obtained. An electrode having a thickness of 150 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain the organic EL device shown in FIG. This device emitted light of 150 cd / m 2 at a DC voltage of 5 V.
[0049]
Example 2
Compound (3) was dissolved in tetrahydrofuran on a washed glass plate with an ITO electrode, and a hole injection layer having a thickness of 50 nm was obtained by spin coating. Next, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to form a light-emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1. Thus, an organic EL device shown in FIG. 2 was obtained. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emitted light of about 270 cd / m 2 at a DC voltage of 5 V.
[0050]
Example 3
Compound (5) was dissolved in tetrahydrofuran on a washed glass plate with an ITO electrode, and a hole injection layer having a thickness of 50 nm was obtained by spin coating. Next, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to form a light-emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1. Thus, an organic EL device shown in FIG. 2 was obtained. The light emitting layer was deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emitted light of about 450 cd / m 2 at a DC voltage of 5 V.
[0051]
Example 4
The compound (6) was vacuum-deposited on the washed glass plate with an ITO electrode to obtain a 20-nm-thick hole injection layer. Further, N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine was vacuum-deposited to obtain a hole transport layer having a thickness of 30 nm. Was. Next, a tris (8-hydroxyquinoline) aluminum complex was vacuum-deposited to form a light-emitting layer having a thickness of 30 nm, and an electrode having a thickness of 100 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1. Thus, an organic EL device was obtained. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emitted light of about 330 cd / m 2 at a DC voltage of 5 V.
[0052]
Example 5
N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-biphenyl-4,4'-diamine is vacuum-deposited on the washed glass plate with the ITO electrode to form a film. A 50-nm hole injection layer was obtained. Next, a tris (8-hydroxyquinoline) aluminum complex and the compound (10) were vacuum-deposited at a ratio of 3: 1 to form a 50 nm-thick light-emitting layer, on which magnesium and silver were mixed at a ratio of 10: 1. An electrode having a thickness of 150 nm was formed from the alloy thus obtained to obtain an organic EL device shown in FIG. The hole injection layer and the light emitting layer were deposited in a vacuum of 10 −6 Torr at a substrate temperature of room temperature. This device emitted light of about 370 cd / m 2 at a DC voltage of 5 V.
[0053]
Example 6
Compound (4) was dissolved in chloroform on the washed glass plate with an ITO electrode, and a hole injection layer having a thickness of 50 nm was obtained by spin coating. Next, a 50 nm-thick luminescent layer of a tris (8-hydroxyquinoline) aluminum complex was formed by a vacuum evaporation method, and [2- (4-tert-butylphenyl) -5- (biphenyl) -1 was further formed by a vacuum evaporation method. , 3,4-oxadiazole] with a thickness of 20 nm. An electrode having a thickness of 150 nm was formed thereon using an alloy in which magnesium and silver were mixed at a ratio of 10: 1 to obtain the organic EL device shown in FIG. This device emitted light of about 550 cd / m 2 at a DC voltage of 5 V.
[0054]
When continuous light emission was performed at 1 mA / cm 2 for all of the organic EL elements shown in this example, stable light emission could be observed for 1000 hours or more.
The organic EL device of the present invention achieves improvement in luminous efficiency, luminous luminance and long life, and is used together with a luminescent substance, a luminescent auxiliary material, a hole transport material, an electron transport material, a sensitizer, It does not limit the resin, the electrode material and the like, and the element manufacturing method.
[0055]
Example 7
4 g of ε-type copper phthalocyanine, 2 g of the compound (1), and 14 g of a polyester resin (Vylon 200: manufactured by Toyo Defense Co., Ltd.) were dispersed together with 80 g of tetrahydrofuran in a ball mill for 5 hours. This dispersion was applied on an aluminum substrate and dried to produce a single-layer electrophotographic photosensitive member having a thickness of 20 μm as shown in FIG.
[0056]
Example 8
6 g of dibromoanthanthrone, 2 g of the compound (3), and 12 g of a polyester resin (Vylon 200: manufactured by Toyo Defense Co., Ltd.) were dispersed together with 80 g of tetrahydrofuran in a ball mill for 5 hours. This dispersion was applied on an aluminum substrate and dried to produce a single-layer electrophotographic photosensitive member having a thickness of 20 μm as shown in FIG.
[0057]
Example 9
2 g of τ-type metal-free phthalocyanine and 2 g of polyvinyl butyral resin (BH-3: manufactured by Sekisui Chemical Co., Ltd.) were dispersed together with 96 g of tetrahydrofuran in a ball mill for 2 hours. This dispersion was applied on an aluminum substrate and dried to form a charge generation layer having a thickness of 0.3 μm. Next, 10 g of the compound (4) and 10 g of a polycarbonate resin (L-1250; manufactured by Teijin Chemicals Ltd.) were dissolved in 80 g of dichloromethane. This coating liquid was applied on the charge generating layer and dried to form a charge transporting layer having a thickness of 20 μm, thereby producing a laminated electrophotographic photosensitive member shown in FIG.
[0058]
Example 10
2 g of N, N'-bis (2,6-dichlorophenyl) -3,4,9,10-perylenedicarboximide and 2 g of polyvinyl butyral resin (BH-3: manufactured by Sekisui Chemical Co., Ltd.) together with 96 g of tetrahydrofuran in a ball mill. Dispersed for 2 hours. This dispersion was applied on an aluminum substrate and dried to form a charge generation layer having a thickness of 0.3 μm. Next, 10 g of the compound (6) and 10 g of a polycarbonate resin (L-1250; manufactured by Teijin Chemicals Ltd.) were dissolved in 80 g of dichloromethane. This coating liquid was applied on the charge generating layer and dried to form a charge transporting layer having a thickness of 20 μm, thereby producing a laminated electrophotographic photosensitive member shown in FIG.
[0059]
The electrophotographic characteristics of the electrophotographic photosensitive member were measured by the following method.
[0060]
[Table 2]
When the electrophotographic characteristics were measured repeatedly 10,000 times or more, stable surface potential and sensitivity could be obtained for all the electrophotographic photosensitive members shown in this example.
[0062]
【The invention's effect】
According to the present invention, a compound having excellent hole transporting ability can be obtained. The compound provided by the present invention has higher luminous efficiency and higher brightness than conventional ones, and has excellent long-lifetime organic EL devices and excellent initial electrophotographic properties such as sensitivity, hole transport properties, initial surface potential, and dark decay rate. Thus, an electrophotographic photoreceptor having less fatigue due to repeated use could be obtained.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view illustrating a schematic structure of an organic EL element used in an example. FIG. 2 is a cross-sectional view illustrating a schematic structure of an organic EL element used in an example. FIG. 3 is an organic EL element used in an example. FIG. 4 is a cross-sectional view illustrating a schematic structure of an electrophotographic photoreceptor used in Examples. FIG. 5 is a cross-sectional view illustrating a schematic structure of an electrophotographic photoreceptor used in Examples. Infrared absorption spectrum of Compound 1 [Figure 7] Infrared absorption spectrum of Compound 3 [Explanation of symbols]
1.
3. 3. hole injection layer Light emitting layer5. 5. electron injection layer Electrode B
7. 7. Al substrate Photosensitive layer9.
Claims (5)
一般式［１］
一般式［２］
General formula [1]
General formula [2]
一般式［３］
General formula [3]
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP18320194A JP3593719B2 (en) | 1994-08-04 | 1994-08-04 | Novel triphenylamine derivative, its production method and use |
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| JP18320194A JP3593719B2 (en) | 1994-08-04 | 1994-08-04 | Novel triphenylamine derivative, its production method and use |
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| CN1123278C (en) | 1996-05-15 | 2003-10-01 | 高化化成株式会社 | Multicolor organic element, method for manufacturing the same, and display using the same |
| JPH10270171A (en) * | 1997-01-27 | 1998-10-09 | Junji Kido | Organic electroluminescent element |
| JP2998707B2 (en) | 1997-07-09 | 2000-01-11 | 日本電気株式会社 | Organic electroluminescence device |
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| JPH11251067A (en) | 1998-03-02 | 1999-09-17 | Junji Kido | Organic electroluminescence element |
| JP2956691B1 (en) | 1998-05-22 | 1999-10-04 | 日本電気株式会社 | Organic electroluminescence device |
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| US6180267B1 (en) | 1999-01-08 | 2001-01-30 | Nec Corporation | Organic electroluminescent device containing a 1,3-dibenzylideneindane compound |
| KR20010050711A (en) | 1999-09-29 | 2001-06-15 | 준지 키도 | Organic electroluminescent device, group of organic electroluminescent devices and controlling method of emission spectrum in such devices |
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| US6899961B2 (en) | 1999-12-15 | 2005-05-31 | Samsung Sdi Co., Ltd. | Organic electroluminescence device |
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| US6746784B2 (en) | 2000-11-07 | 2004-06-08 | Samsung Electronics Co., Ltd. | Organic electroluminescent device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2840372B2 (en) * | 1990-04-11 | 1998-12-24 | 出光興産株式会社 | Method for producing hydroxyarylamine compound |
| JP3150330B2 (en) * | 1990-09-19 | 2001-03-26 | 株式会社東芝 | Organic thin film element |
| JPH04178487A (en) * | 1990-11-13 | 1992-06-25 | Nec Corp | Organic thin film el element |
| JP3476855B2 (en) * | 1992-01-07 | 2003-12-10 | 株式会社東芝 | Organic EL device |
| JP3296147B2 (en) * | 1994-08-04 | 2002-06-24 | 東洋インキ製造株式会社 | Triphenylamine polymer, its production method and use |
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