JP2004269698A - Organic electroluminescent device material and organic electroluminescent device using the same - Google Patents
Organic electroluminescent device material and organic electroluminescent device using the same Download PDFInfo
- Publication number
- JP2004269698A JP2004269698A JP2003062620A JP2003062620A JP2004269698A JP 2004269698 A JP2004269698 A JP 2004269698A JP 2003062620 A JP2003062620 A JP 2003062620A JP 2003062620 A JP2003062620 A JP 2003062620A JP 2004269698 A JP2004269698 A JP 2004269698A
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- organic
- light emitting
- general formula
- emitting layer
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Abstract
Description
【０００１】
【発明の属する技術分野】
本発明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）素子などに用いられる発光材料および高輝度の発光素子に関するものである。
【０００２】
【従来の技術】
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素子は、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、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。
【０００３】
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（非特許文献１参照）。この方法は、金属キレート錯体を発光層、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１０００ｃｄ／ｍ２に達している。しかしながら、有機化合物の蒸着操作を伴うＥＬ素子作成は、生産性に問題が有り、製造工程の簡略化、大面積化の観点から、塗布方式の素子作成が望ましい。
【０００４】
生産性に有利な塗布方式のＥＬ素子作成で使用されるＥＬ素子の発光材料としては、ポリフェニレンビニレン系ポリマーが知られているが、（非特許文献２および３参照）、発光部をポリマー主鎖に持つため、発光材料の濃度制御が難しく、色調、発光強度の微妙な制御が難しい等の問題があった。同じく、塗布方式を用いるＥＬ素子として、例えばポリビニルカルバゾール中に、低分子量色素を分散する素子（特許文献１参照）がある。色素種、色素濃度を任意に変更出来るので、色調、発光強度の調整が比較的容易であるが、駆動電圧が高く、連続駆動時の耐久性に問題がある。
【０００５】
塗布方式に用いる有機発光素子材料として溶解性に優れた発光ポリマー（特許文献２〜４参照）を、また塗布方式に用いる電荷輸送材料として電荷輸送性ポリエーテルの提案がある（特許文献５参照）。これらの材料は塗布による薄膜化が可能であり、エレクトロルミネセンス素子の発光が開示されている。しかしながら、発光特性に乏しく、耐久性にも問題があった。
赤色発光する発光材料としては、ＤＰＰ（ジケトピロロピロール）骨格を含有する発光ポリマー（特許文献６参照）がある。しかし、このポリマーはＤＰＰと１：１で重合すると汎用性溶媒に対する溶解性が乏しくなり、製膜性も悪い。従って、ＥＬ素子の発光面に、輝度ムラが見られる。
【０００６】
【非特許文献１】アプライド・フィジクス・レターズ、５１巻、９１３ページ、１９８７年
【非特許文献２】アドバンストマテーリアルズ ２巻、４ページ １９９２年
【非特許文献３】アドバンストマテーリアルズ ９巻、５５１ページ １９９７年
【特許文献１】特開平４−２１２２８６号公報
【特許文献２】特開平５−３２０６３５号公報
【特許文献３】特開平１０−３３５０６５号公報
【特許文献４】特開平８−２５９６７８号公報
【特許文献５】特開２００２−７５６５４号公報
【特許文献６】特開２００１−９８０５４号公報
【０００７】
【発明が解決しようとする課題】
【０００８】
本発明の目的は、発光輝度が高く、長い発光寿命を持つ有機ＥＬ素子用発光材料およびそれを用いた有機ＥＬ素子の提供にある。本発明者らが鋭意検討した結果、一般式［１］で示される特定の共役ユニットを有するポリマーを発光材料として使用する事により、有機ＥＬ素子は発光輝度および発光効率が飛躍的に向上することを見いだした。
【０００９】
【課題を解決するための手段】
本発明は、共役ユニットと、非共役ユニットからなる重量平均分子量１０００以上のポリマーからなる有機エレクトロルミネッセンス素子材料であって、共役ユニットが、下記一般式［１］で示されるユニットを含む有機エレクトロルミネッセンス素子材料に関する。
一般式［１］
【化３】
【００１０】
また、本発明は、非共役ユニットが、下記一般式［２］で示されるユニットのいずれかである上記エレクトロルミネッセンス素子材料に関する。
一般式［２］
【化４】
Ｒ３は、水素原子、アルキル基またはアリール基を表す。］
【００１１】
また、本発明は、共役ユニットが、一般式［１］以外のアリール基もしくは複素環式基と、一般式［１］で示されるユニットとからなる上記エレクトロルミネッセンス素子材料に関する。
【００１２】
また、本発明は、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形成してなる有機エレクトロルミネセンス素子において、前記有機層のうち少なくとも１層が、上記材料を単独もしくは混合物として含有することを特徴とする有機エレクトロルミネセンス素子に関する。
【００１３】
また、本発明は、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形成してなる有機エレクトロルミネッセンス素子において、発光層が、上記材料を単独もしくは混合物として含有することを特徴とする有機エレクトロルミネセンス素子に関する。
【００１４】
【発明の実施の形態】
本発明は、有機エレクトロルミネッセンス素子において、発光層に、一般式［１］で示されるポリマーが新規な有機発光材料として含まれることを特徴とする。
【００１５】
本発明は、共役ユニットと、非共役ユニット（Ｂ）からなる分子量１０００以上のポリマーからなる有機エレクトロルミネッセンス素子材料に関する。
本発明において、共役ユニットは、一般式［１］で示されるＤＰＰ骨格のユニットと、一般式［１］以外の共役ユニット（Ａ）からなる。一般式［１］以外の共役ユニット（Ａ）は、さらに、アリール基、複素環式基、エテニル基などを含む。
本発明において、非共役ユニット（Ｂ）として、一般式［２］で示される非共役ユニットが挙げられる。
本発明における一般式［１］および一般式［２］のＲ１〜Ｒ３で示されるアルキル基としては、好ましくは炭素数６から３０であり、置換もしくは無置換の、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。
アルコキシ基としては、好ましくは炭素数６から３０であり、置換もしくは無置換の、メトキシ基、エトキシ基、プロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、ステアリルオキシ基等がある。
チオアルコキシ基としては、好ましくは炭素数６から３０であり、置換もしくは無置換の、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ｓｅｃ−ブチルチオ基、ｔｅｒｔ−ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、オクチルチオ基等がある。
【００１６】
本発明における一般式［１］および一般式［２］のＲ１〜Ｒ３で示される、炭素数６から３０のアリール基としては、置換もしくは無置換の、フェニル基、ビフェニレニル基、トリフェニレニル基、テトラフェニレニル基、３−ニトロフェニル基、４−メチルチオフェニル基、３，５−ジシアノフェニル基、ｏ−，ｍ−およびｐ−トリル基、キシリル基、ｏ−，ｍ−およびｐ−クメニル基、メシチル基、ペンタレニル基、インデニル基、ナフチル基、アズレニル基、ヘプタレニル基、アセナフチレニル基、フェナレニル基、フルオレニル基、アントリル基、アントラキノニル基、３−メチルアントリル基、フェナントリル基、トリフェニレニル基、ピレニル基、クリセニル基、２−エチル−１−クリセニル基、ピセニル基、ペリレニル基、６−クロロペリレニル基、ペンタフェニル基、ペンタセニル基、テトラフェニレニル基、ヘキサフェニル基、ヘキサセニル基、ルビセニル基、コロネニル基、トリナフチレニル基、ヘプタフェニル基、ヘプタセニル基、ピラントレニル基、オバレニル基等がある。
【００１７】
複素環式基としては、置換もしくは無置換の、チオニル基、フリル基、ピロリル基、イミダゾリル基、ピラゾリル基、ピリジル基、ピラジニル基、ピリミジニル基、ピリダジニル基、インドリル基、キノリル基、イソキノリル基、フタラジニル基、キノキサリニル基、キナゾリニル基、カルバゾリル基、アクリジニル基、フェナジニル基、フルフリル基、イソチアゾリル基、イソキサゾリル基、フラザニル基、フェノキサジニル基、ベンゾチアゾリル基、ベンゾオキサゾリル基、ベンズイミダゾリル基、２−メチルピリジル基、３−シアノピリジル基等がある。
【００１８】
本発明における共役ユニット（Ａ）は、前記置換もしくは無置換の、アリール基もしくは複素環式基から水素原子を１個除いた二価の基を上げる事が出来る。さらに、エテニル基、エチニル基などが挙げられる。また、同種または異種の共役ユニットが連続していても良い。
【００１９】
一般式［１］で示される共役ユニット（Ａ）の代表例を具体的に表１に例示するが、これらに限定されるものではない。
表１
【００２０】
【表１】
次に、一般式［１］で示される非共役ユニット（Ｂ）の代表例を具体的に表２に例示するが、これらに限定されるものではない。
表２
【００２４】
【表２】
本発明における置換基とは、ハロゲン原子、置換もしくは未置換のアルキル基、置換もしくは未置換のアルコキシ基、置換もしくは未置換のチオアルコキシ基、シアノ基、アミノ基、モノもしくはジ置換アミノ基、水酸基、メルカルト基、置換もしくは未置換のアリールオキシ基、置換もしくは未置換のアリールチオ基、置換もしくは未置換のアリール基、置換もしくは未置換のヘテロアリール基が挙げられ、また置換基は、隣接した置換基同士で置換もしくは未置換の環を形成しても良い。
【００２８】
置換もしく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、２−エチルヘキシル基、ヘプチル基、オクチル基、イソオクチル基、ステアリル基、トリクロロメチル基、トリフロロメチル基、シクロプロピル基、シクロヘキシル基、１，３−シクロヘキサジエニル基、２−シクロペンテン−１−イル基、２，４−シクロペンタジエン−１−イリデニル基などがある。
【００２９】
置換もしくは未置換のアルコキシ基としては、メトキシ基、エトキシ基、プロポキシ基、ｎ−ブトキシ基、ｓｅｃ−ブトキシ基、ｔｅｒｔ−ブトキシ基、ペンチルオキシ基、ヘキシルオキシ基、２−エチルヘキシルオキシ基、ステアリルオキシ基、トリフロロメトキシ基等がある。
【００３０】
置換もしくは未置換のチオアルコキシ基としては、メチルチオ基、エチルチオ基、プロピルチオ基、ブチルチオ基、ｓｅｃ−ブチルチオ基、ｔｅｒｔ−ブチルチオ基、ペンチルチオ基、ヘキシルチオ基、ヘプチルチオ基、オクチルチオ基等がある。
【００３１】
置換もしくは未置換のアリールオキシ基としては、フェノキシ基、ｐ−ｔｅｒｔ−ブチルフェニキシ基、３−フルオロフェニキシ基等がある。
【００３２】
置換もしくは未置換のアリールチオ基としては、フェニルチオ基、３−フルオロフェニルチオ基等がある。
【００３３】
モノまたはジ置換アミノ基としては、メチルアミノ基、ジメチルアミノ基、エチルアミノ基、ジエチルアミノ基、ジプロピルアミノ基、ジブチルアミノ基、ジフェニルアミノ基、ビス（アセトオキシメチル）アミノ基、ビス（アセトオキシエチル）アミノ基、ビス（アセトオキシプロピル）アミノ基、ビス（アセトオキシブチル）アミノ基、ジベンジルアミノ基等がある。
【００３４】
好ましい置換基しては、水素原子、炭素数が１〜２０のアルキル基、もしくはアルコキシ基である。また、隣接した置換基同士で５ないし７員環の酸素原子、窒素原子、硫黄原子等が含まれてもよい脂肪族、炭素環式芳香族、複素環式芳香族、複素環を形成してもよく、これらの環の任意の位置にさらに置換基を有してもよい。
【００３５】
なお、本発明の高分子ＥＬ発光材料はランダム、ブロック、またはグラフト共重合体であってもよく、それらの中間的な構造を有する高分子たとえばブロック性をもつランダム共重合体であってもよい。発光効率の高い共重合体を得る観点からは完全なランダム共重合体よりもブロック性を帯びたランダム共重合体やブロックまたはグラフト共重合体が好ましい。
【００３６】
ポリマー中に含まれる共役ユニットと、非共役ユニットとの比率については、非共役ユニット１に対して共役ユニットが重量比で１〜５０が好ましい。
また、本発明のエレクトロルミネッセンス素子材料は、重量平均分子量が１０００以上が汎用性有機溶媒に対する溶解性の点で好ましい。
本発明のエレクトロルミネッセンス素子材料は主鎖に剛直な共役部分と柔軟な連結部分を有するため基本的には溶剤に溶解させて製膜することは困難ではないがより溶解性に優れ製膜性のよい重合体を得るためにはポリマー１分子あたり少なくとも一つ一般式［２］で表されるユニットを含むことが好ましい。
【００３７】
本発明で使用されるポリマーの製造方法について述べる。本発明で使用されるポリマーは種々の方法で合成が可能である。たとえばアリールハライドをニッケルまたは銅誘導体存在下ホモカップリングし、炭素炭素結合を生成する重合法、アリールハライド誘導体とビニルベンゼン誘導体をパラジウム触媒下反応させ炭素炭素結合を生成する重合法、ホウ酸誘導体またはホウ酸エステル誘導体とアリールハライド誘導体をパラジウム触媒存在下反応させて炭素炭素結合を生成する重合法、アリールスズ誘導体とアリールハライド誘導体をパラジウム触媒存在下反応させて炭素炭素結合を生成する重合法が挙げられるが、ホウ酸誘導体またはホウ酸エステル誘導体とアリールハライド誘導体をパラジウム触媒存在下反応させて炭素炭素結合を生成する重合法およびアリールハライドをニッケルまたは銅誘導体存在下ホモカップリングし、炭素炭素結合を生成する重合法が特に好ましい。
【００３８】
ホウ酸誘導体としては置換または未置換アリールホウ素誘導体、置換または未置換へテロアリールホウ素誘導体があり、置換または未置換アリールホウ素誘導体としては１、４−フェニルジホウ酸、４、４’−ビフェニルジホウ酸等が挙げられ、置換または未置換へテロアリールホウ素誘導体としてはピリジルジホウ酸、チエニルジホウ酸等が挙げられる。ホウ酸エステル誘導体としては置換または未置換のアリールホウ酸エステル誘導体、置換または未置換のヘテロアリールホウ酸エステル誘導体があり、例えば置換または未置換のアリールホウ酸エステル誘導体ではフェニルジホウ酸ピナコールエステル、置換または未置換のヘテロアリールホウ酸エステル誘導体ではチエニルジホウ酸ピナコールエステル等が挙げられる。
【００３９】
アリールハライド誘導体としてはハロゲン原子として塩素原子、臭素原子、ヨウ素原子があり、好ましくは臭素原子である。アリールハライド誘導体としてはジブロモベンゼン誘導体、ジブロモフルオレン誘導体、ジブロモナフタレン誘導体等が挙げられ、ヘテロアリールハライド誘導体としてはジブロモチオフェン誘導体、ジブロモピリジン誘導体等が挙げられる。
【００４０】
本発明においてパラジウム触媒としてはテトラキストリフェニルホスフフィンパラジウム、パラジウムカーボン、パラジウムジクロライド１，１’−ビスジフェニルホスフィノフェロセン等が挙げられる。トリフェニルホスフィンなどの配位子を同時に添加してもよい。また、本反応は塩基を用いることが好ましい。塩基としては炭酸ナトリウム、炭酸水素ナトリウム、酢酸ナトリウム、トリエチルアミン等が挙げられる。
【００４１】
本発明において、ニッケル触媒としてはビスシクロオクタジエンニッケル等があり、同時に２−２’−ビピリジンやシクロオクタジエンなどの配位子を同時に添加してもよい。
【００４２】
本発明で使用されるポリマーの代表例を表３に具体的に示すが、本発明で使用されるポリマーは以下の代表例に限定されるものではない。なお、表の構造式は、組成比を示すものであって、必ずしもブロック共重合体の配列を取っているものではない。
【００４３】
【表３】
本発明の発光材料は、同一層中で他の発光材料、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。本発明の発光材料は発光性、正孔輸送性に優れているので、正孔輸送性発光材料としても有効に使用することができる。
【００４５】
本発明の発光材料と共に発光層に使用できる発光材料またはドーパント材料としては、ポリアルキルフルオレン誘導体、およびポリフェニレン誘導体、ポリフェニレンビニレン誘導体、ポリチオフェン誘導体、その他発光性高分子を使用できる。また、この他に、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、キノリン金属錯体、アミノキノリン金属錯体、ベンゾキノリン金属錯体、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、ルブレンおよび色素レーザー用や増感用の蛍光色素等があるが、これらに限定されるものではない。
【００４６】
本発明の発光材料および共に発光層に使用できる上記の化合物の発光層中での存在比率はどれが主成分であってもよい。つまり、上記の化合物および本発明における化合物のそれぞれの組み合わせにより、本発明における化合物は発光層を形成する主材料にも他の主材料中へのドーパント材料にも成り得る。
【００４７】
本発明でいうドーピング材料には含まれる共役系高分子とは、炭素−炭素または炭素−ヘテロ原子を含む二重結合（または、三重結合）が単結合と交互に長く連なった共役系を分子骨格とした共役系高分子である。さらに詳しくは、炭素−炭素の単結合と二重結合が交互に長く連なった脂肪族共役系であるポリアセチレン、芳香族炭化水素が長く結合する事により共役が発達した芳香族共役系であるポリ（パラフェニレン）、ポリ（アルキルフルオレン）誘導体、複素環化合物が結合して共役系が発達した複素環式共役系であるポリピロール、ポリチオフェン、脂肪族または芳香族の共役系をヘテロ原子で結合した含ヘテロ原子共役系であるポリアニリン、上記各種共役系の構成単位が交互に結合した混合型共役系であるポリ（フェニレンビニレン）等が上げられる。
【００４８】
本発明の一般式［１］で表される化合物の発光層中での存在比率はどれが主成分であってもよい。つまり、発光層を形成する主材料にも他の主材料中へのドーピンク材料にも成り得る。上記共役系高分子に、本発明の一般式［１］で表される化合物を混合させる条件としては、両者全体に対して、１〜９０重量％の割合で用いる。この含有比率が１重量％未満では、一般式［１］で表される化合物の効果が充分に発揮されず、本発明の目的が達成されない。此処で言う効果とは、一般式［１］で表される化合物を加えたことにより、ＥＬの発光輝度の向上、効率に向上、発光開始電圧の低電圧化を示している。両者を混合する方法は、公知の方法が用いられ、例えば、上記共役系高分子と、一般式［１］で表される化合物を正確に秤量し、遮光密閉容器中で混合し、これに、トルエン、キシレンのような汎用性有機溶媒を両者全体に対して０．５〜５．０重量％になる割合で加え、超音波もしくは緩い加熱により溶解させる。
【００４９】
発光層には、必要があれば、本発明の発光材料に加えて、さらなる正孔注入材料や電子注入材料を使用することもできる。有機ＥＬ素子は、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。必要があれば、発光材料、ドーパント材料、正孔注入材料や電子注入材料を組み合わせて使用することが出来る。また、ドーパント材料により、発光輝度や発光効率の向上、赤色や青色の発光を得ることもできる。また、正孔注入帯域、発光層、電子注入帯域は、それぞれ二層以上の層構成により形成されても良い。その際には、正孔注入帯域の場合、電極から正孔を注入する層を正孔注入層、正孔注入層から正孔を受け取り発光層まで正孔を輸送する層を正孔輸送層と呼ぶ。同様に、電子注入帯域の場合、電極から電子を注入する層を電子注入層、電子注入層から電子を受け取り発光層まで電子を輸送する層を電子輸送層と呼ぶ。これらの各層は、材料のエネルギー準位、耐熱性、有機層もしくは金属電極との密着性等の各要因により選択されて使用される。
【００５０】
正孔注入材料としては、正孔を輸送する能力を持ち、陽極からの正孔注入効果、発光層または発光材料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帯域または電子注入材料への移動を防止し、かつ薄膜形成能力の優れた化合物が挙げられる。具体的には、ＰＥＤＯＴ、フタロシアニン誘導体、ナフタロシアニン誘導体、ポルフィリン誘導体、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、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、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。
【００５１】
電子注入材料としては、電子を輸送する能力を持ち、陰極からの正孔注入効果、発光層または発光材料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帯域への移動を防止し、かつ薄膜形成能力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、オキサゾール、オキサジアゾール、トリアゾール、イミダゾール、ペリレンテトラカルボン酸、フレオレニリデンメタン、アントラキノジメタン、アントロン等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、正孔注入材料に電子受容物質を、電子注入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。
【００５２】
本発明の発光材料は、ガラス転移点や融点が高い為、電界発光時における有機層中、有機層間もしくは、有機層と金属電極間で発生するジュール熱に対する耐性（耐熱性）が向上するので、有機ＥＬ素子材料として使用した場合、高い発光輝度を示し、長時間発光させる際にも有利である。
【００５３】
本発明の高分子の成膜方法としては、特に限定はなく、例えば粉末状態からの真空蒸着法、溶媒に溶解した後、塗布する方法（例えばインクジェット法、スプレイ法、印刷法、スピンコーテング法、キャスチング法、デッピング法、バーコート法、ロールコート法など）などを用いることが出来るが、素子製造工程の簡略化、加工性、大面積化の観点から塗布方式が好ましい。塗布方式で成膜する場合に用いる溶媒としては、ジクロロエタン、ジクロロメタン、クロロホルム、などの有機ハロゲン系溶媒、テトラヒドロフラン、１．４−ジオキサンなどのエーテル系溶媒、トルエン、キシレンなどの芳香族炭化水素系溶媒、ジメチルホルムアミド、ジメチルアセトアミドなどのアミド系溶媒、酢酸エチル、酢酸ブチルなどのエステル系溶媒、またはこれらの混合溶媒であっても良い。高分子の構造、分子量によっても異なるが、通常溶媒の０．０１から１０重量％、好ましくは０．１から５重量％溶解した溶液を用いて成膜する。
【００５４】
有機ＥＬ素子は、陽極と陰極間に一層もしくは多層の有機薄膜を形成した素子である。一層型の場合、陽極と陰極との間に発光層を設けている。発光層は、発光材料を含有し、それに加えて陽極から注入した正孔、もしくは陰極から注入した電子を発光材料まで輸送させるために、正孔注入材料もしくは電子注入材料を含有しても良い。多層型は、（陽極／正孔注入帯域／発光層／陰極）、（陽極／発光層／電子注入帯域／陰極）、（陽極／正孔注入帯域／発光層／電子注入帯域／陰極）の多層構成で積層した有機ＥＬ素子がある。
【００５５】
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、バリウム、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。
【００５６】
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。
【００５７】
【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。説明中、部は重量部、％は重量％を表す。
製造例１
化合物１の合成方法
【００５８】
反応モノマーとして以下の化合物（７）を用いた。
化合物（７）
【００５９】
【化５】
四つ口フラスコに２ｍｌのＤＭＦと２， ２’−ビピリジン（０．３４ｇ， ２．１６ｍｍｏｌ）とＮｉ（ｃｏｄ）２ （０．６ｇ， ２．１６ｍｍｏｌ） を加え、撹拌した。Ｎｉ（ｃｏｄ）２（ｂｐｙ） の生成に伴い、反応溶液は黄色から褐色に変化した。あらかじめＤＭＦに溶かしておいた９， ９’−（２−エチルヘキシル）ジブロモフルオレン （０．８２ｇ， １．５ ｍｍｏｌ）、化合物（７）（０．４ｇ， ０．６ｍｍｏｌ）、ビス（４−ブロモフェニル）エーテル（０．２ｇ０．６ｍｍｏｌ）を滴下した。滴下終了後、四つ口フラスコに冷却管を装着し、８０℃で２４時間撹拌させた。反応終了後、大過剰のメタノールに注ぎ、３時間洗浄した。沈殿物をろ過した後、沈殿物を少量のＴＨＦに溶かし、再び大過剰のメタノールに注いだ。２４時間撹拌した後、沈殿物をろ過し、真空乾燥して目的物を得た。生成物は元素分析、ＩＲスペクトル、ＮＭＲにより目的物であることを確認した。収率は６８％であった。
化合物２の合成方法
【００６１】
反応モノマーとして以下の化合物（８）を用いた。
化合物（８）
【００６２】
【化６】
四つ口フラスコに冷却管をつけ、化合物（８）（０．６２ｇ， １．００ｍｍｏｌ）、９， ９’−（ヘキシル）フルオレン−２，７−ボロニックアシッド１， ３ − プロパンジオールジエステル （１．００ｇ， ２．００ｍｍｏｌ） 、ビス（４−ブロモフェニル）エーテル（０．３３ｇ、１．００ｍｍｏｌ）にＴＨＦ （３０ｍｌ） を加えて撹拌した。ここにＮａＨＣＯ３ （３．１７ｇ， ３７．８ｍｍｏｌ） およびＨ２Ｏ （３０ｍｌ） を加えた。テトラキストリフェニルホスフィンパラジウム（０） （Ｐｄ（ＰＰｈ３）） （４３．７ｍｇ， ３７．８μｍｏｌ） およびＴＨＦ （６０ｍｌ） を加え、８０℃で７２時間環留した。目的物をメタノールで洗浄した。収率は６９％であった。化合物（２）の、フイルムの蛍光スペクトルを、図１に示す。
【００６４】
以下に本発明の発光材料を用いた実施例を具体的に示すが、本発明はこれにより限定されるものではない。
実施例１
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴ（ポリエチレンオキシチオフェン ポリスチレンスルホネート共重合体）をスピンコート法で５０ｎｍの膜厚に製膜し、次に、表３の化合物（２）を２％の濃度でトルエンに溶解させ、スピンコーティング法により７０ｎｍの膜厚の発光層を得た。その上に、Ｃａを４０ｎｍ、Ａｌを８０ｎｍの膜厚の電極を形成して、有機ＥＬ素子を得た。この素子は、直流電圧６Ｖで、発光を開始し、最大発光輝度２００ｃｄ／ｍ２、発光効率０．０２１ｍ／Ｗが得られた。この素子の発光スペクトルを図２に示す。
【００６５】
実施例２
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴをスピンコート法で５０ｎｍの膜厚に製膜し、次に、表３の化合物（２）と４Ｍｅ−ＴＰＤ（Ｎ，Ｎ‘−ジフェニル−Ｎ，Ｎ’−ジ−ｍ−トリル−３，３‘−ジメチル−４，４’−ビフェニルジアミン）を６：４の割合で混合した２％の濃度でトルエンに溶解させ、スピンコーティング法により６０ｎｍの膜厚の発光層を得た。その上に、Ｃａを４０ｎｍ、Ａｌを８０ｎｍの膜厚の電極を形成して、有機ＥＬ素子を得た。この素子は、直流電圧５Ｖで、発光を開始し、最大発光輝度５００ｃｄ／ｍ２、発光効率０．０５１ｍ／Ｗが得られた。この素子の発光スペクトルを図３にしめす。
【００６６】
実施例３−７
洗浄したＩＴＯ電極付きガラス板上に、ＰＥＤＯＴをスピンコート法で５０ｎｍの膜厚に製膜し、次に、６０ｍｇのポリ（Ｎ−ビニルカルバゾール）（ＰＶＫ）、３８ｍｇの２−（４‘−ｔ−ブチルフェニル）−５−（４“−（フェニル）フェニル）−１，３，４−オキサジアゾール（ＰＢＤ）、２ｍｇの表３に示した化合物を１５ｇの１，２−ジクロロエタンに溶解させ、スピンコーティング法により７０ｎｍの膜厚の発光層を得た。その上に、Ｃａを４０ｎｍ、Ａｌを８０ｎｍの膜厚の電極を形成して、有機ＥＬ素子を得た。この素子は、直流電圧１０Ｖで、表４に示した発光輝度を得た。
【００６７】
表４
【表４】
比較例１
実施例１の化合物（１）に代えて化合物（９）を発光層に使用し、ほかは実施例１と同様にして有機ＥＬ素子を作成した。
【００６９】
化合物（９）
【化７】
発光層に化合物（９）のみを使用した実施例１の有機ＥＬ素子を作成した。この素子は、直流電圧８Ｖで発光輝度約４０ｃｄ／ｍ２発光効率０．００９ｌｍ／Ｗが得られた。
この素子の発光スペクトルを図４に示す。
【００７１】
本実施例で示された全ての有機ＥＬ素子について、連続発光させたところ、１０００時間以上初期輝度の５０％以上の輝度を観測出来たが、比較例１および２の素子を同様の条件で連続発光させたところ、１０時間で初期感度の５０％以下の輝度になり、ダークスポットの数も極めて多くなった。本発明の発光性ドーパントは、共役高分子発光材料と組み合わせることにより、そのＥＬ特性が大きく改良されていることがわかる。
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。
【００７２】
【発明の効果】
本発明により、従来に比べて高発光効率、高輝度であり、長寿命の有機ＥＬ素子を得ることができた。
【図面の簡単な説明】
【図１】化合物（１）のフイルムの蛍光スペクトル図
【図２】実施例１の素子の、発光スペクトル図
【図３】実施例２の素子の、発光スペクトル図
【図４】比較例１の素子の、発光スペクトル図[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a light emitting material used for a flat light source, an organic electroluminescence (EL) element used for display, and the like, and a high brightness light emitting element.
[0002]
[Prior art]
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. In general, an EL element includes a light emitting layer and a pair of opposed electrodes sandwiching the light emitting layer. In light emission, when an electric field is applied between both electrodes, electrons are injected from the cathode side, holes are injected from the anode side, the electrons recombine with holes in the light emitting layer, and the energy level is changed from the conduction band. This is a phenomenon in which energy is emitted as light when returning to the valence band.
[0003]
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 element in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported, and has attracted attention (see Non-Patent Document 1). This method uses a metal chelate complex for a light emitting layer and an amine compound for a hole injection layer to obtain high-luminance green light emission. The luminance reaches several thousand cd / m 2 at a DC voltage of 6 to 7 V. ing. However, the production of an EL device involving the operation of vapor-depositing an organic compound has a problem in productivity, and from the viewpoint of simplifying the production process and increasing the area, it is desirable to produce the device by a coating method.
[0004]
A polyphenylenevinylene-based polymer is known as a light-emitting material of an EL element used for producing a coating-type EL element that is advantageous in productivity (see Non-Patent
[0005]
There has been proposed a light-emitting polymer (see
As a light-emitting material that emits red light, there is a light-emitting polymer having a DPP (diketopyrrolopyrrole) skeleton (see Patent Document 6). However, when this polymer is polymerized with DPP at a ratio of 1: 1, the solubility in a general-purpose solvent is poor, and the film-forming property is poor. Accordingly, luminance unevenness is observed on the light emitting surface of the EL element.
[0006]
[Non-Patent Document 1] Applied Physics Letters, Vol. 51, pp. 913, 1987 [Non-Patent Document 2]
[Problems to be solved by the invention]
[0008]
An object of the present invention is to provide a light-emitting material for an organic EL device having a high light emission luminance and a long light-emitting life, and an organic EL device using the same. As a result of diligent studies by the present inventors, the use of a polymer having a specific conjugated unit represented by the general formula [1] as a light-emitting material allows the organic EL device to dramatically improve light-emitting luminance and light-emitting efficiency. Was found.
[0009]
[Means for Solving the Problems]
The present invention relates to an organic electroluminescence device material comprising a polymer comprising a conjugated unit and a non-conjugated unit and having a weight average molecular weight of 1000 or more, wherein the conjugated unit comprises a unit represented by the following general formula [1]. It relates to an element material.
General formula [1]
Embedded image
[0010]
The present invention also relates to the electroluminescent device material, wherein the non-conjugated unit is any of the units represented by the following general formula [2].
General formula [2]
Embedded image
R 3 represents a hydrogen atom, an alkyl group or an aryl group. ]
[0011]
In addition, the present invention relates to the above electroluminescent device material, wherein the conjugate unit comprises an aryl group or a heterocyclic group other than the general formula [1] and a unit represented by the general formula [1].
[0012]
Further, the present invention provides an organic electroluminescence element in which a light-emitting layer or a plurality of organic compound thin films including a light-emitting layer is formed between a pair of electrodes, wherein at least one of the organic layers is made of the above material alone. Alternatively, the present invention relates to an organic electroluminescence device characterized in that it is contained as a mixture.
[0013]
Further, the present invention provides an organic electroluminescence device in which a light emitting layer or a plurality of organic compound thin films including a light emitting layer is formed between a pair of electrodes, wherein the light emitting layer contains the above material alone or as a mixture. The present invention relates to a characteristic organic electroluminescent element.
[0014]
BEST MODE FOR CARRYING OUT THE INVENTION
The present invention is characterized in that, in the organic electroluminescence element, the polymer represented by the general formula [1] is contained in the light emitting layer as a novel organic light emitting material.
[0015]
The present invention relates to an organic electroluminescent device material comprising a polymer having a molecular weight of 1000 or more, comprising a conjugate unit and a non-conjugate unit (B).
In the present invention, the conjugate unit comprises a unit having a DPP skeleton represented by the general formula [1] and a conjugate unit (A) other than the general formula [1]. The conjugate unit (A) other than the general formula [1] further includes an aryl group, a heterocyclic group, an ethenyl group and the like.
In the present invention, the non-conjugated unit (B) includes a non-conjugated unit represented by the general formula [2].
In the present invention, the alkyl group represented by R 1 to R 3 in the general formulas [1] and [2] preferably has 6 to 30 carbon atoms and is a substituted or unsubstituted methyl group, ethyl group, Examples include propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, stearyl and the like.
The alkoxy group preferably has 6 to 30 carbon atoms and is a substituted or unsubstituted methoxy group, ethoxy group, propoxy group, n-butoxy group, sec-butoxy group, tert-butoxy group, pentyloxy group, hexyl. Examples include an oxy group and a stearyloxy group.
The thioalkoxy group preferably has 6 to 30 carbon atoms and is substituted or unsubstituted, methylthio, ethylthio, propylthio, butylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio, Examples include a heptylthio group and an octylthio group.
[0016]
As the aryl group having 6 to 30 carbon atoms represented by R 1 to R 3 in the general formulas [1] and [2] in the present invention, a substituted or unsubstituted phenyl group, biphenylenyl group, triphenylenyl group, Tetraphenylenyl, 3-nitrophenyl, 4-methylthiophenyl, 3,5-dicyanophenyl, o-, m- and p-tolyl, xylyl, o-, m- and p-cumenyl , Mesityl group, pentalenyl group, indenyl group, naphthyl group, azulenyl group, heptalenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, anthryl group, anthraquinonyl group, 3-methylanthryl group, phenanthryl group, triphenylenyl group, pyrenyl group, A chrysenyl group, a 2-ethyl-1-chrysenyl group, a picenyl group, a perylenyl group, - chloroperylenyl groups, pentaphenyl group, pentacenyl group, tetraphenylenyl les group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.
[0017]
As the heterocyclic group, substituted or unsubstituted, thionyl, furyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, indolyl, quinolyl, isoquinolyl, phthalazinyl Group, quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, 2-methylpyridyl group , 3-cyanopyridyl groups and the like.
[0018]
The conjugated unit (A) in the present invention can be a divalent group obtained by removing one hydrogen atom from the substituted or unsubstituted aryl group or heterocyclic group. Furthermore, an ethenyl group, an ethynyl group, etc. are mentioned. Further, the same or different conjugate units may be continuous.
[0019]
Representative examples of the conjugated unit (A) represented by the general formula [1] are specifically shown in Table 1, but are not limited thereto.
Table 1
[0020]
[Table 1]
Next, typical examples of the non-conjugated unit (B) represented by the general formula [1] are specifically shown in Table 2, but are not limited thereto.
Table 2
[0024]
[Table 2]
The substituent in the present invention is a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted thioalkoxy group, a cyano group, an amino group, a mono- or di-substituted amino group, a hydroxyl group. , A Mercart group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted arylthio group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, and the substituent is an adjacent substituent May form a substituted or unsubstituted ring with each other.
[0028]
Examples of the substituted or unsubstituted alkyl group include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, and isooctyl. , Stearyl, trichloromethyl, trifluoromethyl, cyclopropyl, cyclohexyl, 1,3-cyclohexadienyl, 2-cyclopenten-1-yl, 2,4-cyclopentadiene-1-yridenyl and the like There is.
[0029]
Examples of the substituted or unsubstituted alkoxy group include methoxy, ethoxy, propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, and stearyloxy. And a trifluoromethoxy group.
[0030]
Examples of the substituted or unsubstituted thioalkoxy group include methylthio, ethylthio, propylthio, butylthio, sec-butylthio, tert-butylthio, pentylthio, hexylthio, heptylthio, octylthio, and the like.
[0031]
Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a p-tert-butylphenoxy group, and a 3-fluorophenoxy group.
[0032]
Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a 3-fluorophenylthio group.
[0033]
Mono- or di-substituted amino groups include methylamino, dimethylamino, ethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino, bis (acetooxymethyl) amino, bis (acetooxy) Examples include an ethyl) amino group, a bis (acetooxypropyl) amino group, a bis (acetooxybutyl) amino group, and a dibenzylamino group.
[0034]
Preferred substituents are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group. Adjacent substituents form an aliphatic, carbocyclic aromatic, heteroaromatic, or heterocyclic ring which may contain a 5- to 7-membered oxygen atom, nitrogen atom, sulfur atom, etc. And may further have a substituent at any position of these rings.
[0035]
The polymer EL light-emitting material of the present invention may be a random, block, or graft copolymer, or may be a polymer having an intermediate structure between them, such as a random copolymer having a block property. . From the viewpoint of obtaining a copolymer having high luminous efficiency, a random copolymer having block properties or a block or graft copolymer is preferable to a completely random copolymer.
[0036]
As for the ratio between the conjugated unit and the non-conjugated unit contained in the polymer, the weight ratio of the conjugated unit to the non-conjugated unit 1 is preferably 1 to 50.
Further, the electroluminescent device material of the present invention preferably has a weight average molecular weight of 1,000 or more in terms of solubility in a general-purpose organic solvent.
Since the electroluminescent device material of the present invention has a rigid conjugated portion and a flexible connecting portion in the main chain, it is basically not difficult to form a film by dissolving it in a solvent, but it is more soluble and has excellent film forming properties. In order to obtain a good polymer, it is preferable to include at least one unit represented by the general formula [2] per polymer molecule.
[0037]
The method for producing the polymer used in the present invention will be described. The polymer used in the present invention can be synthesized by various methods. For example, a polymerization method in which an aryl halide is homocoupled in the presence of a nickel or copper derivative to form a carbon-carbon bond, a polymerization method in which an aryl halide derivative and a vinylbenzene derivative are reacted under a palladium catalyst to form a carbon-carbon bond, a boric acid derivative or A polymerization method in which a borate ester derivative and an aryl halide derivative are reacted in the presence of a palladium catalyst to form a carbon-carbon bond, and a polymerization method in which an aryltin derivative and an aryl halide derivative are reacted in the presence of a palladium catalyst to form a carbon-carbon bond. Is a polymerization method in which a boric acid derivative or a borate ester derivative is reacted with an aryl halide derivative in the presence of a palladium catalyst to form a carbon-carbon bond, and a homo-coupling of the aryl halide in the presence of a nickel or copper derivative to form a carbon-carbon bond Polymerization It is particularly preferred.
[0038]
The boric acid derivative includes a substituted or unsubstituted aryl boron derivative and a substituted or unsubstituted heteroaryl boron derivative, and the substituted or unsubstituted aryl boron derivative includes 1,4-phenyldiboric acid, 4,4′-biphenyldiboric acid. And the substituted or unsubstituted heteroarylboron derivatives include pyridyldiboric acid, thienyldiboric acid and the like. Examples of the borate derivative include a substituted or unsubstituted aryl borate derivative and a substituted or unsubstituted heteroaryl borate ester derivative.For example, a substituted or unsubstituted aryl borate derivative includes phenyl diborate pinacol ester, substituted or unsubstituted aryl borate derivative. Examples of the substituted heteroaryl borate derivative include thienyl diborate pinacol ester and the like.
[0039]
As the aryl halide derivative, there are a chlorine atom, a bromine atom and an iodine atom as a halogen atom, and a bromine atom is preferable. Examples of the aryl halide derivative include a dibromobenzene derivative, a dibromofluorene derivative, and a dibromonaphthalene derivative, and examples of the heteroaryl halide derivative include a dibromothiophene derivative and a dibromopyridine derivative.
[0040]
In the present invention, examples of the palladium catalyst include tetrakistriphenylphosphine palladium, palladium carbon, palladium dichloride 1,1′-bisdiphenylphosphinoferrocene, and the like. A ligand such as triphenylphosphine may be added at the same time. In this reaction, it is preferable to use a base. Examples of the base include sodium carbonate, sodium hydrogen carbonate, sodium acetate, triethylamine and the like.
[0041]
In the present invention, the nickel catalyst includes nickel biscyclooctadiene and the like, and a ligand such as 2-2′-bipyridine and cyclooctadiene may be added at the same time.
[0042]
Typical examples of the polymer used in the present invention are specifically shown in Table 3, but the polymer used in the present invention is not limited to the following typical examples. The structural formulas in the table show the composition ratios, and do not always have the arrangement of the block copolymer.
[0043]
[Table 3]
The luminescent material of the present invention may be used in a mixture with another luminescent material, a hole or electron transporting compound in the same layer. Since the light emitting material of the present invention is excellent in light emitting property and hole transporting property, it can be effectively used as a hole transporting light emitting material.
[0045]
As a light emitting material or a dopant material that can be used in the light emitting layer together with the light emitting material of the present invention, a polyalkylfluorene derivative, a polyphenylene derivative, a polyphenylenevinylene derivative, a polythiophene derivative, and other light-emitting polymers can be used. In addition, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bis Benzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelated oxinoid compound, Quinacridone, rubrene and dyes such as fluorescent dyes for laser and sensitization, but are not limited to these. Not shall.
[0046]
The light emitting material of the present invention and any of the above compounds which can be used together in the light emitting layer may be present in any ratio in the light emitting layer. That is, by the respective combinations of the above-mentioned compound and the compound of the present invention, the compound of the present invention can be a main material for forming the light emitting layer or a dopant material in another main material.
[0047]
The conjugated polymer contained in the doping material according to the present invention refers to a conjugated system in which a double bond (or triple bond) containing a carbon-carbon or carbon-hetero atom is alternately and long connected to a single bond in a molecular skeleton. Conjugated polymer. More specifically, polyacetylene, which is an aliphatic conjugated system in which carbon-carbon single bonds and double bonds are alternately and continuously long, and poly (a), which is an aromatic conjugated system in which conjugation has developed due to long bonding of aromatic hydrocarbons Hetero-containing heteroatom in which polypyrrole, polythiophene, aliphatic or aromatic conjugated system, which is a heterocyclic conjugated system in which a conjugated system is developed by bonding a polyphenylene), poly (alkylfluorene) derivative, or heterocyclic compound, with a heteroatom Examples include polyaniline, which is an atom conjugated system, and poly (phenylenevinylene), which is a mixed conjugated system in which constituent units of the various conjugated systems are alternately bonded.
[0048]
Regarding the abundance ratio of the compound represented by the general formula [1] of the present invention in the light-emitting layer, any may be the main component. That is, it can be a main material forming the light emitting layer or a doping material in another main material. As a condition for mixing the compound represented by the general formula [1] of the present invention with the conjugated polymer, a ratio of 1 to 90% by weight based on the whole of both is used. When the content is less than 1% by weight, the effect of the compound represented by the general formula [1] is not sufficiently exhibited, and the object of the present invention is not achieved. The effects referred to here indicate that the addition of the compound represented by the general formula [1] improves the emission luminance of the EL, improves the efficiency, and lowers the emission start voltage. As a method of mixing both, a known method is used. For example, the conjugated polymer and the compound represented by the general formula [1] are accurately weighed and mixed in a light-tight closed container. A general-purpose organic solvent such as toluene and xylene is added at a ratio of 0.5 to 5.0% by weight based on the whole, and dissolved by ultrasonic waves or mild heating.
[0049]
In the light emitting layer, if necessary, in addition to the light emitting material of the present invention, a further hole injection material or electron injection material can be used. When the organic EL element has a multilayer structure, it is possible to prevent a decrease in luminance and life due to quenching. If necessary, a combination of a light emitting material, a dopant material, a hole injection material, and an electron injection material can be used. Further, with the dopant material, the emission luminance and the luminous efficiency can be improved, and red and blue luminescence can be obtained. Further, each of the hole injection zone, the light emitting layer, and the electron injection zone may be formed by a layer structure of two or more layers. At that time, in the case of the hole injection zone, a layer for injecting holes from the electrode is a hole injection layer, and a layer for receiving holes from the hole injection layer and transporting holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of the electron injection zone, a layer that injects electrons from the electrode is called an electron injection layer, and a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer is called an electron transport layer. These layers are selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or the metal electrode.
[0050]
As a hole injecting material, it has the ability to transport holes, has a hole injecting effect from the anode, an excellent hole injecting effect on the light emitting layer or the light emitting material, and has a function of excitons generated in the light emitting layer. Compounds that prevent migration to the electron injection zone or the electron injection material and have excellent thin film forming ability are mentioned. Specifically, PEDOT, phthalocyanine derivative, naphthalocyanine derivative, porphyrin derivative, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acylhydrazone, polyarylalkane, stilbene, Examples include butadiene, benzidine-type triphenylamine, styrylamine-type triphenylamine, diamine-type triphenylamine, and derivatives thereof, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers, but are not limited thereto. It is not done.
[0051]
As an electron injection material, it has the ability to transport electrons, has the effect of injecting holes from the cathode, has an excellent electron injection effect on the light emitting layer or the light emitting material, and injects excitons generated in the light emitting layer. Compounds that prevent migration to a zone and have an excellent ability to form a thin film may be mentioned. For example, there are fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and derivatives thereof. However, the present invention is not limited to these. Alternatively, the electron injecting material may be sensitized by adding an electron accepting substance to the hole injecting material and the electron donating substance to the electron injecting material.
[0052]
Since the light-emitting material of the present invention has a high glass transition point and a high melting point, resistance to Joule heat generated in an organic layer during organic electroluminescence, between organic layers or between an organic layer and a metal electrode (heat resistance) is improved. When used as an organic EL device material, it exhibits high emission luminance and is advantageous when emitting light for a long time.
[0053]
The method for forming a film of the polymer of the present invention is not particularly limited. For example, a vacuum deposition method from a powder state, a method of dissolving in a solvent, and then applying (for example, an inkjet method, a spray method, a printing method, a spin coating method, A casting method, a dipping method, a bar coating method, a roll coating method, etc.) can be used, but a coating method is preferable from the viewpoint of simplification of the element manufacturing process, workability, and increase in area. Solvents used for forming a film by the coating method include organic halogen-based solvents such as dichloroethane, dichloromethane, and chloroform; ether-based solvents such as tetrahydrofuran and 1.4-dioxane; and aromatic hydrocarbon-based solvents such as toluene and xylene. And amide solvents such as dimethylformamide and dimethylacetamide, ester solvents such as ethyl acetate and butyl acetate, or a mixed solvent thereof. Although it depends on the structure and molecular weight of the polymer, the film is usually formed using a solution in which 0.01 to 10% by weight, preferably 0.1 to 5% by weight of a solvent is dissolved.
[0054]
An organic EL device is a device in which a single or multilayer organic thin film is formed between an anode and a cathode. In the case of a single layer type, a light emitting layer is provided between the anode and the cathode. The light-emitting layer contains a light-emitting material and may further contain a hole-injection material or an electron-injection material for transporting holes injected from an anode or electrons injected from a cathode to the light-emitting material. The multilayer type includes (anode / hole injection zone / emission layer / cathode), (anode / emission layer / electron injection zone / cathode), (anode / hole injection zone / emission layer / electron injection zone / cathode) There is an organic EL element stacked in a configuration.
[0055]
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, barium, 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.
[0056]
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.
[0057]
【Example】
Hereinafter, the present invention will be described in more detail with reference to Examples. In the description, parts represent parts by weight, and% represents% by weight.
Production Example 1
Method for synthesizing compound 1
The following compound (7) was used as a reaction monomer.
Compound (7)
[0059]
Embedded image
2 ml of DMF, 2,2′-bipyridine (0.34 g, 2.16 mmol) and Ni (cod) 2 (0.6 g, 2.16 mmol) were added to a four-neck flask and stirred. The reaction solution changed from yellow to brown with the production of Ni (cod) 2 (bpy). 9,9 ′-(2-ethylhexyl) dibromofluorene (0.82 g, 1.5 mmol), compound (7) (0.4 g, 0.6 mmol), bis (4-bromophenyl) previously dissolved in DMF ) Ether (0.2 g 0.6 mmol) was added dropwise. After completion of the dropwise addition, a cooling tube was attached to the four-necked flask, and the mixture was stirred at 80 ° C. for 24 hours. After completion of the reaction, the mixture was poured into a large excess of methanol and washed for 3 hours. After filtration of the precipitate, the precipitate was dissolved in a small amount of THF and poured into a large excess of methanol again. After stirring for 24 hours, the precipitate was filtered and dried under vacuum to obtain the desired product. The product was confirmed to be the target product by elemental analysis, IR spectrum and NMR. The yield was 68%.
Method for synthesizing
The following compound (8) was used as a reaction monomer.
Compound (8)
[0062]
Embedded image
A condenser tube was attached to the four-necked flask, and compound (8) (0.62 g, 1.00 mmol), 9,9 ′-(hexyl) fluorene-2,7-boronic acid 1,3-propanediol diester (1 0.000 g, 2.00 mmol) and bis (4-bromophenyl) ether (0.33 g, 1.00 mmol) were added with THF (30 ml) and stirred. To this was added NaHCO 3 (3.17 g, 37.8 mmol) and H 2 O (30 ml). Tetrakistriphenylphosphine palladium (0) (Pd (PPh 3 )) (43.7 mg, 37.8 μmol) and THF (60 ml) were added, and the mixture was refluxed at 80 ° C. for 72 hours. The desired product was washed with methanol. The yield was 69%. FIG. 1 shows the fluorescence spectrum of the film of the compound (2).
[0064]
Hereinafter, Examples using the light emitting material of the present invention will be specifically described, but the present invention is not limited thereto.
Example 1
PEDOT (polyethylene oxythiophene polystyrene sulfonate copolymer) was formed into a film having a thickness of 50 nm on a washed glass plate with an ITO electrode by a spin coating method. Was dissolved in toluene, and a light-emitting layer having a thickness of 70 nm was obtained by a spin coating method. An electrode having a thickness of 40 nm for Ca and 80 nm for Al was formed thereon to obtain an organic EL device. This device started emitting light at a DC voltage of 6 V, and a maximum light emission luminance of 200 cd / m 2 and a light emission efficiency of 0.021 m / W were obtained. FIG. 2 shows the emission spectrum of this device.
[0065]
Example 2
PEDOT was formed into a film having a thickness of 50 nm on a washed glass plate with an ITO electrode by spin coating, and then compound (2) shown in Table 3 and 4Me-TPD (N, N'-diphenyl-N, N '-Di-m-tolyl-3,3'-dimethyl-4,4'-biphenyldiamine) was dissolved in toluene at a concentration of 2% mixed at a ratio of 6: 4, and a film thickness of 60 nm was obtained by a spin coating method. Was obtained. An electrode having a thickness of 40 nm for Ca and 80 nm for Al was formed thereon to obtain an organic EL device. This device started emitting light at a DC voltage of 5 V, and a maximum light emission luminance of 500 cd / m 2 and a light emission efficiency of 0.051 m / W were obtained. FIG. 3 shows the emission spectrum of this device.
[0066]
Example 3-7
PEDOT was formed to a thickness of 50 nm on a washed glass plate with ITO electrodes by spin coating, and then 60 mg of poly (N-vinylcarbazole) (PVK) and 38 mg of 2- (4′-t). -Butylphenyl) -5- (4 "-(phenyl) phenyl) -1,3,4-oxadiazole (PBD), 2 mg of the compound shown in Table 3 were dissolved in 15 g of 1,2-dichloroethane, An emissive layer having a thickness of 70 nm was obtained by spin coating, and an electrode having a thickness of 40 nm was formed on Ca and 80 nm was formed on Al to obtain an organic EL device. Thus, the emission luminance shown in Table 4 was obtained.
[0067]
Table 4
[Table 4]
Comparative Example 1
An organic EL device was prepared in the same manner as in Example 1 except that the compound (9) was used in the light emitting layer instead of the compound (1) of Example 1.
[0069]
Compound (9)
Embedded image
An organic EL device of Example 1 using only the compound (9) for the light emitting layer was produced. This device had a light emission luminance of about 40 cd / m 2 and a light emission efficiency of 0.009 lm / W at a DC voltage of 8 V.
FIG. 4 shows the emission spectrum of this device.
[0071]
When all the organic EL elements shown in this example were continuously lit, luminance of 50% or more of the initial luminance could be observed for 1000 hours or more, but the elements of Comparative Examples 1 and 2 were continuously emitted under the same conditions. When light was emitted, the brightness became 50% or less of the initial sensitivity in 10 hours, and the number of dark spots became extremely large. It can be seen that the EL characteristics of the luminescent dopant of the present invention are greatly improved by combining with the conjugated polymer luminescent material.
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.
[0072]
【The invention's effect】
According to the present invention, an organic EL device having higher luminous efficiency and higher luminance than the conventional one and having a long life can be obtained.
[Brief description of the drawings]
FIG. 1 is a fluorescence spectrum of a film of compound (1). FIG. 2 is an emission spectrum of the device of Example 1. FIG. 3 is an emission spectrum of a device of Example 2. FIG. Emission spectrum of the device
Claims (5)
一般式［１］
General formula [1]
一般式［２］
Ｒ３は、水素原子、アルキル基またはアリール基を表す。］The electroluminescent device material according to claim 1, wherein the non-conjugated unit is any of units represented by the following general formula [2].
General formula [2]
R 3 represents a hydrogen atom, an alkyl group or an aryl group. ]
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