JP3972565B2 - ORGANIC ELECTROLUMINESCENT DEVICE, COMPOUND HAVING POLYMERIZABLE CYCLIC STRUCTURE OR POLYMER THEREOF, AND FLUORESCENT THIN FILM - Google Patents

Description

〔式中、Ｘは２価の反応性基を表し、−Ｏ−，−Ｓ−，−ＮＲ−，−ＣＯＯ−，−ＣＯＮＲ−，−ＣＲ＝ＣＲ−，−Ｏ−ＣＲ＝Ｎ−又は−Ｏ−ＣＲ＝ＣＲ−を示す。Ｒは水素原子又は置換基を表す。Ｚは置換基を有してよい脂肪族炭化水素鎖であり、Ｘと共に環構造を形成する。［Ｌ］は１価の発光性化合物残基を表し、［Ｓ］はＸとＺで形成される環と［Ｌ］を連結する連結基を表す。〕
【化Ｄ】

〔式中、Ｑ ₁ は−Ｏ−，−Ｓ−又は−ＮＲ ₂₅ −を表し、ｎ２は１〜５の整数を表す。Ｒ ₂₁ ，Ｒ ₂₂ ，Ｒ ₂₃ ，Ｒ ₂₄ 及びＲ ₂₅ は各々、水素原子又は置換基を表すが、いずれか一つは−［Ｓ］−［Ｌ］である。又、Ｒ ₂₁ 〜Ｒ ₂₅ は互いに連結して環構造を形成してもよい。［Ｌ］及び［Ｓ］は、それぞれ一般式（１）における［Ｌ］及び［Ｓ］と同義である。〕
【化Ｅ】

〔式中、ｎ４は１〜５の整数を表し、Ｒ ₄₁ ，Ｒ ₄₂ ，Ｒ ₄₃ ，Ｒ ₄₄ ，Ｒ ₄₅ 及びＲ ₄₆ は各々、水素原子又は置換基を表すが、いずれか一つは−［Ｓ］−［Ｌ］である。又、Ｒ ₄₁ 〜Ｒ ₄₆ は互いに連結して環構造を形成してもよい。［Ｌ］及び［Ｓ］は、それぞれ一般式（１）における［Ｌ］及び［Ｓ］と同義である。〕
【化Ｆ】

〔式中、ｎ５は１又は２の整数を表し、Ｒ ₅₁ ，Ｒ ₅₂ ，Ｒ ₅₃ ，Ｒ ₅₄ 及びＲ ₅₅ は各々、水素原子又は置換基を表すが、いずれか一つは−［Ｓ］−［Ｌ］である。又、Ｒ ₅₁ 〜Ｒ ₅₅ は互いに連結して環構造を形成してもよい。［Ｌ］及び［Ｓ］は、それぞれ一般式（１）における［Ｌ］及び［Ｓ］と同義である。〕
【化Ｇ】

〔式中、Ｒ ₆₁ ，Ｒ ₆₂ ，Ｒ ₆₃ ，Ｒ ₆₄ ，Ｒ ₆₅ 及びＲ ₆₆ は各々、水素原子又は置換基を表すが、いずれか一つは−［Ｓ］−［Ｌ］である。又、Ｒ ₆₁ 〜Ｒ ₆₆ は互いに連結して環構造を形成してもよい。［Ｌ］及び［Ｓ］は、それぞれ一般式（１）における［Ｌ］及び［Ｓ］と同義である。〕
【化Ｈ】

〔式中、Ｒ ₇₁ は水素原子又は置換基を表し、Ａ ₁ ，Ａ ₂ ，Ａ ₃ 及びＡ ₄ は各々、Ｃ，Ｎ，Ｏ，Ｓ，Ｐのいずれかを表すが、Ａ ₁ 〜Ａ ₄ が全てＣになることはない。Ｙ ₁ は連結基又は結合手を表し、Ｙ ₂ はＡ ₁ ，Ａ ₂ と共に４〜８員環を形成する基を表し、Ｙ ₃ はＡ ₃ ，Ａ ₄ と共に４〜８員環を形成する基を表す。〕
【化Ｉ】

〔式中、Ｒ ₈₁ ，Ｒ ₈₂ 及びＲ ₈₃ は各々、水素原子又は置換基を表す。［Ｌ］及び［Ｓ］は、それぞれ一般式（１）における［Ｌ］及び［Ｓ］と同義である。〕
【００１６】
更に、一般式（１）で表される化合物又はその重合体、付加反応体、縮合反応体を少なくとも１種含有してなる蛍光性薄膜もその一態様である。
【００１７】
これらの構成によって、蛍光性残基を高分子主鎖に対して２〜７の任意の原子おきに自由度を制限された状態で適度に分散することができ、発光特性、安定性、加工特性の何れもが良い有機ＥＬ素子材料を得ることができる。
【００１８】
以下、詳細に説明する。まず、一般式（１）〜（８）で表される化合物又は置換基について説明する。
【００１９】
一般式（１）において、Ｘは、重合開始剤であるラジカル、カチオン、アニオン、金属錯体などに反応し、新たに反応の活性点となることのできる２価の官能基で、−Ｏ−，−Ｓ−，−ＮＲ−，−ＣＯＯ−，−ＣＯＮＲ−，−ＣＲ＝ＣＲ−，−Ｏ−ＣＲ＝Ｎ−又は−Ｏ−ＣＲ＝ＣＲ−（Ｒは水素原子又は置換基）を示す。Ｚで表される置換基を有してもよい脂肪族炭化水素鎖は、好ましくは炭素数２〜６であって、Ｘと共に環構造を形成する。
【００２０】
［Ｓ］はＸとＺで形成される環構造と１価の発光性化合物残基［Ｌ］を連結する２価の連結基で、例えばフェニレン、エチレン、−Ｏ−，−ＮＲ−，−ＣＯ−（Ｒは水素原子又は置換基）等、２価の基、又はこれらが複数連結したものである。［Ｌ］は１価の発光性化合物残基であり、室温下で発光を示す化合物の任意の位置から水素原子又は置換基を一つ取り除いたものを表す。該室温下で発光を示す化合物の「発光」は蛍光発光でも燐光発光でもよい。
【００２１】
発光性化合物残基と成り得る発光性化合物としては、レーザー色素のように可視領域に吸収を有する蛍光色素でも、蛍光増白剤のように紫外領域に吸収を有する蛍光化合物でも、更にポルフィリンのプラチナ錯体やビアセチル体のような燐光発光化合物でもよく、具体的には、八木國夫，吉田善一，太田利一共著「蛍光−理論・測定・応用−」（南江堂）の９９〜１２２頁に記載される有機蛍光物質、同書２５１〜２７０頁に記載の蛍光増白剤、更に同書２７４〜２８７頁に記載の蛍光色素が、代表例として挙げられる。
【００２２】
中でも好ましくは、トリフェニレンやペリレン等に代表される縮合環式芳香族炭化水素環化合物；ｐ−ターフェニルやクオーターフェニル等に代表される線状共役多環式炭化水素化合物；アクリジン、キノリン、カルバゾール、カルバゾン、フルオレン、キサンチオン、アロキサジン、アクリドン、フラボン、クマリン、ナフトイミダゾール、ベンゾオキサゾール及びジベンゾフェナジン等に代表される縮合環式芳香族複素環化合物；チアゾール、オキサゾール、オキサジアゾール、チアジアゾール及びトリアゾール等に代表される芳香族複素環化合物；アミノクロロマレイックイミド、メチルアミノシトラコニックメチルイミド、デカペンタエンカルボン酸及びデカペンタエンジカルボン酸等に代表される共役系脂肪族化合物；メチレンブルー、フルオロセイン、エオシン、ローダミン及びベンソフラビン等に代表される蛍光色素化合物；オキサカルボシアニン、カルボシアニン、チアカルボシアニン及び２−（アニリノポリエチニル）ベンゾチアゾール等の感光色素化合物；ポルフィリン、クロロフィル及びリボフラビン等に代表される天然色素化合物；ジアミノスチルベン、ジスチリルベンゼン、ベンジジン、ジアミノカルバゾール、トリアゾール、イミダゾール、チアゾール、オキサゾール、イミダゾロン、ジヒドロピリジン、クマリン、カルボスチリル、ジアミノジベンゾチオフェンオキシド、シアミノフルオレン、オキサシアニン、アミノナフタルイミド、ピラゾリン及びオキサジアゾール系の蛍光増白剤等が挙げられ、更にこれらは置換基を有してもよく、更に縮合環を形成してもよい。
【００２３】
ここで言う置換基としては、アルキル基（メチル、エチル、ｉ−プロピル、ヒドロキシエチル、メトキシメチル、トリフルオロメチル、ｔ−ブチル等）、シクロアルキル基（シクロペンチル、シクロヘキシル等）、アラルキル基（ベンジル、２−フェネチル等）、アリール基（フェニル、ナフチル、ｐ−トリル、ｐ−クロロフェニル等）、アルコキシ基（メトキシ、エトキシ、ｉ−プロポキシ、ブトキシ等）、アリールオキシ基（フェノキシ、ナフトキシ等）等が挙げられる。これらの基は更に置換されていてもよく、置換基として、ハロゲン原子、トリフルオロメチル基、シアノ基、ニトロ基、アルキル基、アリール基、アルコキシ基、アリールオキシ基、アルキルチオ基、ジアルキルアミノ基、ジベンジルアミノ基、ジアリールアミノ基等が挙げられる。
【００２４】
一般式（２）の化合物は３〜６員の環状エーテル（Ｑ₁＝Ｏ）、環状スルフィド（Ｑ₁＝Ｓ）、環状イミン（Ｑ₁＝ＮＲ₂₅）の誘導体である。式中、ｎ２は１〜５で、Ｒ₂₁〜Ｒ₂₅は水素原子又は置換基を表すが、これらのうち一つは−［Ｓ］−［Ｌ］である。又、これらは互いに連結して環構造を形成してもよい。
【００２５】
一般式（３）の化合物は４〜７員のラクトン（Ｑ₂＝Ｏ）又はラクタム（Ｑ₂＝ＮＲ₃₅）の誘導体である。式中、ｎ３は１〜６で、Ｒ₃₁〜₃₅は水素原子又は置換基を表すが、これらのうち一つは−［Ｓ］−［Ｌ］である。又、これらは互いに連結して環構造を形成してもよい。
【００２６】
一般式（４）の化合物は４〜７員のシクロアルケン誘導体である。式中、ｎ４は１〜５で、Ｒ₄₁〜₄₆は水素原子又は置換基を表巣が、これらのうち一つは−［Ｓ］−［Ｌ］である。又、これらは互いに連結して環構造を形成してもよい。
【００２７】
一般式（５）の化合物はオキサゾリン誘導体（ｎ＝１）又はジヒドロオキサジン誘導体（ｎ＝２）である。式中、ｎ５は１又は２で、Ｒ₅₁〜₅₅は水素原子又は置換基を表すが、これらのうち一つは−［Ｓ］−［Ｌ］である。又、これらは互いに連結して環構造を形成してもよい。
【００２８】
一般式（６）の化合物はジヒドロフラン誘導体である。Ｒ₆₁〜₆₆は水素原子又は置換基を表すが、これらのうち一つは−［Ｓ］−［Ｌ］である。又、これらは互いに連結して環構造を形成してもよい。
【００２９】
特に好ましい［Ｌ］成分を表す一般式（７）の構造は、置換基を有してもよい縮合複素芳香環である。式中、Ａ₁〜Ａ₄はＣ，Ｎ，Ｏ，Ｓ，Ｐの何れかを表すが、Ａ₁〜Ａ₄が全てＣになることはない。Ｙ₁は−ＣＲ₇₂−，−Ｎ−，−ＣＯ−のような連結基又は結合手で、Ｙ₂はＡ₁，Ａ₂と共に、Ｙ₃はＡ₂，Ａ₃と共に、それぞれ４〜８員環を形成する。該４〜８員環としては、置換基を有してもよい芳香族炭化水素環又は芳香族複素環が挙げられ、例えばベンゼン、ナフタレン、アントラセン、アズレン、フェナントレン、トリフェニレン、ピレン、クリセン、ナフタセン、ペリレン、ペンタセン、ヘキサセン、コロネン、トリナフチレン、フラン、チオフェン、ピロール、イミダゾール、ピラゾール、１，２，４−トリアゾール、１，２，３−トリアゾール、オキサゾール、チアゾール、イソオキサゾール、イソチアゾール、フラザン、ピリジン、ピラジン、ピリミジン、ピリダジン、インドリジン、キノリン、イソインドール、インドール、イソキノリン、フタラジン、プリン、ナフチリジン、キノキサリン、キナゾリン、シンノリン、プテリジン、カルバソール、フェナントリジン、アクリジン、ペリミジン、フェナントロリン、フェナジン等である。
【００３０】
これらは、任意の置換基を複数個それぞれ独立に有してもよく、その複数の置換基が互いに縮合して更に環を形成してもよい。これらの環は置換基を有してもよい。又、Ｒ₇₁及びＲ₇₂は各々、水素原子又は置換基である。
【００３１】
一般式（７）で表される縮合複素芳香環の代表例を以下に挙げるが、これらに限定されない。
【００３２】
【化９】

【００３３】
一般式（８）の化合物はエチレン誘導体である。Ｒ₈₁〜Ｒ₈₃は各々、水素原子又は置換基を表すが、これらのうち一つは−［Ｓ］−［Ｌ］であり、［Ｌ］は一般式（７）で示される複素芳香環である。
【００３４】
一般式（１），（２），（３），（４），（５），（６）及び（８）に共通な連結基［Ｓ］としては、フェニレン（ｏ，ｐ，ｍ）、メチレン、−Ｏ−、−Ｎ（Ｒ）−（Ｒは水素原子又は置換基）、−ＣＯ−等が挙げられるが、これらの複合系も含まれる。
【００３５】
以下に、本発明における一般式（１）〜（８）で表わされる化合物の具体例を示すが、これらに限定されるものではない。尚、化合物Ｅ−１〜Ｅ−１２は一般式（２）の、Ｌ−１〜Ｌ−１２は一般式（３）の、Ｎ−１〜Ｎ−１２は一般式（４）の、Ｘ−１〜Ｘ−６は一般式（５）の、Ｆ−１〜Ｆ−６は一般式（６）の、Ｖ−１〜Ｖ−１２は一般式（８）の、それぞれ代表例である。
【００３６】
【化１０】

【００３７】
【化１１】

【００３８】
【化１２】

【００３９】
【化１３】

【００４０】
【化１４】

【００４１】
以下に、例示化合物の代表的合成例を示す。
合成例１
【００４２】
【化１５】

【００４３】
（化合物Ｑ−１の合成）
アントラニル酸メチルエステル９０．６ｇをキシレン中、含水ヒドラジン５４ｍｌと共に加熱・還流下９．５時間反応させた。その後、溶媒を減圧・溜去し、少量のエタノールを加えて粗結晶を得た。更にエタノールで再結晶すると中間体（ａ）が６４．９ｇ（収率７２％）で得られた。
【００４４】
次に１５．０ｇの中間体ａと２１．０ｇのエチルベンゾイルアセテートをキシレン中１２０℃で一時間反応させ、その後、更に還流下８時間反応させた。この際、生成する水とエタノールを溜去した。放冷後、析出した結晶を濾取した。この結晶をＮ，Ｎ−ジメチルホルムアミド（以下、ＤＭＦと略称）とメタノールの混合溶媒で再結晶することにより化合物（Ｑ−１）が１４．７ｇ（収率５６％）得られた。
【００４５】
ＮＭＲ及びマススペクトルにより、Ｑ−１であることを確認した。又、この化合物Ｑ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００４６】
合成例２
【００４７】
【化１６】

【００４８】
（化合物Ｅ−１の合成）
化合物（Ｑ−１）１．３１ｇ（５．０ｍｍｏｌ）を、ジメチルアセトアミド中炭酸カリウム１．４８ｇ（１４ｍｍｏｌ）及びエピクロルヒドリン０．４３ｍｌ（５．５ｍｍｏｌ）と共に３時間５０℃で反応させた。その後、水中にあけ１ｍｏｌ／Ｌ塩酸で中和した。生成物を濾取し、アセトニトリルで再結晶することで化合物（Ｅ−１）が０．９２ｇ（収率５８％）得られた。
【００４９】
ＮＭＲ及びマススペクトルにより、Ｅ−１であることを確認した。又、この化合物Ｅ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００５０】
（Ｅ−１の重合）
重合開始剤として無水塩化鉄（III）１００ｍｇを三つ口フラスコに入れ、減圧下で加熱して完全に脱水した後、乾燥窒素ガスを封入する。窒素気流下でＥ−１の０．６３ｇ（２ｍｍｏｌ）と、脱水ＤＭＦ１０ｍｌを添加し、３時間１００℃で反応させた。その後、反応溶媒を大過剰のメタノールに注いで淡黄色沈澱を得た。この沈澱を少量のテトラヒドロフラン（以下ＴＨＦと略称）に溶解させ、大過剰のヘキサンに注いで、０．３８ｇ（収率６０％）の白色沈澱（ＰＥ−１）を得た。
【００５１】
この沈殿物をＧＰＣにより測定したところ、数平均分子量約４．５００程度のポリマーであることを確認した。又、この重合体ＰＥ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００５２】
合成例３
【００５３】
【化１７】

【００５４】
（ラクトンＬ−０の合成）
ヨード酢酸−３−ブテニル６．０ｇ（２５ｍｍｏｌ）と蒸留水２．５リットルを、４リットル四つ口フラスコに入れ、乾燥アルゴンでフラスコ内を置換した。撹拌しながら、トリエチルボランの１ｍｏｌ／Ｌメタノール溶液２．５ｍｌ（２．５ｍｍｏｌ）を滴下した。滴下終了後、５時間室温で撹拌した後、酢酸エチルで抽出した。酢酸エチルを留去して得た組成物を、シリカゲルカラムクロマトグラフィーにより精製し、３．３ｇ（収率５５％）の３−ヨードメチル−δラクトン（Ｌ−０）を得た。
【００５５】
（化合物Ｌ−１の合成）
化合物Ｑ−１の１．３１ｇ（５．０ｍｍｏｌ）を、ジメチルアセトアミド中炭酸カリウム１．４８ｇ（１４ｍｍｏｌ）及びＬ−０の３．４ｇ（５．５ｍｍｏｌ）と共に３時間５０℃で反応させた。その後、水中にあけ、１ｍｏｌ／Ｌ塩酸で中和した。生成物を濾取しアセトニトリルで再結晶することで、化合物（Ｌ−１）が１．０２ｇ（収率５５％）得られた。
【００５６】
ＮＭＲ及びマススペクトルにより、目的化合物であることを確認した。又、この化合物Ｌ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００５７】
（Ｌ−１の重合）
トリエチルアルミニウムを脱水トルエンに溶解させて３％溶液とし、この溶液を開始剤とした。又、脱水ＴＨＦ２リットルに対し、蒸溜水を０．２ｍｌ添加した反応溶媒１８ｍｌを、５０ｍｌ三つ口フラスコに注ぎ、更に化合物Ｌ−１の０．９３ｇ（２．５ｍｍｏｌ）と、前記トリエチルアルミニウムの３％トルエン溶液を０．４ｍｌ（０．１ｍｍｏｌ：４．０ｍｏｌ％）を０℃にて添加した。その後、ＴＨＦを４日間還流した。反応終了後、反応溶液を大量のジエチルエーテル中に注ぎ、沈澱してくる白色固体を濾別し、０．１ｍｏｌ／Ｌ塩酸溶液で洗浄後、クロロホルムに溶解させ、大量のヘキサンに注いで再沈澱を行い、０．４１ｇ（収率４４％）の白色沈澱（ＰＬ−１）を得た。
【００５８】
この沈殿物をＧＰＣにより測定したところ、数平均分子量約５４００程度のポリマーであることを確認した。又、この重合体ＰＬ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００５９】
合成例４
【００６０】
【化１８】

【００６１】
（化合物Ｎ−１の合成）
化合物Ｑ−１の１．３１ｇ（５．０ｍｍｏｌ）をジメチルアセトアミド中、炭酸カリウム１．４８ｇ（１４ｍｍｏｌ）及び４−クロロメチルノルボルネン０．７８ｇ（５．５ｍｍｏｌ）と共に３時間５０℃で反応させた。その後、水中にあけ、１ｍｏｌ／Ｌ塩酸で中和した。生成物を濾取し、アセトニトリルで再結晶することで、化合物（Ｎ−１）が０．８５ｇ（収率４６％）得られた。
【００６２】
ＮＭＲ及びマススペクトルにより、化合物Ｎ−１であることを確認した。又、この化合物Ｎ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００６３】
（Ｎ−１の重合）
化合物Ｎ−１の０．７４ｇ（２．０ｍｍｏｌ）と、塩化イリジウム（III）３水和物７１ｍｇ（０．０２ｍｍｏｌ，１．０ｍｏｌ％）を２０ｍｌのｉ−プロパノールに溶解させ、８時間還流を行ったところ、不溶物として灰色の不溶物が析出した。この組成物を濾別し、アセトンで洗浄後、熱トルエンに溶解させ、大過剰のメタノールで再沈澱を行い、０．４３ｇ（収率５８％）の淡灰色の重合体（ＰＮ−１）を得た。
【００６４】
この重合体をＧＰＣにより測定したところ、数平均分子量約５４００程度のポリマーであることを確認した。又、この重合体ＰＮ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００６５】
合成例５
【００６６】
【化１９】

【００６７】
（化合物Ｘ−１の合成）
化合物Ｑ−１の１．３１ｇ（５．０ｍｍｏｌ）を、ジメチルアセトアミド中で二塩化スクシニル０．７８ｇ（５．０ｍｍｏｌ）、トリエチルアミン１．５ｍｌ（１１ｍｍｏｌ）と共に３時間室温で反応させた。放冷後、エチレンイミン０．３ｍｌ（５．５ｍｍｏｌ）のジエチルエーテル溶液（３ｍｌ）を添加し、５０℃で５時間反応させた。放冷後、沈澱したトリエチルアミンの塩酸塩を濾別し、溶液に炭酸カリウム１．４８ｇ（１４ｍｍｏｌ）を添加し、３時間５０℃で反応させた。その後、水中にあけ、１ｍｏｌ／Ｌ塩酸で中和した。生成物を濾取し、アセトニトリルで再結晶することで、化合物（Ｘ−１）が１．２０ｇ（収率６１％）得られた。
【００６８】
ＮＭＲ及びマススペクトルにより、Ｘ−１であることを確認した。又、この化合物Ｘ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００６９】
（Ｘ−１の重合）
重合開始剤として、ｐ−クロロフェニルオキサゾリニウム過塩素酸塩の２％アセトニトリル溶液を調整しておく。化合物Ｘ−１の０．７７ｇ（２．０ｍｍｏｌ）をジメチルアセトアミド１０ｍｌに溶解させ、窒素雰囲気下で０．１ｍｌを加え、１２０℃で１８時間反応させた。反応終了後、溶液を大過剰のメタノールに注ぎ、白色の沈殿物を得た。この白色固体を再びＴＨＦに溶解させ、大過剰のジエチルエーテルに再沈澱を行い、白色固体（ＰＸ−１）を０．５９ｇ（７７％）得た。
【００７０】
この重合体をＧＰＣにより測定したところ、数平均分子量約６６００程度のポリマーであることを確認した。又、この重合体ＰＸ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００７１】
合成例６
【００７２】
【化２０】

【００７３】
（化合物Ｆ−０の合成）
化合物Ｑ−１の１．３１ｇ（５．０ｍｍｏｌ）を、ジメチルアセトアミド中で４−ヨード安息香酸クロリド１．４７ｇ（５．５ｍｍｏｌ）、トリエチルアミン０．８ｍｌ（６．０ｍｍｏｌ）と共に３時間室温で反応させた。放冷後、沈澱したトリエチルアミンの塩酸塩を濾別後、溶液を酢酸エチルで分液し、有機層を硫酸ナトリウムで脱水し、溶媒を溜去して粗成物を得た。アセトニトリルで再結晶することで、白色固体（Ｆ−０）が２．２６ｇ（収率９１％）得られた。
【００７４】
ＮＭＲ及びマススペクトルにより、Ｆ−０であることを確認した。又、この化合物Ｆ−０にＵＶライトを照射したが、蛍光の発光は観測されなかった。
【００７５】
（化合物Ｆ−１の合成）
上記化合物Ｆ−０の１．９６ｇ（４．０ｍｍｏｌ）を、ジメチルホルムアミド中で酢酸パラジウム（II）２２．４ｍｇ（０．０１ｍｍｏｌ、２．５ｍｏｌ％）、トリフェニルホスフィン２６．２ｍｇ（０．０１ｍｍｏｌ、２．５ｍｏｌ％）、塩化ブチルアンモニウム０．４３ｇ（４．０ｍｍｏｌ）及び酢酸カリウム１．１８ｇ（１２ｍｍｏｌ）と共に２４時間８０℃で反応させた。放冷後、溶液を酢酸エチルで分液し、有機層を硫酸ナトリウムで脱水し、溶媒を溜去して白色粗成物を得た。組成物をアセトニトリルで再結晶することで、化合物（Ｆ−１）が１．２６ｇ（収率７３％）得られた。
【００７６】
ＮＭＲ及びマススペクトルにより、Ｆ−１であることを確認した。又、この化合物Ｆ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００７７】
（Ｆ−１の重合）
化合物Ｆ−１の０．８６ｇ（２．０ｍｍｏｌ）を、ジメチルアセトアミド中ヘキサフルオロアンチモン酸・４−メトキシ−２−オキソ−２，２，６，６−テトラメチルピペリジニウム８．４ｍｇ（０．０２ｍｍｏｌ、１．０％）を窒素下で添加し、室温で４時間反応させた。得られた反応溶液を大過剰のメタノールに再沈澱させ、白色固体（ＰＦ−１）０．６１ｇ（収率７１％）を得た。
【００７８】
この重合体をＧＰＣにより測定したところ、数平均分子量約５３００程度のポリマーであることを確認した。又、この重合体ＰＦ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００７９】
合成例７
【００８０】
【化２１】

【００８１】
（化合物Ｖ−１の合成）
化合物Ｑ−１の１．３１ｇ（５．０ｍｍｏｌ）のメタノール溶液をメタノール／ナトリウムメトキシド２８％溶液中に滴下し、室温で３時間反応させた後、溶媒を溜去した。得られた灰色の固形物を再びメタノール３０ｍｌ中に溶解させ、０℃で０．８ｍｌ（５．５ｍｍｏｌ）の４−クロロメチルスチレンを溶解させたＴＨＦ溶液５ｍｌを滴下した。３時間撹拌後、溶媒を溜去して、白色の固体を１．４８ｇ（１４０ｍｍｏｌ）及びエピクロルヒドリン０．５１ｇと共に３時間１００℃で反応させた。その後、水中にあけ、１ｍｏｌ／Ｌ塩酸で中和した。生成物を濾取し、アセトニトリルで再結晶することで、化合物（Ｖ−１）が１．７３ｇ（収率９２％）得られた。
【００８２】
ＮＭＲ及びマススペクトルにより、Ｖ−１であることを確認した。又、この化合物Ｖ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００８３】
（Ｖ−１の重合）
上記化合物Ｖ−１の０．７５ｇ（２．０ｍｍｏｌ）をＴＨＦ中に溶解させ、窒素雰囲気下でアゾビスイソブチロニトリル（ＡＩＢＮ、０．１ｍｍｏｌ、５ｍｏｌ％）を０℃で添加した後、１０時間還流を行った。放冷後、反応溶液を大過剰のメタノール中に沈澱させて白色固体（ＰＶ−１）を０．６６ｇ（収率８８％）得た。
【００８４】
この重合体をＧＰＣにより測定したところ、数平均分子量約７３００程度のポリマーであることを確認した。又、この重合体ＰＶ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００８５】
合成例８
【００８６】
【化２２】

【００８７】
（Ｘ−１とγ−プロピオラクトンとの共重合）
前記化合物Ｘ−１の０．３９ｇ（１．０ｍｍｏｌ）をＤＭＦ中に溶解させ、窒素雰囲気下でγ−プロピオラクトンの１．０％ＤＭＦ溶液６．３ｍｌ（１．０ｍｍｏｌ）を０℃で添加した後、１０時間１００℃で反応を行った。放冷後、反応溶液を大過剰のメタノール中に沈澱させて白色固体（ＰＬＸ−１）を０．４０ｇ（収率８７％）得た。
【００８８】
この重合体をＧＰＣにより測定したところ、数平均分子量約６１００程度のポリマーであることを確認した。又、この重合体ＰＬＸ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００８９】
合成例９
（Ｌ−１のグラフト共重合）
Ｊ．Ｐｏｌｙｍｅｒ Ｓｃｉ．３４，３０９（１９５９）に従って、スチレンとメタクリロイルカプロラクタムをＡＩＢＮにより重合し、ポリ（メタクリロイルカプロラクタム）とポリ（スチレン）の共重合体（ＰＭＳ）を得た（収率２７％）。この重合体をＧＰＣにより測定したところ、数平均分子量約１３万程度のポリマーであることを確認した。この重合体１．０ｇと前記化合物Ｌ−１の１．０ｇを、トルエン中、９５℃にて重合開始剤にカプロラクトンナトリウムを用いてグラフト重合を行った。反応中にゲル化が起こったので、放冷後、濾過、洗浄し、乾燥することで白色固体ＰＧＬ−１を１．４２ｇ（収率７１％）得た。
【００９０】
この重合体をＧＰＣにより測定したところ、数平均分子量約１７万程度のポリマーであることを確認した。又、この重合体ＰＧＬ−１にＵＶライトを照射したところ、青紫色の蛍光を発した。
【００９１】
本発明の有機ＥＬ素子は、基本的には一対の電極の間に発光層を挾持し、必要に応じ正孔注入層や電子注入層を介在させた構造を有する。具体的には、（ｉ）陽極／発光層／陰極、（ii）陽極／正孔注入層／発光層／陰極、（iii）陽極／発光層／電子注入層／陰極、（iv）陽極／正孔注入層／発光層／電子注入層／陰極などの構造がある。
【００９２】
上記発光層は、（１）電界印加時に陽極又は正孔注入層により正孔を注入することができ、かつ陰極又は電子注入層より電子を注入することができる注入機能、（２）注入した電荷（電子と正孔）を電界の力で移動させる輸送機能、（３）電子と正孔の再結合の場を発光層内部に提供し、これを発光に繋げる発光機能などを有している。ただし、正孔の注入され易さと電子の注入され易さに違いがあってもよく、又、正孔と電子の移動度で表される輸送機能に大小があってもよいが、少なくともどちらか一方の電荷を移動させる機能を有するものが好ましい。
【００９３】
この発光層に用いられる発光材料の種類については特に制限はなく、従来、有機ＥＬ素子における発光材料として公知のものを用いることができる。このような発光材料は主に有機化合物であり、所望の色調により、例えば、Ｍａｃｒｏｍｏｌ．Ｓｙｍｐ．１２５巻，１７〜２６頁に記載の化合物が挙げられる。
【００９４】
上記材料を用いて発光層を形成する方法としては、例えば蒸着法、キャスト法、ＬＢ法などの公知の方法により薄膜化することにより形成することができるが、生産性を考えると、発光材料を溶剤に溶かして溶液とした後、これをスピンコート法などにより薄膜化して形成することが好ましい。このようにして形成された発光層の膜厚については特に制限はなく、状況に応じて適宜選択することができるが、通常は５ｎｍ〜５μｍの範囲である。
【００９５】
ＥＬ素子における陽極としては、仕事関数の大きい（４ｅＶ以上）金属、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが好ましく用いられる。このような電極物質の具体例としては、Ａｕ等の金属、ＣｕＩ、インジウムチンオキシド（ＩＴＯ）、ＳｎＯ₂、ＺｎＯ等の導電性透明材料が挙げられる。該陽極は、これらの電極物質を蒸着やスパッタリングなどの方法により、薄膜を形成させ、フォトリソグラフィー法で所望の形状のパターンを形成してもよく、又はパターン精度を余り必要としない場合は（１００μｍ以上程度）、上記電極物質の蒸着やスパッタリング時に所望の形状のマスクを介してパターンを形成してもよい。この陽極より発光を取り出す場合には、透過率を１０％より大きくすることが望ましく、又、陽極としてのシート抵抗は数百Ω／□以下が好ましい。更に、膜厚は材料にもよるが、通常１０ｎｍ〜１μｍ、好ましくは１０〜２００ｎｍの範囲で選ばれる。
【００９６】
一方、陰極としては、仕事関数の小さい（４ｅＶ以下）金属（電子注入性金属と称する）、合金、電気伝導性化合物及びこれらの混合物を電極物質とするものが用いられる。このような電極物質の具体例としては、ナトリウム、ナトリウム−カリウム合金、マグネシウム、リチウム、マグネシウム／銅混合物、マグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ₂Ｏ₃）混合物、インジウム、リチウム／アルミニウム混合物、希土類金属などが挙げられる。これらの中で、電子注入性及び酸化などに対する耐久性の点から、電子注入性金属とこれより仕事関数の値が大きく安定な金属である第２金属との混合物、例えばマグネシウム／銀混合物、マグネシウム／アルミニウム混合物、マグネシウム／インジウム混合物、アルミニウム／酸化アルミニウム（Ａｌ₂Ｏ₃）混合物、リチウム／アルミニウム混合物などが好適である。該陰極は、これらの電極物質を蒸着やスパッタリングなどの方法により、薄膜を形成させることにより、作製することができる。又、陰極としてのシート抵抗は数百Ω／□以下が好ましく、膜厚は通常１０ｎｍ〜１μｍ、好ましくは５０〜２００ｎｍの範囲で選ばれる。尚、発光を透過させるため、有機ＥＬ素子の陽極又は陰極の何れか一方が、透明又は半透明であれば発光効率が向上し好都合である。
【００９７】
次に、必要に応じて設けられる正孔注入層は、陽極より注入された正孔を発光層に伝達する機能を有し、この正孔注入層を陽極と発光層の間に介在させることにより、より低い電界強度で多くの正孔が発光層に注入され、その上、発光層に陰極又は電子注入層より注入された電子は、発光層と正孔注入層の界面に存在する電子の障壁により、発光層内の界面に累積され発光効率が向上するなど発光性能の優れた素子となる。この正孔注入層の材料（以下、正孔注入材料と言う）については、前記の好ましい性質を有するものであれば特に制限はなく、従来、光導伝材料において、正孔の電荷注入輸送材料として慣用されているものやＥＬ素子の正孔注入層に使用される公知のものの中から任意のものを選択して用いることができる。
【００９８】
上記正孔注入材料は、正孔の注入、電子の障壁性の何れかを有するものであり、有機物、無機物の何れであってもよい。この正孔注入材料としては、例えばトリアゾール誘導体、オキサジアゾール誘導体、イミダゾール誘導体、ポリアリールアルカン誘導体、ピラゾリン誘導体及びピラゾロン誘導体、フェニレンジアミン誘導体、アリールアミン誘導体、アミノ置換カルコン誘導体、オキサゾール誘導体、スチリルアントラセン誘導体、フルオレノン誘導体、ヒドラゾン誘導体、スチルベン誘導体、シラザン誘導体、アニリン系共重合体、又、導電性高分子オリゴマー、特にチオフェンオリゴマー等が挙げられる。正孔注入材料としては、上記のものを使用することができるが、ポルフィリン化合物、芳香族第三級アミン化合物及びスチリルアミン化合物、特に芳香族第三級アミン化合物を用いることが好ましい。
【００９９】
上記芳香族第三級アミン化合物及びスチリルアミン化合物の代表例としては、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラフェニル−４，４′−ジアミノフェニル、Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ビス（３−メチルフェニル）−〔１，１′−ビフェニル〕−４，４′−ジアミン（ＴＰＤ）、２，２−ビス（４−ジ−ｐ−トリルアミノフェニル）プロパン、１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）シクロヘキサン、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラ−ｐ−トリル−４，４′−ジアミノビフェニル、１，１−ビス（４−ジ−ｐ−トリルアミノフェニル）−４−フェニルシクロヘキサン、ビス（４−ジメチルアミノ−２−メチルフェニル）フェニルメタン、ビス（４−ジ−ｐ−トリルアミノフェニル）フェニルメタン、Ｎ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ジ（４−メトキシフェニル）−４，４′−ジアミノビフェニル、Ｎ，Ｎ，Ｎ′，Ｎ′−テトラフェニル−４，４′−ジアミノジフェニルエーテル、４，４′−ビス（ジフェニルアミノ）クオードリフェニル、Ｎ，Ｎ，Ｎ−トリ（ｐ−トリル）アミン、４−（ジ−ｐ−トリルアミノ）−４′−〔４−（ジ−ｐ−トリルアミノ）スチリル〕スチルベン、４−Ｎ，Ｎ−ジフェニルアミノ−（２−ジフェニルビニル）ベンゼン、３−メトキシ−４′−Ｎ，Ｎ−ジフェニルアミノスチルベンゼン、Ｎ−フェニルカルバゾール、更には、米国特許５，０６１，５６９号に記載される２個の縮合芳香族環を分子内に有するもの、例えば４，４′−ビス〔Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ〕ビフェニル（ＮＰＤ）、特開平４−３０８６８８号に記載されるトリフェニルアミンユニットが三つスターバースト型に連結された４，４′，４″−トリス〔Ｎ−（３−メチルフェニル）−Ｎ−フェニルアミノ〕トリフェニルアミン（ｍ−ＴＤＡＴＡ）等が挙げられる。
【０１００】
又、ｐ型−Ｓｉ、ｐ型−ＳｉＣ等の無機化合物も正孔注入材料として使用することができる。この正孔注入層は、上記正孔注入材料を、例えば真空蒸着法、スピンコート法、キャスト法、ＬＢ法などの公知の方法により、薄膜化することにより形成することができる。正孔注入層の膜厚については特に制限はないが、通常は５ｎｍ〜５μｍ程度である。この正孔注入層は、上記材料の１種又は２種以上から成る１層構造であってもよく、同一組成又は異種組成の複数層から成る積層構造であってもよい。更に、必要に応じて用いられる電子注入層は、陰極より注入された電子を発光層に伝達する機能を有していればよく、その材料としては従来公知の化合物の中から任意のものを選択して用いることができる。
【０１０１】
この電子注入層に用いられる材料（以下、電子注入材料と言う）の例としては、ニトロ置換フルオレン誘導体、ジフェニルキノン誘導体、チオピランジオキシド誘導体、ナフタレンペリレン等の複素環テトラカルボン酸無水物；カルボジイミド、フレオレニリデンメタン誘導体、アントラキノジメタン及びアントロン誘導体、オキサジアゾール誘導体などが挙げられる。又、特開昭５９−１９４３９３号に記載される一連の電子伝達性化合物は、該公報では発光層を形成する材料として開示されているが、本発明者らが検討の結果、電子注入材料として用い得ることが判った。更に、上記オキサジアゾール誘導体において、オキサジアゾール環の酸素原子を硫黄原子に置換したチアジアゾール誘導体、電子吸引基として知られているキノキサリン環を有するキノキサリン誘導体も、電子注入材料として用いることができる。
【０１０２】
又、８−キノリノール誘導体の金属錯体、例えばトリス（８−キノリノール）アルミニウム（Ａｌｑ）、トリス（５，７−ジクロロ−８−キノリノール）アルミニウム、トリス（５，７−ジブロモ−８−キノリノール）アルミニウム、トリス（２−メチル−８−キノリノール）アルミニウム、トリス（５−メチル−８−キノリノール）アルミニウム、ビス（８−キノリノール）亜鉛（Ｚｎｑ）等、及びこれらの金属錯体の中心金属がＩｎ，Ｍｇ，Ｃｕ，Ｃａ，Ｓｎ，Ｇａ又はＰｂに置き替わった金属錯体も、電子注入材料として用いることができる。その他、メタルフリーもしくはメタルフタロシアニン、又はそれらの末端がアルキル基やスルホン酸基などで置換されているものも、電子注入材料として好ましく用いることができる。又、発光層の材料として例示したジスチリルピラジン誘導体も、電子注入材料として用いることができるし、正孔注入層と同様に、ｎ型−Ｓｉ、ｎ型−ＳｉＣ等の無機半導体も電子注入材料として用いることができる。
【０１０３】
この電子注入層は、上記化合物を、例えば真空蒸着法、スピンコート法、キャスト法、ＬＢ法などの公知の薄膜化法により製膜して形成することができる。電子注入層としての膜厚は、特に制限はないが、通常は５ｎｍ〜５μｍの範囲で選ばれる。この電子注入層は、これらの電子注入材料１種又は２種以上から成る１層構造であってもよいし、あるいは、同一組成又は異種組成の複数層から成る積層構造であってもよい。
【０１０４】
次に、該有機ＥＬ素子を作製する好適な例を説明する。例として、前記の陽極／正孔注入層／発光層／電子注入層／陰極から成るＥＬ素子の作製法について説明すると、まず適当な基板上に、所望の電極物質、例えば陽極用物質から成る薄膜を、１μｍ以下、好ましくは１０〜２００ｎｍの範囲の膜厚になるように、蒸着やスパッタリング等の方法により形成させ、陽極を作製する。次に、この上に、素子材料である正孔注入層、発光層、電子注入層、陰極層の材料から成る薄膜を順次形成させる。
【０１０５】
この薄膜化の方法には、スピンコート法、キャスト法、蒸着法などがある。生産性を考えると、前記の如くスピンコート法が良いが、スピンコート法では低分子化合物、金属電極などは、現状では製膜することができない。これらの薄膜層の形成には、化合物均質な膜が得られ易く、かつピンホールが生成し難い等の点から真空蒸着法が好ましい。この薄膜化に、この蒸着法を採用する場合、その蒸着条件は、使用する化合物の種類、分子堆積膜の目的とする結晶構造、会合構造などにより異なるが、一般に、ボート加熱温度５０〜４５０℃、真空度１０^-6〜１０^-3Ｐａ、蒸着速度０．０１〜５０ｎｍ／秒、基板温度−５０〜３００℃、膜厚５ｎｍ〜５μｍの範囲で適宜選ぶことが望ましい。
【０１０６】
このようにして得られたＥＬ素子に、直流電圧を印加する場合には、陽極を＋、陰極を−の極性として電圧３〜４０Ｖ程度を印加すると、発光が観測できる。又、逆の極性で電圧を印加しても電流は流れずに発光は全く生じない。更に、交流電圧を印加する場合には、陽極が＋、陰極が−の状態になった時のみ発光する。尚、印加する交流の波形は任意でよい。
【０１０７】
【実施例】
以下、実施例を挙げて本発明を詳細に説明するが、本発明の態様はこれに限定されない。
【０１０８】
実施例１
（有機ＥＬ素子の作製）
陽極として、ガラス上にＩＴＯ（前出）を１５０ｎｍ成膜した基板（ＮＨテクノグラス社製：ＮＡ−４５）にパターニングを行った後、このＩＴＯ透明電極を設けた透明支持基板をｉ−プロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、ＵＶオゾン洗浄を５分間行った。この透明支持基板上に、ポリマーＰＥ−１の２０ｍｇをＴＨＦ３ｍｌに溶解させ、１０００ｒｐｍ、３ｓｅｃの条件下スピンコートした。精製した有機薄膜の膜厚は、約１００ｎｍであった。
【０１０９】
この基板を、市販の真空蒸着装置の基板ホルダーに固定した後、真空槽を４×１０^-4Ｐａまで減圧した後、Ａｌｑ３の入った前記加熱ボートを通電して２５０℃まで加熱し、蒸着速度０．１ｎｍ／ｓｅｃで前記発光層の上に蒸着して膜厚２０ｎｍの電子注入層を設けた。尚、蒸着時の基板温度は室温であった。更にその上に、リチウムとアルミニウムを異なる蒸着源から、蒸着速度１．５〜２．０ｎｍ／ｓｅｃで質量比６：１で共蒸着して、前記リチウムとアルミニウムとの混合物から成る対向電極とすることにより、有機ＥＬ素子ＤＥ−１を作製した。
【０１１０】
実施例２〜８
実施例１において、ＰＥ−１の代わりに、それぞれＰＬ−１、ＰＮ−１、ＰＸ−１、ＰＦ−１、ＰＶ−１、ＰＬＸ−１及びＰＧＬ−１を用いて１００ｎｍの厚さにスピンコートし発光層とした以外は実施例１と全く同じ方法で、有機ＥＬ素子ＤＬ−１、ＤＮ−１、ＤＸ−１、ＤＦ−１、ＤＶ−１、ＤＬＸ−１及びＤＧＬ−１を作製した。
【０１１１】
実施例９
実施例１において、スピンコートするポリマーＰＥ−１の２０ｍｇ、ＴＨＦ３ｍｌ溶液に、４−ジシアノメチレン−２−メチル−６−（４−ジメチルアミノスチリル）−４Ｈ−ピラン（ＤＣＭ１）０．２ｍｇを溶解させ、１０００ｒｐｍ、３ｓｅｃの条件下でスピンコートした以外は全く同じ方法で、有機ＥＬ素子ＤＤ−１を作製した。
【０１１２】
【化２３】

【０１１３】
比較例１
陽極としてガラス上にＩＴＯを１５０ｎｍ成膜した基板（ＮＡ−４５：前出）にパターニングを行った後、このＩＴＯ透明電極を設けた透明支持基板をｉ−プロピルアルコールで超音波洗浄し、乾燥窒素ガスで乾燥し、ＵＶオゾン洗浄を５分間行った。
【０１１４】
この透明支持基板を、市販の真空蒸着装置の基板ホルダーに固定した後、真空槽を４×１０^-4Ｐａまで減圧した後、４，４′，４″−トリス（−Ｎ−（ｍ−トリル）−Ｎ−フェニルアミノ）トリフェニルアミン（ｍ−ＴＤＡＴＡ）を蒸着速度０．２ｎｍ／ｓｅｃで４０ｎｍの厚さに蒸着し、正孔注入層とし、次いでＮ，Ｎ′−ジフェニル−Ｎ，Ｎ′−ジ（ｍ−トリル）−４，４′−ジアミノ−１，１′−ビフェニル（ＴＰＤ）を蒸着速度０．２ｎｍ／ｓｅｃで３５ｎｍの厚さに蒸着し、正孔輸送層兼発光層とした。更に減圧を保ったまま、トリス（８−キノリノラト）アルミニウム（Ａｌｑ３）を蒸着速度０．２ｎｍ／ｓｅｃで５０ｎｍの厚さに蒸着し、電子輸送層とした。次いで減圧を保ったまま、リチウムとアルミニウムを異なる蒸着源から、蒸着速度１．５〜２．０ｎｍ／ｓｅｃで質量比６：１で共蒸着して、前記リチウムとアルミニウムとの混合物から成る対向電極とすることにより、比較の有機ＥＬ素子ＤＴ−１を作製した。
【０１１５】
【化２４】

【０１１６】
比較例２
比較例１において、ＴＰＤの代わりに化合物Ｑ−１を用いて正孔輸送層兼発光層とした以外は実施例１と全く同じ方法で、有機ＥＬ素子ＤＱ−１を作製した。
【０１１７】
（ＥＬ素子の特性評価）
東陽テクニカ社製ソースメジャーユニット２４００型を用いて、有機ＥＬ素子ＤＥ−１、ＤＬ−１、ＤＮ−１、ＤＸ−１、ＤＦ−１、ＤＶ−１、ＤＬＸ−１、ＤＧＬ−１、ＤＤ−１及び比較用の有機ＥＬ素子ＤＴ−１、ＤＱ−１に素子のＩＴＯ電極を陽極、リチウムとアルミニウムからなる対向電極を陰極として直流１０Ｖを印加し発光させ、その輝度をトプコン社製の輝度計ＢＭ−８、発光波長を浜松フォトニクス社製スペクトルアナライザーＰＭＡ−１１を用いて測定した。
【０１１８】
まず比較例ＤＴ−１では、青色に均一に面発光し、初期状態ではダークスポットの発生が認められなかったが、１時間駆動後には直径１００μｍ以下のダークスポットが１０〜１５個確認された。
【０１１９】
次に比較例ＤＱ−１では、青白色に均一に面発光し、初期状態ではダークスポットの発生が認められないことを確認したが、１時間駆動後には直径１００μｍ以下のダークスポットが１〜４個確認された。又、電界発光スペクトルを測定すると、４２４ｎｍと４５４ｎｍに発光ピークがあり、ｍ−ＴＤＡＴＡ層界面、Ａｌｑ層界面、又は発光層内で何らかの相互作用を起こして２色性のスペクトルになっていることが判った。
【０１２０】
一方、ＤＥ−１では、青紫色に均一に面発光し、初期状態では勿論、１時間駆動後でもダークスポットの発生は確認されなかった。又、電界発光スペクトルを測定すると、ＤＱ−１では確認された４５４ｎｍの発光ピークが消失し、４２５ｎｍの発光波長のみのスペクトルが観測された。この素子と、他の実施例による素子、ＤＬ−１、ＤＮ−１、ＤＸ−１、ＤＦ−１、ＤＶ−１、ＤＬＸ−１、ＤＧＬ−１、ＤＤ−１の結果について纏めて表１示す。
【０１２１】
【表１】

【０１２２】
【発明の効果】
表１に示される通り、発光性化合物を高分子化することにより、高い熱安定性、経時安定性と生産性を得ることができた。又、発光特性においても、低分子発光性化合物の輝度を低下させることなく、エキシマー発光の発生を抑え、色純度の良い素子を得ることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic electroluminescence (hereinafter also referred to as organic EL) element, and more particularly, to an organic electroluminescence element material having excellent light emission luminance and an organic electroluminescence element using the material.
[0002]
[Prior art]
Conventionally, an inorganic electroluminescence (hereinafter also referred to as “inorganic EL”) element has been used as a planar light source. However, in order to drive the light emitting element, an alternating high voltage is required. A recently developed organic EL device has a structure in which a thin film containing a fluorescent organic compound is sandwiched between a cathode and an anode, and excitons (excitons) are formed by injecting electrons and holes into the thin film and recombining them. And emits light using the emission of light (fluorescence / phosphorescence) when the exciton is deactivated, and can emit light at a low voltage of several volts to several tens of volts direct current. Since it is a light-emitting type, it is rich in viewing angle dependency, has high visibility, and is a thin-film type complete solid-state device, and thus has attracted attention from the viewpoints of space saving and portability.
[0003]
Various organic EL elements have been reported so far. For example, Appl. Phys. Lett. Vol. 51, page 913, or a combination of a hole injection layer described in JP-A-59-194393 and an organic light-emitting layer, hole injection layer described in JP-A-63-295695, and electron injection transport In combination with a layer, Jpn. Journal of Applied Physics, vol 127, no. A combination of the hole transfer layer, the light emitting layer, and the electron transfer layer described on pages 2,269 to 271 is disclosed.
[0004]
However, a device with higher luminance is demanded, and further improvement in energy conversion efficiency and light emission quantum efficiency is expected. In addition, a problem that the light emission life is short has been pointed out. The cause of such deterioration in luminance over time has not been completely elucidated, but the electroluminescent device during light emission is decomposed by the organic compound itself that constitutes the thin film by the light emitted by itself and the heat generated at that time, Degradation factors derived from an organic compound as an organic EL element material, such as intramolecular movement, aggregation, orientation, and crystallization of the organic compound in the thin film caused by a high electric field applied to the element, have been pointed out.
[0005]
In addition, an EL element accompanied by an organic compound vapor deposition operation has a problem in productivity. From the viewpoint of simplification of the manufacturing process, workability, and increase in area, it is desirable to manufacture an element by a coating method.
[0006]
Thus, as an EL element material used in the production of an EL element of a coating method advantageous in productivity, for example, there is an element (Japanese Patent Laid-Open No. 4-212286) in which a low molecular weight dye is dispersed in polyvinyl carbazole. Since the dye type and dye concentration can be changed arbitrarily, it is relatively easy to adjust the color tone and emission intensity. However, since these elements have low molecular weight compounds dispersed in the polymer, a high electric field is applied as described above. Dye aggregation and layer separation are likely to occur, and it is difficult to obtain uniform light emission.
[0007]
Similarly, as an EL element material using a coating method, for example, a paraphenylene vinylene polymer is known (Advanced Materials, Item 4, 1992). However, since the polymer main chain has a light emitting portion, the concentration control of the light emitting material is possible. There is a problem that it is difficult to delicately control the color tone and light emission intensity.
[0008]
Similarly, as an EL element material using a coating method, a polycarbonate obtained by reacting a bifunctional monomer containing a fluorescent residue such as tetraphenylbenzidine with phosgene, for example (Japanese Patent Laid-Open No. 5-247458) However, in the polymer obtained by such polycondensation, the acid to be eliminated is likely to remain, and the remaining impurities tend to become trap levels and cause deterioration of the device such as generation of dark spots. There is a problem that it is difficult to obtain uniform light emission and the light emission characteristics are not excellent.
[0009]
Further, for example, there is a polymer obtained by addition polymerization of a monomer in which a fluorescent residue such as triphenylamine and a vinyl group are linked with a radical initiator or the like (JP-A-7-53953, etc.), Closely linked fluorescent residues interact with each other in the excited state to form an exciplex that stabilizes the light, making the emission longer and facilitating excimer emission with low emission efficiency. Is difficult to control.
[0010]
In order to avoid such excimer emission, it is necessary to dilute and disperse the fluorescent residues in the molecule so that the fluorescent residues do not interact with each other in the molecule. As one of the means, a means of copolymerizing a monomer containing a fluorescent residue and a monomer having a structure that hardly interacts with the fluorescent residue can be considered. For example, an organic EL element material obtained by copolymerizing a fluorescent monomer such as vinyl anthracene and a charge transporting monomer such as vinyl carbazole is disclosed (JP-A-8-48726, etc.). Such a technique has the advantage that the dilution ratio can be freely selected depending on the mixing ratio of the monomers before polymerization, but there is a possibility of causing block copolymerization during the polymerization, and the fluorescent residue is expected. It is not always diluted / dispersed.
[0011]
It is considered that such interaction between fluorescent residues is likely to occur because the fluorescent residues are linked to the vicinity of the polymer main chain and are originally close to each other. Therefore, a method of preventing excimer emission due to the interaction between the fluorescent residues by adjusting the length of the linking group connecting the vinyl group which is a polymerization group and the fluorescent residue is also considered, for example, a methacryloyl group And an organic EL device material in which a coumarin, which is a fluorescent compound, is linked with mono- (or di-) ethylene oxide and the distance between the polymerizable group and the fluorescent residue is increased (Japanese Patent Laid-Open No. 8-157815). issue). However, when the linking group is lengthened in this way, there is a problem that the degree of freedom of movement of the fluorescent residue is increased, and the orientation and aggregation of the arrow-ringed fluorescent residue are liable to occur due to the applied high electric field.
[0012]
[Problems to be solved by the invention]
Accordingly, an object of the present invention is to provide an organic luminescence device containing a polymer having excellent light emission characteristics and processing stability.
[0013]
[Means for Solving the Problems]
As a result of examining the above problems, the present invention has been completed by finding that it is effective to lengthen the repeating unit of the polymer main chain in order to achieve intramolecular dispersion of the fluorescent residue. It is. That is, in the vinyl group polymer, every two fluorescent residues exist with respect to the polymer main chain, but when the polymerizable group has a cyclic structure, three, four, five It is possible to obtain a polymer material having a fluorescent residue accurately for each of two or more arbitrary repeating units, such as a fluorescent substance at a desired concentration while limiting the degree of freedom of the fluorescent residue. Residues can be dispersed in the polymer, excimer emission based on the interaction between fluorescent residues is prevented, and organic EL element materials with excellent emission characteristics, stability, and processing characteristics are obtained. be able to. In addition, any linking group may be introduced between the polymerizable cyclic structure and the fluorescent residue, and such a polymerizable monomer may be copolymerized with a monomer having an appropriate charge transporting group. In addition, it is possible to design organic EL device materials in a more free range by mixing a dopant in such a polymer at an appropriate concentration, or by adding, condensing, or graft-polymerizing a reactive polymer.
[0014]
  The object of the present invention is to provide an organic electroluminescence device in which a light emitting layer composed of a single layer or a plurality of layers of organic compound thin film is sandwiched between an anode and a cathode facing each other, and at least one layer of the organic compound thin film is formula(3)This is achieved by an organic electroluminescent device containing at least one compound having a polymerizable cyclic structure represented by the formula, or a polymer thereof.
[0015]
  still,Although it is an invention different from the present invention,General formula (3In place of the compound having a polymerizable cyclic structure represented by the formula:1), (4)~ (6)ofContains a compound having a polymerizable cyclic structure represented by any one or a polymer thereofThe embodiment is also the same invention. In addition, the luminescent compound residue [L] is represented by the general formula (7)soA general formula (a monovalent substituent derived from the fluorescent compound represented by the formula (1), (4)The compound of (6) or a polymer thereofIn the inventionpreferable. Furthermore, it is represented by the general formula (8).RuSuch a compound having a luminescent compound residue [L] of the general formula (7) or a polymer thereof, a compound of the general formulas (1) to (6) or (8), or a co-weight with other monomers. At least one organic compound thin film containing at least one polymer compound obtained by addition reaction, condensation reaction or graft polymerization of a compound, a compound of general formulas (1) to (8) and a polymer having a reactive group Contains organic electroluminescence elementsSoIs a preferred embodiment.
[C]

  [Wherein X represents a divalent reactive group, -O-, -S-, -NR-, -COO-, -CONR-, -CR = CR-, -O-CR = N- or- O-CR = CR- is shown. R represents a hydrogen atom or a substituent. Z is an aliphatic hydrocarbon chain which may have a substituent, and forms a ring structure together with X. [L] represents a monovalent luminescent compound residue, and [S] represents a linking group that links [L] with the ring formed by X and Z. ]
[Chemical D]

  [In the formula, Q ₁ Is —O—, —S— or —NR _{twenty five} -And n2 represents an integer of 1 to 5. R _{twenty one} , R _{twenty two} , R _{twenty three} , R _{twenty four} And R _{twenty five} Each represents a hydrogen atom or a substituent, and any one of them represents-[S]-[L]. R _{twenty one} ~ R _{twenty five} May be linked to each other to form a ring structure. [L] and [S] are synonymous with [L] and [S] in general formula (1), respectively. ]
[Chemical E]

  [Wherein n4 represents an integer of 1 to 5; ₄₁ , R ₄₂ , R ₄₃ , R ₄₄ , R ₄₅ And R ₄₆ Each represents a hydrogen atom or a substituent, and any one of them represents-[S]-[L]. R ₄₁ ~ R ₄₆ May be linked to each other to form a ring structure. [L] and [S] are synonymous with [L] and [S] in general formula (1), respectively. ]
[Chemical F]

  [Wherein n5 represents an integer of 1 or 2, R ₅₁ , R ₅₂ , R ₅₃ , R ₅₄ And R ₅₅ Each represents a hydrogen atom or a substituent, and any one of them represents-[S]-[L]. R ₅₁ ~ R ₅₅ May be linked to each other to form a ring structure. [L] and [S] are synonymous with [L] and [S] in general formula (1), respectively. ]
[Chemical G]

  [In the formula, R ₆₁ , R ₆₂ , R ₆₃ , R ₆₄ , R ₆₅ And R ₆₆ Each represents a hydrogen atom or a substituent, and any one of them represents-[S]-[L]. R ₆₁ ~ R ₆₆ May be linked to each other to form a ring structure. [L] and [S] are synonymous with [L] and [S] in general formula (1), respectively. ]
[Chemical H]

  [In the formula, R ₇₁ Represents a hydrogen atom or a substituent, and A ₁ , A ₂ , A _Three And A _Four Each represents one of C, N, O, S, and P, but A ₁ ~ A _Four Are not all C. Y ₁ Represents a linking group or a bond, and Y ₂ Is A ₁ , A ₂ And represents a group that forms a 4- to 8-membered ring together with Y _Three Is A _Three , A _Four And a group that forms a 4- to 8-membered ring. ]
[Chemical I]

  [In the formula, R ₈₁ , R ₈₂ And R ₈₃ Each represents a hydrogen atom or a substituent. [L] and [S] are synonymous with [L] and [S] in general formula (1), respectively. ]
[0016]
  Further, a fluorescent thin film comprising at least one compound represented by the general formula (1) or a polymer thereof, an addition reactant, or a condensation reactant is also provided.SoIt is one aspect | mode.
[0017]
With these configurations, the fluorescent residue can be appropriately dispersed in a state where the degree of freedom is limited every 2 to 7 atoms with respect to the polymer main chain, and the light emission characteristics, stability, processing characteristics Either of these can provide a good organic EL element material.
[0018]
  Less than, DetailsExplain in detail. First, the compounds or substituents represented by the general formulas (1) to (8) will be described.
[0019]
In the general formula (1), X is a divalent functional group that reacts with a polymerization initiator such as a radical, a cation, an anion, or a metal complex, and can newly become an active site of the reaction. -S-, -NR-, -COO-, -CONR-, -CR = CR-, -O-CR = N- or -O-CR = CR- (R is a hydrogen atom or a substituent). The aliphatic hydrocarbon chain which may have a substituent represented by Z preferably has 2 to 6 carbon atoms and forms a ring structure together with X.
[0020]
[S] is a divalent linking group linking the ring structure formed by X and Z and the monovalent luminescent compound residue [L], such as phenylene, ethylene, -O-, -NR-, -CO. A divalent group such as-(R is a hydrogen atom or a substituent), or a combination thereof. [L] is a monovalent luminescent compound residue, which is obtained by removing one hydrogen atom or substituent from any position of a compound that emits light at room temperature. The “light emission” of the compound that emits light at room temperature may be fluorescence or phosphorescence.
[0021]
Luminescent compounds that can serve as luminescent compound residues include fluorescent dyes that absorb in the visible region such as laser dyes, fluorescent compounds that absorb in the ultraviolet region such as fluorescent whitening agents, and platinum in porphyrins. It may be a phosphorescent compound such as a complex or a biacetyl compound. Specifically, it is described on pages 99 to 122 of Kuroo Yagi, Zenichi Yoshida and Toshikazu Ota, “Fluorescence-Theory, Measurement, and Application” (Nanedo). Typical examples thereof include organic fluorescent substances, fluorescent brighteners described on pages 251 to 270, and fluorescent dyes described on pages 274 to 287.
[0022]
Among them, preferably, a condensed cyclic aromatic hydrocarbon ring compound typified by triphenylene or perylene; a linear conjugated polycyclic hydrocarbon compound typified by p-terphenyl or quarterphenyl; acridine, quinoline, carbazole, Condensed aromatic heterocyclic compounds represented by carbazone, fluorene, xanthion, alloxazine, acridone, flavone, coumarin, naphthimidazole, benzoxazole and dibenzophenazine; represented by thiazole, oxazole, oxadiazole, thiadiazole and triazole Conjugated aliphatic compounds represented by aminochloromaleic imide, methylaminocitraconic methylimide, decapentaene carboxylic acid, decapentaene dicarboxylic acid, etc .; -Fluorescent dye compounds represented by fluorescein, eosin, rhodamine and benzoflavin; photosensitive dye compounds such as oxacarbocyanine, carbocyanine, thiacarbocyanine and 2- (anilinopolyethynyl) benzothiazole; porphyrin, chlorophyll and Natural pigment compounds typified by riboflavin and the like; diaminostilbene, distyrylbenzene, benzidine, diaminocarbazole, triazole, imidazole, thiazole, oxazole, imidazolone, dihydropyridine, coumarin, carbostyril, diaminodibenzothiophene oxide, siaminofluorene, oxacyanine , Aminonaphthalimide, pyrazoline and oxadiazole-based fluorescent whitening agents, and the like. It may be formed.
[0023]
Examples of the substituent include alkyl groups (methyl, ethyl, i-propyl, hydroxyethyl, methoxymethyl, trifluoromethyl, t-butyl, etc.), cycloalkyl groups (cyclopentyl, cyclohexyl, etc.), aralkyl groups (benzyl, 2-phenethyl etc.), aryl groups (phenyl, naphthyl, p-tolyl, p-chlorophenyl etc.), alkoxy groups (methoxy, ethoxy, i-propoxy, butoxy etc.), aryloxy groups (phenoxy, naphthoxy etc.) etc. It is done. These groups may be further substituted, and as a substituent, a halogen atom, a trifluoromethyl group, a cyano group, a nitro group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, a dialkylamino group, A dibenzylamino group, a diarylamino group, etc. are mentioned.
[0024]
The compound of the general formula (2) is a 3-6 membered cyclic ether (Q₁= O), cyclic sulfide (Q₁= S), cyclic imine (Q₁= NR_{twenty five}) Derivatives. In the formula, n2 is 1 to 5, R_{twenty one}~ R_{twenty five}Represents a hydrogen atom or a substituent, and one of these is-[S]-[L]. These may be connected to each other to form a ring structure.
[0025]
The compound of general formula (3) is a 4- to 7-membered lactone (Q₂= O) or lactam (Q₂= NR₃₅) Derivatives. In the formula, n3 is 1 to 6, and R3₃₁~₃₅Represents a hydrogen atom or a substituent, and one of these is-[S]-[L]. These may be connected to each other to form a ring structure.
[0026]
The compound of the general formula (4) is a 4- to 7-membered cycloalkene derivative. In the formula, n4 is 1 to 5, and R4₄₁~₄₆Is a hydrogen atom or substituent, one of which is-[S]-[L]. These may be connected to each other to form a ring structure.
[0027]
The compound of the general formula (5) is an oxazoline derivative (n = 1) or a dihydrooxazine derivative (n = 2). In the formula, n5 is 1 or 2, and R₅₁~₅₅Represents a hydrogen atom or a substituent, and one of these is-[S]-[L]. These may be connected to each other to form a ring structure.
[0028]
The compound of the general formula (6) is a dihydrofuran derivative. R₆₁~₆₆Represents a hydrogen atom or a substituent, and one of these is-[S]-[L]. These may be connected to each other to form a ring structure.
[0029]
The structure of the general formula (7) representing the particularly preferred [L] component is a condensed heteroaromatic ring which may have a substituent. Where A₁~ A_FourRepresents any of C, N, O, S, and P, but A₁~ A_FourAre not all C. Y₁Is -CR₇₂A linking group or bond such as-, -N-, -CO-,₂Is A₁, A₂Along with Y_ThreeIs A₂, A_ThreeTogether with this, a 4- to 8-membered ring is formed. Examples of the 4- to 8-membered ring include an aromatic hydrocarbon ring or aromatic heterocycle which may have a substituent, such as benzene, naphthalene, anthracene, azulene, phenanthrene, triphenylene, pyrene, chrysene, naphthacene, Perylene, pentacene, hexacene, coronene, trinaphthylene, furan, thiophene, pyrrole, imidazole, pyrazole, 1,2,4-triazole, 1,2,3-triazole, oxazole, thiazole, isoxazole, isothiazole, furazane, pyridine, Pyrazine, pyrimidine, pyridazine, indolizine, quinoline, isoindole, indole, isoquinoline, phthalazine, purine, naphthyridine, quinoxaline, quinazoline, cinnoline, pteridine, carbazole, phenanthridine, a Lysine, perimidine, phenanthroline, phenazine and the like.
[0030]
These may have a plurality of arbitrary substituents independently, and the plurality of substituents may be condensed with each other to further form a ring. These rings may have a substituent. R₇₁And R₇₂Each is a hydrogen atom or a substituent.
[0031]
Typical examples of the condensed heteroaromatic ring represented by the general formula (7) are shown below, but are not limited thereto.
[0032]
[Chemical 9]

[0033]
The compound of general formula (8) is an ethylene derivative. R₈₁~ R₈₃Each represents a hydrogen atom or a substituent, one of which is-[S]-[L], and [L] is a heteroaromatic ring represented by the general formula (7).
[0034]
Examples of the linking group [S] common to the general formulas (1), (2), (3), (4), (5), (6) and (8) include phenylene (o, p, m) and methylene. , -O-, -N (R)-(wherein R is a hydrogen atom or a substituent), -CO-, and the like, and these composite systems are also included.
[0035]
Specific examples of the compounds represented by the general formulas (1) to (8) in the present invention are shown below, but are not limited thereto. Compounds E-1 to E-12 are represented by the general formula (2), L-1 to L-12 are represented by the general formula (3), and N-1 to N-12 are represented by the general formula (4). 1 to X-6 are representative examples of the general formula (5), F-1 to F-6 are general formulas (6), and V-1 to V-12 are representative examples of the general formula (8).
[0036]
[Chemical Formula 10]

[0037]
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[0038]
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[0039]
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[0040]
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[0041]
Below, the typical synthesis example of an exemplary compound is shown.
Synthesis example 1
[0042]
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[0043]
(Synthesis of Compound Q-1)
90.6 g of anthranilic acid methyl ester was reacted with 54 ml of hydrous hydrazine in xylene under heating and refluxing for 9.5 hours. Thereafter, the solvent was distilled off under reduced pressure, and a small amount of ethanol was added to obtain crude crystals. Further recrystallization with ethanol yielded 64.9 g of intermediate (a) (yield 72%).
[0044]
Next, 15.0 g of intermediate a and 21.0 g of ethyl benzoyl acetate were reacted in xylene at 120 ° C. for 1 hour, and then further reacted under reflux for 8 hours. At this time, generated water and ethanol were distilled off. After allowing to cool, the precipitated crystals were collected by filtration. By recrystallizing this crystal with a mixed solvent of N, N-dimethylformamide (hereinafter abbreviated as DMF) and methanol, 14.7 g (yield 56%) of Compound (Q-1) was obtained.
[0045]
It was confirmed to be Q-1 by NMR and mass spectrum. When this compound Q-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0046]
Synthesis example 2
[0047]
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[0048]
(Synthesis of Compound E-1)
Compound (Q-1) 1.31 g (5.0 mmol) was reacted with 1.48 g (14 mmol) of potassium carbonate in dimethylacetamide and 0.43 ml (5.5 mmol) of epichlorohydrin at 50 ° C. for 3 hours. Then, it opened in water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile to obtain 0.92 g (yield 58%) of Compound (E-1).
[0049]
It was confirmed to be E-1 by NMR and mass spectrum. Moreover, when this compound E-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0050]
(Polymerization of E-1)
100 mg of anhydrous iron chloride (III) as a polymerization initiator is placed in a three-necked flask, heated under reduced pressure to completely dehydrate, and then filled with dry nitrogen gas. Under a nitrogen stream, 0.63 g (2 mmol) of E-1 and 10 ml of dehydrated DMF were added and reacted at 100 ° C. for 3 hours. Thereafter, the reaction solvent was poured into a large excess of methanol to obtain a pale yellow precipitate. This precipitate was dissolved in a small amount of tetrahydrofuran (hereinafter abbreviated as THF) and poured into a large excess of hexane to obtain 0.38 g (yield 60%) of a white precipitate (PE-1).
[0051]
When this precipitate was measured by GPC, it was confirmed to be a polymer having a number average molecular weight of about 4.500. When this polymer PE-1 was irradiated with UV light, blue-violet fluorescence was emitted.
[0052]
Synthesis example 3
[0053]
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[0054]
(Synthesis of Lactone L-0)
6.0 g (25 mmol) of iodoacetic acid-3-butenyl and 2.5 liters of distilled water were placed in a 4 liter four-necked flask, and the inside of the flask was replaced with dry argon. While stirring, 2.5 ml (2.5 mmol) of a 1 mol / L methanol solution of triethylborane was added dropwise. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours and extracted with ethyl acetate. The composition obtained by distilling off ethyl acetate was purified by silica gel column chromatography to obtain 3.3 g (yield 55%) of 3-iodomethyl-δ lactone (L-0).
[0055]
(Synthesis of Compound L-1)
1.31 g (5.0 mmol) of compound Q-1 was reacted with 1.48 g (14 mmol) of potassium carbonate in dimethylacetamide and 3.4 g (5.5 mmol) of L-0 at 50 ° C. for 3 hours. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile, whereby 1.02 g (yield 55%) of compound (L-1) was obtained.
[0056]
It was confirmed by NMR and mass spectrum that it was the target compound. When this compound L-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0057]
(L-1 polymerization)
Triethylaluminum was dissolved in dehydrated toluene to make a 3% solution, and this solution was used as an initiator. Further, 18 ml of a reaction solvent in which 0.2 ml of distilled water was added to 2 liters of dehydrated THF was poured into a 50 ml three-necked flask, and further 0.93 g (2.5 mmol) of Compound L-1 and 3 of the above triethylaluminum. 0.4 ml (0.1 mmol: 4.0 mol%) of a% toluene solution was added at 0 ° C. Thereafter, THF was refluxed for 4 days. After completion of the reaction, the reaction solution is poured into a large amount of diethyl ether, and the precipitated white solid is filtered off, washed with a 0.1 mol / L hydrochloric acid solution, dissolved in chloroform, poured into a large amount of hexane and reprecipitated. And 0.41 g (yield 44%) of white precipitate (PL-1) was obtained.
[0058]
When this precipitate was measured by GPC, it was confirmed to be a polymer having a number average molecular weight of about 5400. When this polymer PL-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0059]
Synthesis example 4
[0060]
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[0061]
(Synthesis of Compound N-1)
1.31 g (5.0 mmol) of compound Q-1 was reacted with 1.48 g (14 mmol) of potassium carbonate and 0.78 g (5.5 mmol) of 4-chloromethylnorbornene in dimethylacetamide at 50 ° C. for 3 hours. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile, whereby 0.85 g (yield 46%) of compound (N-1) was obtained.
[0062]
By NMR and mass spectrum, it was confirmed to be Compound N-1. Further, when this compound N-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0063]
(Polymerization of N-1)
0.74 g (2.0 mmol) of Compound N-1 and 71 mg (0.02 mmol, 1.0 mol%) of iridium (III) chloride trihydrate were dissolved in 20 ml of i-propanol and refluxed for 8 hours. As a result, a gray insoluble material was deposited as an insoluble material. This composition was filtered off, washed with acetone, dissolved in hot toluene, reprecipitated with a large excess of methanol, and 0.43 g (yield 58%) of a light gray polymer (PN-1) was obtained. Obtained.
[0064]
When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 5400. When this polymer PN-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0065]
Synthesis example 5
[0066]
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[0067]
(Synthesis of Compound X-1)
1.31 g (5.0 mmol) of Compound Q-1 was reacted with 0.78 g (5.0 mmol) of succinyl dichloride and 1.5 ml (11 mmol) of triethylamine in dimethylacetamide for 3 hours at room temperature. After allowing to cool, a solution of ethyleneimine 0.3 ml (5.5 mmol) in diethyl ether (3 ml) was added and reacted at 50 ° C. for 5 hours. After allowing to cool, the precipitated triethylamine hydrochloride was filtered off, 1.48 g (14 mmol) of potassium carbonate was added to the solution, and the mixture was reacted at 50 ° C. for 3 hours. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile to obtain 1.20 g (yield 61%) of compound (X-1).
[0068]
It was confirmed to be X-1 by NMR and mass spectrum. When this compound X-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0069]
(Polymerization of X-1)
A 2% acetonitrile solution of p-chlorophenyloxazolinium perchlorate is prepared as a polymerization initiator. 0.77 g (2.0 mmol) of Compound X-1 was dissolved in 10 ml of dimethylacetamide, 0.1 ml was added under a nitrogen atmosphere, and the mixture was reacted at 120 ° C for 18 hours. After completion of the reaction, the solution was poured into a large excess of methanol to obtain a white precipitate. This white solid was dissolved again in THF and reprecipitated in a large excess of diethyl ether to obtain 0.59 g (77%) of a white solid (PX-1).
[0070]
When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 6600. When this polymer PX-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0071]
Synthesis Example 6
[0072]
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[0073]
(Synthesis of Compound F-0)
1.31 g (5.0 mmol) of Compound Q-1 was reacted with 1.47 g (5.5 mmol) of 4-iodobenzoyl chloride and 0.8 ml (6.0 mmol) of triethylamine in dimethylacetamide for 3 hours at room temperature. It was. After allowing to cool, the precipitated triethylamine hydrochloride was filtered off, and the solution was partitioned with ethyl acetate. The organic layer was dehydrated with sodium sulfate, and the solvent was distilled off to obtain a crude product. By recrystallization from acetonitrile, 2.26 g (yield 91%) of a white solid (F-0) was obtained.
[0074]
NMR and mass spectrum confirmed that it was F-0. Further, this compound F-0 was irradiated with UV light, but no fluorescence emission was observed.
[0075]
(Synthesis of Compound F-1)
1.96 g (4.0 mmol) of the above compound F-0 was mixed with 22.4 mg (0.01 mmol, 2.5 mol%) of palladium (II) acetate and 26.2 mg (0.01 mmol, triphenylphosphine) in dimethylformamide. 2.5 mol%), 0.43 g (4.0 mmol) of butylammonium chloride and 1.18 g (12 mmol) of potassium acetate, and reacted at 80 ° C. for 24 hours. After allowing to cool, the solution was separated with ethyl acetate, the organic layer was dehydrated with sodium sulfate, and the solvent was distilled off to obtain a white crude product. By recrystallizing the composition with acetonitrile, 1.26 g (yield 73%) of Compound (F-1) was obtained.
[0076]
It was confirmed to be F-1 by NMR and mass spectrum. When this compound F-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0077]
(F-1 polymerization)
0.86 g (2.0 mmol) of Compound F-1 was added to 8.4 mg (0. 0) of hexafluoroantimonic acid 4-methoxy-2-oxo-2,2,6,6-tetramethylpiperidinium in dimethylacetamide. 02 mmol, 1.0%) was added under nitrogen and allowed to react for 4 hours at room temperature. The obtained reaction solution was reprecipitated in a large excess of methanol to obtain 0.61 g (yield 71%) of a white solid (PF-1).
[0078]
When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 5300. When this polymer PF-1 was irradiated with UV light, blue-violet fluorescence was emitted.
[0079]
Synthesis example 7
[0080]
Embedded image

[0081]
(Synthesis of Compound V-1)
A methanol solution of Compound Q-1 (1.31 g, 5.0 mmol) was dropped into a methanol / sodium methoxide 28% solution and reacted at room temperature for 3 hours, and then the solvent was distilled off. The obtained gray solid was dissolved again in 30 ml of methanol, and 5 ml of THF solution in which 0.8 ml (5.5 mmol) of 4-chloromethylstyrene was dissolved was added dropwise at 0 ° C. After stirring for 3 hours, the solvent was distilled off, and the white solid was reacted with 1.48 g (140 mmol) and epichlorohydrin 0.51 g for 3 hours at 100 ° C. Thereafter, it was poured into water and neutralized with 1 mol / L hydrochloric acid. The product was collected by filtration and recrystallized from acetonitrile to obtain 1.73 g (yield 92%) of compound (V-1).
[0082]
It was confirmed to be V-1 by NMR and mass spectrum. When this compound V-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0083]
(Polymerization of V-1)
0.75 g (2.0 mmol) of the above compound V-1 was dissolved in THF, and azobisisobutyronitrile (AIBN, 0.1 mmol, 5 mol%) was added at 0 ° C. under a nitrogen atmosphere. Reflux for a period of time. After allowing to cool, the reaction solution was precipitated in a large excess of methanol to obtain 0.66 g (yield 88%) of a white solid (PV-1).
[0084]
When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 7300. When this polymer PV-1 was irradiated with UV light, blue-violet fluorescence was emitted.
[0085]
Synthesis Example 8
[0086]
Embedded image

[0087]
(Copolymerization of X-1 and γ-propiolactone)
0.39 g (1.0 mmol) of the compound X-1 was dissolved in DMF, and 6.3 ml (1.0 mmol) of a 1.0% DMF solution of γ-propiolactone was added at 0 ° C. under a nitrogen atmosphere. Then, the reaction was carried out at 100 ° C. for 10 hours. After allowing to cool, the reaction solution was precipitated in a large excess of methanol to obtain 0.40 g (yield 87%) of a white solid (PLX-1).
[0088]
When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 6100. When this polymer PLX-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0089]
Synthesis Example 9
(L-1 graft copolymerization)
J. et al. Polymer Sci. 34,309 (1959), styrene and methacryloylcaprolactam were polymerized with AIBN to obtain a copolymer (PMS) of poly (methacryloylcaprolactam) and poly (styrene) (yield 27%). When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 130,000. 1.0 g of this polymer and 1.0 g of the compound L-1 were graft-polymerized in toluene at 95 ° C. using sodium caprolactone as a polymerization initiator. Since gelation occurred during the reaction, the mixture was allowed to cool, filtered, washed, and dried to obtain 1.42 g (yield 71%) of white solid PGL-1.
[0090]
When this polymer was measured by GPC, it was confirmed that the polymer had a number average molecular weight of about 170,000. When this polymer PGL-1 was irradiated with UV light, it emitted blue-violet fluorescence.
[0091]
The organic EL device of the present invention basically has a structure in which a light emitting layer is held between a pair of electrodes, and a hole injection layer or an electron injection layer is interposed as necessary. Specifically, (i) anode / light emitting layer / cathode, (ii) anode / hole injection layer / light emitting layer / cathode, (iii) anode / light emitting layer / electron injection layer / cathode, (iv) anode / positive There are structures such as hole injection layer / light emitting layer / electron injection layer / cathode.
[0092]
The light emitting layer has (1) an injection function capable of injecting holes from an anode or a hole injection layer when an electric field is applied, and (2) an injected charge. It has a transport function that moves (electrons and holes) by the force of an electric field, and (3) a light-emitting function that provides a field for recombination of electrons and holes inside the light-emitting layer and connects it to light emission. However, there may be a difference in the ease of hole injection and the ease of electron injection, and the transport function represented by the mobility of holes and electrons may be large or small, but at least either Those having a function of moving one charge are preferable.
[0093]
There is no restriction | limiting in particular about the kind of luminescent material used for this light emitting layer, The conventionally well-known thing can be used as a luminescent material in an organic EL element. Such a light-emitting material is mainly an organic compound, and may have a desired color tone, for example, Macromol. Symp. 125, pages 17-26.
[0094]
As a method for forming a light emitting layer using the above material, for example, it can be formed by thinning by a known method such as a vapor deposition method, a casting method, or an LB method. It is preferable to form a solution by dissolving in a solvent and then forming a thin film by spin coating or the like. There is no restriction | limiting in particular about the film thickness of the light emitting layer formed in this way, Although it can select suitably according to a condition, Usually, it is the range of 5 nm-5 micrometers.
[0095]
As the anode in the EL element, an electrode material made of a metal, an alloy, an electrically conductive compound, or a mixture thereof having a high work function (4 eV or more) is preferably used. Specific examples of such electrode materials include metals such as Au, CuI, indium tin oxide (ITO), SnO.₂And conductive transparent materials such as ZnO. The anode may be formed by forming a thin film from these electrode materials by a method such as vapor deposition or sputtering, and a pattern having a desired shape may be formed by a photolithography method, or (100 μm) when pattern accuracy is not so high. As described above, a pattern may be formed through a mask having a desired shape when the electrode material is deposited or sputtered. When light emission is extracted from the anode, the transmittance is desirably greater than 10%, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. Further, although the film thickness depends on the material, it is usually selected in the range of 10 nm to 1 μm, preferably 10 to 200 nm.
[0096]
On the other hand, as the cathode, a material having a low work function (4 eV or less) metal (referred to as an electron injecting metal), an alloy, an electrically conductive compound, and a mixture thereof as an electrode material is used. Specific examples of such electrode materials include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al₂O_Three) Mixtures, indium, lithium / aluminum mixtures, rare earth metals and the like. Among these, from the viewpoint of electron injectability and durability against oxidation, a mixture of an electron injectable metal and a second metal which is a stable metal having a larger work function value than this, for example, a magnesium / silver mixture, magnesium / Aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al₂O_Three) Mixtures, lithium / aluminum mixtures and the like are preferred. The cathode can be produced by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. The sheet resistance as the cathode is preferably several hundred Ω / □ or less, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. In order to transmit light, if either the anode or the cathode of the organic EL element is transparent or translucent, the light emission efficiency is improved, which is convenient.
[0097]
Next, the hole injection layer provided as necessary has a function of transmitting holes injected from the anode to the light emitting layer, and the hole injection layer is interposed between the anode and the light emitting layer. In addition, many holes are injected into the light emitting layer with lower electric field strength, and the electrons injected from the cathode or the electron injection layer into the light emitting layer are barriers to electrons present at the interface between the light emitting layer and the hole injection layer. Thus, an element having excellent light emission performance such as accumulation at the interface in the light emitting layer and improvement in light emission efficiency is obtained. The material of the hole injection layer (hereinafter referred to as the hole injection material) is not particularly limited as long as it has the above-mentioned preferable properties. Any one of commonly used ones and known ones used for the hole injection layer of EL elements can be selected and used.
[0098]
The hole injection material has either hole injection or electron barrier properties, and may be either organic or inorganic. Examples of the hole injection material include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives. Fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline copolymers, and conductive polymer oligomers, particularly thiophene oligomers. As the hole injecting material, those described above can be used, but it is preferable to use a porphyrin compound, an aromatic tertiary amine compound and a styrylamine compound, particularly an aromatic tertiary amine compound.
[0099]
Representative examples of the aromatic tertiary amine compound and styrylamine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N ′. -Bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD), 2,2-bis (4-di-p-tolylaminophenyl) propane, 1,1- Bis (4-di-p-tolylaminophenyl) cyclohexane, N, N, N ′, N′-tetra-p-tolyl-4,4′-diaminobiphenyl, 1,1-bis (4-di-p- Tolylaminophenyl) -4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N -Di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quadri Phenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene, 4-N, N-diphenyl Amino- (2-diphenylvinyl) benzene, 3-methoxy-4′-N, N-diphenylaminostilbenzene, N-phenylcarbazole, and two condensations described in US Pat. No. 5,061,569 Having an aromatic ring in the molecule, for example, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPD), JP-A-4-308688 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine (m-TDATA), etc., in which three triphenylamine units are linked in a three star burst type Is mentioned.
[0100]
Also, inorganic compounds such as p-type-Si and p-type-SiC can be used as the hole injection material. The hole injection layer can be formed by thinning the hole injection material by a known method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. Although there is no restriction | limiting in particular about the film thickness of a positive hole injection layer, Usually, it is about 5 nm-5 micrometers. The hole injection layer may have a single-layer structure composed of one or more of the above materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Furthermore, the electron injecting layer used as necessary may have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material selected from conventionally known compounds can be selected as the material. Can be used.
[0101]
Examples of materials used for the electron injection layer (hereinafter referred to as electron injection materials) include heterocyclic tetracarboxylic acid anhydrides such as nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, naphthalene perylene; carbodiimides , Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives and the like. In addition, a series of electron transport compounds described in JP-A-59-194393 is disclosed as a material for forming a light emitting layer in the publication, but as a result of studies by the present inventors, as an electron injection material. It turns out that it can be used. Furthermore, in the oxadiazole derivative, a thiadiazole derivative in which the oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron-withdrawing group can also be used as an electron injection material.
[0102]
Also, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-quinolinol) aluminum, Tris (2-methyl-8-quinolinol) aluminum, tris (5-methyl-8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metals of these metal complexes are In, Mg, Cu , Ca, Sn, Ga, or Pb can also be used as the electron injection material. In addition, metal-free or metal phthalocyanine, or those having terminal ends substituted with an alkyl group or a sulfonic acid group can be preferably used as the electron injection material. Further, the distyrylpyrazine derivative exemplified as the material of the light emitting layer can also be used as the electron injecting material. Similarly to the hole injecting layer, inorganic semiconductors such as n-type-Si and n-type-SiC can be used as the electron injecting material. Can be used as
[0103]
This electron injection layer can be formed by forming the above compound by a known thinning method such as a vacuum deposition method, a spin coating method, a casting method, or an LB method. The thickness of the electron injection layer is not particularly limited, but is usually selected in the range of 5 nm to 5 μm. This electron injection layer may have a single layer structure composed of one or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions.
[0104]
Next, a suitable example for producing the organic EL element will be described. As an example, a method for producing an EL device comprising the above-mentioned anode / hole injection layer / light emitting layer / electron injection layer / cathode will be described. First, a thin film made of a desired electrode material, for example, a material for an anode, on a suitable substrate. Is formed by a method such as vapor deposition or sputtering so as to have a film thickness of 1 μm or less, preferably 10 to 200 nm, to produce an anode. Next, a thin film made of materials of a hole injection layer, a light emitting layer, an electron injection layer, and a cathode layer, which are element materials, is sequentially formed thereon.
[0105]
Examples of the thinning method include a spin coating method, a casting method, and a vapor deposition method. Considering productivity, the spin coating method is preferable as described above, but low molecular compounds, metal electrodes, and the like cannot be formed at present under the spin coating method. For the formation of these thin film layers, vacuum vapor deposition is preferred from the standpoint that a compound-homogeneous film is easily obtained and pinholes are not easily generated. When this vapor deposition method is employed for thinning, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, etc., but generally the boat heating temperature is 50 to 450 ° C. , Degree of vacuum 10^-6-10^-3It is desirable to select appropriately within the ranges of Pa, vapor deposition rate of 0.01 to 50 nm / second, substrate temperature of −50 to 300 ° C., and film thickness of 5 nm to 5 μm.
[0106]
In the case where a DC voltage is applied to the EL element thus obtained, light emission can be observed by applying a voltage of about 3 to 40 V with the positive polarity of the anode and the negative polarity of the cathode. Further, even when a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The alternating current waveform to be applied may be arbitrary.
[0107]
【Example】
EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, the aspect of this invention is not limited to this.
[0108]
Example 1
(Production of organic EL element)
After patterning on a substrate (NH Techno Glass Co., Ltd .: NA-45) having a film of 150 nm of ITO (supra) formed on glass as an anode, the transparent support substrate provided with this ITO transparent electrode was converted to i-propyl alcohol. Was subjected to ultrasonic cleaning, dried with dry nitrogen gas, and UV ozone cleaning was performed for 5 minutes. On this transparent support substrate, 20 mg of polymer PE-1 was dissolved in 3 ml of THF, and spin-coated under conditions of 1000 rpm and 3 sec. The film thickness of the purified organic thin film was about 100 nm.
[0109]
  After fixing this board | substrate to the board | substrate holder of a commercially available vacuum evaporation apparatus, a vacuum chamber is set to 4x10.^-FourAfter reducing the pressure to Pa, the heating boat containing Alq3 was energized and heated to 250 ° C., and deposited on the light emitting layer at a deposition rate of 0.1 nm / sec to provide an electron injection layer having a thickness of 20 nm. . In addition, the substrate temperature at the time of vapor deposition was room temperature. Furthermore, lithium and aluminum are co-deposited from different vapor deposition sources at a vapor deposition rate of 1.5 to 2.0 nm / sec at a mass ratio of 6: 1 to form a counter electrode composed of the mixture of lithium and aluminum. By, YesA machine EL element DE-1 was produced.
[0110]
Examples 2-8
In Example 1, instead of PE-1, each of SP-1, PN-1, PX-1, PF-1, PV-1, PLX-1, and PGL-1 was used to spin coat to a thickness of 100 nm Then, organic EL elements DL-1, DN-1, DX-1, DF-1, DV-1, DLX-1, and DGL-1 were produced in the same manner as in Example 1 except that the light emitting layer was used.
[0111]
Example 9
In Example 1, 0.2 mg of 4-dicyanomethylene-2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM1) was dissolved in 20 mg of the polymer PE-1 to be spin-coated and 3 ml of THF. Organic EL element DD-1 was produced in exactly the same manner except that spin coating was performed under the conditions of 1000 rpm and 3 sec.
[0112]
Embedded image

[0113]
Comparative Example 1
After patterning on a substrate (NA-45: supra) with ITO deposited on glass as an anode at 150 nm, the transparent support substrate provided with this ITO transparent electrode was ultrasonically cleaned with i-propyl alcohol and dried nitrogen After drying with gas, UV ozone cleaning was performed for 5 minutes.
[0114]
After fixing this transparent support substrate to the substrate holder of a commercially available vacuum deposition apparatus, the vacuum chamber is set to 4 × 10.^-FourAfter reducing the pressure to Pa, 4,4 ′, 4 ″ -tris (—N- (m-tolyl) -N-phenylamino) triphenylamine (m-TDATA) was deposited to a thickness of 40 nm at a deposition rate of 0.2 nm / sec. Next, N, N'-diphenyl-N, N'-di (m-tolyl) -4,4'-diamino-1,1'-biphenyl (TPD) is deposited at a deposition rate. Vapor deposition was performed at a thickness of 35 nm at 0.2 nm / sec to form a hole transport layer and a light-emitting layer, and tris (8-quinolinolato) aluminum (Alq3) was deposited at a deposition rate of 0.2 nm / sec while maintaining the reduced pressure. Vapor deposition was performed to a thickness of 50 nm to form an electron transport layer, and lithium and aluminum were co-deposited at a vapor deposition rate of 1.5 to 2.0 nm / sec at a mass ratio of 6: 1 while maintaining a reduced pressure. And the lithium and By a counter electrode consisting of a mixture of Miniumu, to produce an organic EL device DT-1 comparison.
[0115]
Embedded image

[0116]
Comparative Example 2
In Comparative Example 1, an organic EL device DQ-1 was produced in exactly the same manner as in Example 1 except that Compound Q-1 was used instead of TPD to form a hole transport layer / light-emitting layer.
[0117]
  (Characteristic evaluation of EL element)
  Using source measure unit model 2400 made by Toyo Technica, YesEL elements DE-1, DL-1, DN-1, DX-1, DF-1, DV-1, DLX-1, DGL-1, DD-1 and organic EL elements DT-1, DQ for comparison -1 is an element with an ITO electrode as an anode and a counter electrode made of lithium and aluminum as a cathode to apply a direct current of 10 V to emit light. The luminance is a luminance meter BM-8 made by Topcon, and the emission wavelength is a spectrum analyzer made by Hamamatsu Photonics. Measurement was performed using PMA-11.
[0118]
First, in Comparative Example DT-1, surface emission was uniformly blue, and no dark spots were observed in the initial state, but 10 to 15 dark spots with a diameter of 100 μm or less were confirmed after driving for 1 hour.
[0119]
Next, in Comparative Example DQ-1, it was confirmed that surface emission was uniformly blue-white, and no dark spots were observed in the initial state, but after driving for 1 hour, dark spots with a diameter of 100 μm or less were 1 to 4 Confirmed. In addition, when the electroluminescence spectrum is measured, there are emission peaks at 424 nm and 454 nm, and some interaction is caused in the m-TDATA layer interface, the Alq layer interface, or the light emitting layer, resulting in a dichroic spectrum. understood.
[0120]
  on the other hand, DIn E-1, surface emission was uniformly blue-violet, and in the initial state, the occurrence of dark spots was not confirmed even after driving for 1 hour. When the electroluminescence spectrum was measured, the confirmed emission peak at 454 nm disappeared in DQ-1, and a spectrum having only an emission wavelength of 425 nm was observed. Table 1 summarizes the results of this element and elements according to other examples, DL-1, DN-1, DX-1, DF-1, DV-1, DLX-1, DGL-1, and DD-1. .
[0121]
[Table 1]

[0122]
【The invention's effect】
As shown in Table 1, it was possible to obtain high thermal stability, stability over time and productivity by polymerizing the luminescent compound. Further, in terms of light emission characteristics, it is possible to obtain an element with good color purity by suppressing the occurrence of excimer light emission without reducing the luminance of the low molecular light emitting compound.

Claims (3)

In an organic electroluminescence device in which a light emitting layer composed of a single layer or multiple layers of organic compound thin film is sandwiched between an anode and a cathode facing each other, at least one layer of the organic compound thin film is represented by the following general formula (3). An organic electroluminescence device comprising at least one compound having a polymerizable cyclic structure or a polymer thereof.

Wherein, Q ₂ is -O- or -NR ₃₅ - represents, n3 is an integer of 1-6. R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ and R ₃₅ each represent a hydrogen atom or a substituent, and any one of them is — [S] — [L]. Further, R ₃₁ to R ₃₅ may be to form a ring structure. [L] represents a monovalent luminescent compound residue represented by the following general formula (7), and [S] represents a linking group for linking [L] with a ring formed with Q ₂ . ]

Wherein, R ₇₁ represents a hydrogen atom or a substituent, each A _1, A _2, A ₃ and A _4, C, N, O, S, represents one of the P, A ₁ to A ₄ Are not all C. Y ₁ represents a linking group or a bond, Y ₂ is a group forming a 4-8 membered ring together with A _1, A _2, Y ₃ forms a 4-8 membered ring together with A _3, A ₄ group Represents. ] An organic electro thin film comprising at least one organic compound thin film containing at least one copolymer containing at least one compound selected from the compound represented by formula (3) of claim 1 as a monomer. Luminescence element. A polymer compound obtained by subjecting at least one compound selected from the compounds represented by the general formula (3) of claim 1 and a polymer having a reactive group to addition reaction, condensation reaction or graft polymerization. An organic electroluminescence device comprising at least one organic compound thin film containing at least one kind.