JP3922051B2 - Electron transporting material, its production method and its use - Google Patents
Electron transporting material, its production method and its use Download PDFInfo
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- JP3922051B2 JP3922051B2 JP2002059139A JP2002059139A JP3922051B2 JP 3922051 B2 JP3922051 B2 JP 3922051B2 JP 2002059139 A JP2002059139 A JP 2002059139A JP 2002059139 A JP2002059139 A JP 2002059139A JP 3922051 B2 JP3922051 B2 JP 3922051B2
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- 150000002431 hydrogen Chemical class 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
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- ORUIBWPALBXDOA-UHFFFAOYSA-L magnesium fluoride Chemical compound [F-].[F-].[Mg+2] ORUIBWPALBXDOA-UHFFFAOYSA-L 0.000 description 1
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
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- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- QZXNDEONRUSYFB-UHFFFAOYSA-N n-[4-(4-aminophenyl)phenyl]-3-methylaniline Chemical compound CC1=CC=CC(NC=2C=CC(=CC=2)C=2C=CC(N)=CC=2)=C1 QZXNDEONRUSYFB-UHFFFAOYSA-N 0.000 description 1
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- 150000004866 oxadiazoles Chemical class 0.000 description 1
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Description
【０００１】
【発明の属する技術分野】
本発明は電子親和力が大きくＮ型半導体となりやすい高分子からなる電子輸送性材料に関する。
また本発明は該電子輸送材料を得るための効果的な製造法に関する。
さらに本発明は該電子輸送性材料を用いた発光効率が高く、長時間発光が可能な発光素子及びその製造方法に関する。
またさらに本発明は該電子輸送性材料を用いた効率が高く、耐久性がすぐれ、オゾン発生が少なく環境への影響の少ない有機光導電体材料に関する。
【０００２】
【従来の技術】
主鎖にπ共役二重結合を有するπ共役系高分子には電子供与性物質添加により酸化され正孔が電気伝導の主役を演じるＰ型有機導電体と電子受容性物質添加により還元され電子が電気伝導の主役を演じるＮ型有機導電体とがある。前者の例としては、ポリ（２，５―チエニレン）、ポリ（２，５−ピロリレン）、ポリパラフェニレンビニレン等数多くあるが、後者の例は極めて少ない。電子伝導体となりうるｎ型有機半導体は、有機ＥＬ素子や有機光導電体電極等の電子輸送層やその他広範な用途として利用でき、その開発が切望されている。
シンセティックメタルズ、２５巻、１０３〜１０７頁（１９８８年）に記載されているポリ（２，５−ピリジンジイル）は、パイ電子共役系高分子として電子吸引性のピリジン骨格を繰り返しとする数少ないｎ型有機導電体のひとつである。しかしながら、ピリジンは電子吸引性が弱く安定なｎ型としては不十分であった。
【０００３】
Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ， Ｖｏｌ． ３２， Ｎｏ．１１， ｐｐ９９１−９９４（２０００）には、ポリ（２，５−ピリジンジイル）にニトロ基を導入した例が報告されているが、その電子輸送性や電子輸送性材料としての応用は何ら説明されていない。
【０００４】
【発明が解決しようとする課題】
本発明は、安定性、加工性、電子輸送性に優れる高分子からなる電子輸送性材料及びその製造方法を提供すること、該電子輸送性材料を用いた発光強度が高く、長寿命の発光素子及びその製造方法を提供すること、及び該電子輸送性を用いたオゾン発生の少ない有機光導電体材料を提供することを目的とする。
【０００５】
【課題を解決するための手段】
本発明者らは前記課題に鑑み鋭意検討した結果、ピリジン骨格にニトロ基を導入したピリジン系高分子は、その電子吸引性が増加し、安定なＮ型半導体になりやすく、電子輸送性材料として好適であることを見いだした。
【０００６】
さらに本発明者らは前記ニトロ基導入ピリジン系高分子を電子輸送性材料に用いることにより、発光強度が高く、長寿命の発光素子が得られることを見いだした。
【０００７】
さらに本発明者らは前記ニトロ基導入ピリジン系高分子を電子輸送性材料に用いることにより、オゾン発生が少なく環境負荷の少ない有機光導電体材料が得られることを見いだした。
すなわち、本発明は、
[１] 下記の一般式（１）
【０００８】
【化４】
（式中、Ｒ1 ，Ｒ2 ，Ｒ3は置換基を示し、該置換基の少なくとも一つはニトロ基であり、残りは水素原子；ヘテロ原子を有してもよい炭素数１以上２０以下のアルキル基；ヘテロ原子を有してもよい炭素数１以上２０以下のエステル基；炭素数２以上２０以下のアルケニル基；炭素数２以上２０以下のアルキニル基；または置換を有してもよいアリール基；炭素数１以上２０以下のカルボン酸基を表し、直鎖状、分岐状または環状のいずれの構造を有するものでもよい。ｎは１以上の整数。）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を含むことを特徴とする電子輸送性材料。
[２]電子輸送性材料が、電子受容性物質を含む前項１に記載の電子輸送性材料。
【０００９】
[３]下記の一般式（２）
【化５】
（式中、Ｒ1 ，Ｒ2 ，Ｒ3は置換基を示し、該置換基の少なくとも一つはニトロ基であり、残りは水素原子；ヘテロ原子を有してもよい炭素数１以上２０以下のアルキル基；ヘテロ原子を有してもよい炭素数１以上２０以下のエステル基；炭素数２以上２０以下のアルケニル基；炭素数２以上２０以下のアルキニル基；または置換を有してもよいアリール基；炭素数１以上２０以下のカルボン酸基を表し、直鎖状、分岐状または環状のいずれの構造を有するものでもよい。Ｘは水素またはハロゲンを表す。）で表されるニトロピリジン化合物を還元性触媒を用いて重合することを特徴とする前項１または２に記載の電子輸送性材料の製造方法。
[４]下記の一般式（３）
【化６】
（式中、Ｒ4 〜 Ｒ9は置換基を示し、該置換基の少なくとも一つはニトロ基であり、残りは水素原子；ヘテロ原子を有してもよい炭素数１以上２０以下のアルキル基；ヘテロ原子を有してもよい炭素数１以上２０以下のエステル基；炭素数２以上２０以下のアルケニル基；炭素数２以上２０以下のアルキニル基；または置換を有してもよいアリール基；炭素数１以上２０以下のカルボン酸基を表し、直鎖状、分岐状または環状のいずれの構造を有するものでもよい。Ｙは水素またはハロゲンを表す。）で表されるニトロビピリジン化合物を還元性触媒を用いて重合することを特徴とする前項１記載の電子輸送性材料の製造方法。
【００１０】
[５]前項１または２に記載の電子輸送性材料を用いることを特徴とする発光素子。
[６]前項１または２に記載の電子輸送性材料を用いることを特徴とする光導電体材料。
【００１１】
[７]発光材料との溶液とした前項１または２に記載の電子輸送材料を、電極またはホール輸送層上で重合し、溶媒を除去し、成膜することを特徴とする前項５に記載の発光素子の製造方法。
【００１２】
[８]前項５に記載の発光素子を用い画素を構成したことを特徴とする画像表示装置。
[９]前項５に記載の発光素子を用いたことを特徴とする照明装置。
【００１３】
【発明の実施の形態】
以下、本発明についてより詳細に説明する。
１．ニトロピリジン骨格の二価基を主鎖に含む高分子
本発明の電子輸送材料は、一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子からなることを特徴とする。
【００１４】
【化７】
（式中、Ｒ1 ，Ｒ2 ，Ｒ3は置換基を示し、該置換基の少なくとも一つはニトロ基であり、残りは水素原子；ヘテロ原子を有してもよい炭素数１以上２０以下のアルキル基；ヘテロ原子を有してもよい炭素数１以上２０以下のエステル基；炭素数２以上２０以下のアルケニル基；炭素数２以上２０以下のアルキニル基；または置換基を有してもよいアリール基；炭素数１以上２０以下のカルボン酸基を表し、直鎖状、分岐状または環状のいずれの構造を有するものでもよい。ｎは１以上の整数。）
【００１５】
本発明の「ニトロピリジン骨格の二価基を主鎖に含む高分子」とは、高分子主鎖の少なくとも一部にニトロピリジン骨格を含むものであればよく、いかなる化学構造の形態であってもよい。
【００１６】
本発明の一般式（１）で表されるＲ1，Ｒ2，Ｒ3は、それぞれ独立に少なくとも一つはニトロ基（例えば、トリニトロ置換体でもよい）であり、残りは水素原子；ヘテロ原子を有してもよい炭素数１以上２０以下のアルキル基；ヘテロ原子を有してもよい炭素数１以上２０以下のエステル基；炭素数２以上２０以下のアルケニル基；炭素数２以上２０以下のアルキニル基；または置換を有してもよいアリール基；炭素数１以上２０以下のカルボン酸基を表す。これらの置換基は、直鎖状、分岐状または環状のいずれの構造を有するものでもよい。ここでいう「それぞれ独立に」とは、Ｒ1，Ｒ2，Ｒ3のいずれもが独立であると言うことのみならず、高分子主鎖のそれぞれ独立したニトロピリジン骨格においても独立であることを示している。すなわち、例えばニトロピリジン主鎖の任意のＲα（αは１、２、３）がメチル基である場合、他のニトロピリジン骨格の相似の位置であるＲαではメチル基でも良いしメチル基以外の他の官能基であっても良いことを示している。従って、一つの高分子にｍ個のニトロピリジン骨格が存在する場合、任意のＲαはｍ個のニトロピリジン骨格において各々独立の官能基であることを示している。
【００１７】
一般式（１）におけるＲ1，Ｒ2，Ｒ3として、ニトロ基以外の具体例としては、水素原子、メチル基、トリフルオロメチル基、エチル基等のアルキル基、エテニル基、２−プロペニル基、１，３−ブタジエニル基、４−メトキシー２−ブテニル基等のアルケニル基、エチニル基、２−プロピニル基等のアルキニル基、フェニル基、チエニル基、ピロリル基、４−メトキシフェニル基、３−トリフルオロメチルフェニル基、ナフチル基、３―メチルチエニル基等のアリール基、フッ素、塩素等のハロゲン基、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基等を挙げることができる。好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、３−トリフリオロメチルフェニル基、ナフチル基、フッ素、カルボン酸基、カルボン酸エステル基、スルホン酸基、スルホン酸エステル基であり、より好ましくは水素原子、メチル基、トリフルオロメチル基、フェニル基、ナフチル基、フッ素、スルホン酸基、スルホン酸エステル基である。
【００１８】
本発明の一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子の具体例としては、Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ， Ｖｏｌ． ３２，Ｎｏ．１１， ｐｐ９９１−９９４（２０００）に記載のポリ（３−ニトロ−ピリジン−２，５−ジイル）以外に、ポリ（４−メチル−３−ニトロ−ピリジン−２，６−ジイル）、ポリ（４−メチル−６−トリフルオロメチル−３−ニトロ−ピリジン−２，５−ジイル）等を挙げることができるが、これらに限定されるものではない。側鎖にメチル等のアルキルを導入すると、ニトロピリジン骨格の二価基を主鎖に含む高分子の電子吸引性は若干低下するが、溶媒への可溶性が増し、加工性が改善される。また側鎖にトリフルオロメチル等のフルオロアルキルを導入すると、ニトロピリジン骨格の二価基を主鎖に含む高分子の電子吸引性及び溶媒への可溶性が増し、加工性も改善される。
【００１９】
本発明の一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子のニトロピリジン骨格は、核磁気共鳴スペクトル（以下、ＮＭＲと略す。）、赤外スペクトル（以下、ＩＲと略す。）、元素分析、質量分析法（以下、ＭＳと略す。）等の方法で分析、同定することが可能である。
【００２０】
本発明の発光素子より、洗浄等の方法により一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を分離し、さらに熱重量分析−質量分析法（以下、ＴＧ−ＭＳと略す）で分解物の構造からニトロピリジン骨格を同定、元素分析で元素の組成比を定量、ＮＭＲ、ＩＲで結合状態を同定等の方法でニトロピリジン骨格を同定することが可能である（Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ， Ｖｏｌ． ３２， Ｎｏ．１１， ｐｐ９９１−９９４（２０００））。
【００２１】
本発明の一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む重合体の分子量は、例えばゲルパーミエーションクロマトグラフィー（以下、ＧＰＣと略す。）等の液体クロマトグラフィーにより測定することができる。具体的には、例えば、ジメチルホルムアミド等の溶媒に溶解し、ＧＰＣにより測定することができる（Ｐｏｌｙｍｅｒ Ｊｏｕｒｎａｌ， Ｖｏｌ． ３２， Ｎｏ．１１， ｐｐ９９１−９９４（２０００））。
【００２２】
本発明の一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子の分子量としては、特に制限はない。モノマー単位の繰り返し数が２以上であれば、使用可能である。本発明の一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を電子輸送層として成膜する場合に、溶媒に溶解して塗布する方法や真空蒸着により塗布する方法を行うが、その場合、分子量が高すぎると溶媒に溶けにくくなったり、蒸着できない場合がある。一方、分子量が高いほど、成膜後の膜強度や均一性が優れており、分子量としてはその加工性、用途等によって使い分けることが好ましい。一般的にはＧＰＣによる分子量測定での質量平均分子量で１０００以上のものが用いられる。
【００２３】
２．ニトロピリジン骨格の二価基を主鎖に含む高分子の合成法、及びその原料
２−１．合成法
本発明の一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子の合成法は特に限定されない。
例えば、合成法としては、一般式（２）で表されるニトロピリジン構造を有する化合物の２つのＸが水素、または臭素等のハロゲンである化合物を単独でもしくは他の２つ以上の水素、またはハロゲンを有する化合物との共存下でＣｕやＮｉ等の金属を含む触媒で重合もしくは共重合する方法が挙げられる。このようなニトロピリジン構造を有する化合物としては、３−ニトロピリジン、３−ニトロ−２，５−ジブロモ−ピリジン、４−エチル−３−ニトロ−２，５−ジクロルピリジン、４−トリフルオロメチル−ニトロ−２，６−イオド−ピリジン等が挙げられる。
【００２４】
触媒としては銅粉、Ｃｕ１価錯体、Ｎｉ０価錯体等の還元性触媒が挙げられる。この中で銅粉はコスト的に有利で好ましい。
また、他の合成法の例としては、一般式（３）で表されるニトロビピリジン構造を有する化合物の２つのＹが水素、またはブロム基等のハロゲンである化合物を単独でもしくは他の２つ以上の水素、またはハロゲンを有する化合物との共存下でＣｕやＮｉ等の金属を含む触媒で重合もしくは共重合する方法が挙げられる。このようなニトロビピリジン構造を有する化合物としては、５−ニトロ−ビピリジン、５，８−ジニトロ−３，１０−ジブロモ−ビピリジン、４−エチル−５，８−ジニトロ−３，１１−ジイオド−ビピリジン、４−トリフルオロメチル−５，８ジニトロ−３，１０−ジイオド−ピリジン等が挙げられる。
【００２５】
触媒としては銅粉、Ｃｕ１価錯体、Ｎｉ０価錯体等の還元性触媒が挙げられる。この中で銅粉はコスト的に有利で好ましい。
【００２６】
３．発光素子
次に、前記一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を用いた本発明の発光素子について説明する。
図１は本発明の発光素子構成の一例を示す断面図であり、透明基板上に設けた陽極と陰極の間にホール輸送層、発光層、電子輸送層を順次設けたものである。また、本発明の発光素子構成は図１の例のみに限定されず、陽極と陰極の間に順次、１）ホール輸送層／発光層、２）発光層／電子輸送層、のいずれかを設けたものでもよく、更には３）ホール輸送材料、発光材料、電子輸送材料を含む層、４）ホール輸送材料、発光材料を含む層、５）発光材料、電子輸送材料を含む層、６）発光材料の単独層、のいずれかの層を一層設けるだけでもよい。また、図１に示した発光層は１層であるが、２つ以上の発光層が直接あるいは他層を間に挟んで積層されていてもよい。
【００２７】
３−１．電子輸送材料
本発明の発光素子においては、前記電子輸送材料に一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を用いることを特徴とする。一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を成膜する方法は特に限定しない。例えば、（Ａ）発光体層の上にニトロピリジン骨格を含む高分子の溶液を塗布し溶媒を揮発除去する方法や、（Ｂ）発光体層の上に一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子を抵抗加熱等による真空蒸着で成膜する方法、（Ｃ）発光体層の上に一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子のモノマーを塗布、成膜後に、モノマーを重合する方法が挙げられる。これらの方法は多層構造素子を作成する場合に好適である。また、発光材料や電子輸送材料、ホール輸送材料の混合単層素子を作成する方法もプロセス上有利である。例えば、（Ｄ）一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子からなる電子輸送材料と発光材料やホール輸送材料を混合した溶液を調製し、電極上に塗布後、溶媒を揮発除去する方法や、（Ｅ）一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子のモノマーと発光材料やホール輸送材料を混合した溶液を調製し、電極上に塗布後、モノマーを重合し、溶媒を揮発除去する方法が挙げられる。前記の重合体溶液やモノマー溶液を塗布する方法も特に限定されない。例えば、印刷法やインクジェット、スピンコート等、種々の方法が挙げられる。電子輸送層の厚さは、電子輸送層の導電率にもよるので一概に限定はできないが、１０ｎｍ〜１０μｍが好ましく、１０ｎｍ〜３μｍが更に好ましく、１０ｎｍ〜１μｍが特に好ましい。
【００２８】
本発明では前記一般式（１）で表されるニトロピリジン骨格の二価基を主鎖に含む高分子に他の電子輸送材料を混合及び／または積層して用いても良い。用いることのできる他の電子輸送材料としては、Ａｌｑ3（トリスアルミニウムキノリノール）などのキノリノール誘導体金属錯体、オキサジアゾール誘導体、トリアゾール誘導体などの既知の電子輸送材料が使用できるが、特にこれらに限定されることはない。
【００２９】
前記の電子輸送材料はそれぞれ単独で電子輸送層を形成するほかに、高分子材料をバインダとして各層を形成することもできる。これに使用される高分子材料としては、ポリメチルメタクリレート、ポリカーボネート、ポリエステル、ポリスルホン、ポリフェニレンオキサイドなどを例示できるが、特にこれらに限定されるものではない。
【００３０】
３−２．発光材料
発光材料としては、例えば、スチルベン構造等の共役系構造を有する化合物、アルミニウムキノリウム錯体等の軽金属錯体や遷移金属錯体等があげられるが、安定性、設計自由性等の面で金属錯体が好ましい。
【００３１】
本発明の発光素子に用いられる発光材料においては、さらに励起三重項状態からの発光あるいは励起三重項状態を経由する発光、いわゆる燐光発光物質を発光部位に有する化合物が好ましい。燐光発光物質は、励起三重項状態の量子効率の値として０．１以上が好ましく、更に好ましくは０．３以上であり、より一層好ましくは０．５以上である。尚、これらの励起三重項状態の量子効率が高い化合物は、例えば“Ｈａｎｄｂｏｏｋ ｏｆ Ｐｈｏｔｏｃｈｅｍｉｓｔｒｙ，Ｓｅｃｏｎｄ Ｅｄｉｔｉｏｎ（Ｓｔｅｖｅｎ Ｌ． Ｍｕｒｏｖほか著，Ｍａｒｃｅｌ Ｄｅｋｋｅｒ Ｉｎｃ．，１９９３）などから選ぶことができる。
【００３２】
本発明の好ましい発光材料の励起三重項状態からの発光あるいは励起三重項状態を経由する燐光発光部位としてはイリジウムや白金等の金属錯体構造及びこれらの誘導体があげられる。燐光性金属錯体構造は励起三重項状態が高温でも比較的安定であり好ましい。
【００３３】
前記の燐光性金属錯体構造に使用される遷移金属としては、周期表において第１遷移元素系列は原子番号２１のＳｃから原子番号３０のＺｎまでを、第２遷移元素系列は原子番号３９のＹから原子番号４８のＣｄまでを、第３遷移元素系列は原子番号７２のＨｆから原子番号８０のＨｇまでを含める。また前記の励起三重項状態を経由して発光する燐光性金属錯体構造の他の具体的な例としては希土類金属錯体構造を例示することができるが、何らこれに限定されるものではない。この希土類金属錯体構造に使用される希土類金属としては、周期表において原子番号５７のＬａから原子番号７１のＬｕまでを含める。
【００３４】
上述した金属錯体構造に使用される配位子の構造としては、アセチルアセトナート、２，２’−ビピリジン、４，４’−ジメチル−２，２’−ビピリジン、１，１０−フェナントロリン、２−フェニルピリジン、ポルフィリン、フタロシアニン、ピリミジン、キノリン及び／またはこれらの誘導体などを例示することができるが、何らこれらに限定されるものではない。これらの配位子は、１つの錯体について１種類または複数種類が配位される。また、前記の錯体化合物として二核錯体構造あるいは多核錯体構造や、２種類以上の錯体の複錯体構造を使用することもできる。
【００３５】
前記の発光体層に用いられる発光材料はそれぞれ単独で各層を形成するほかに、高分子材料をバインダとして各層を形成することもできる。これに使用される高分子材料としては、ポリメチルメタクリレート、ポリカーボネート、ポリエステル、ポリスルホン、ポリフェニレンオキサイドなどを例示できるが、特にこれらに限定されるものではない。
【００３６】
発光体層の厚さは一概に限定はできないが、１０ｎｍ〜１０μｍが好ましく、１０ｎｍ〜３μｍが更に好ましく１０ｎｍ〜１μｍが特に好ましい。
【００３７】
前記の発光層に用いられる発光材料の成膜方法は、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、コーティング法などを用いることが可能で、これらに特に限定されることはないが、低分子化合物に場合は主として抵抗加熱蒸着および電子ビーム蒸着が用いられ、高分子材料の場合は主に溶液塗布法が用いられる。
【００３８】
３−３．ホール輸送材料
本発明の発光素子にホール輸送材料も用いることもできる。発光材料にホール輸送機能がない場合は特にホール輸送材料を用いることにより、発光効率の向上、駆動電圧の低下等、素子の性能向上が図れる。用いるホール輸送材料に特に制限はなく、発光材料やキノキサリン構造を有する重合体からなる電子輸送材料との組み合わせで適したものを選べばよい。
【００３９】
ホール輸送材料としては、低分子化合物として、フタロシアニン類、金属フタロシアニン類、ナフタロシアニン類、金属ナフタロシアニン類、ビスアゾ化合物類、トリスアゾ化合物類、ＴＰＤ（Ｎ，Ｎ’−ジメチル−Ｎ，Ｎ’−（３−メチルフェニル）−１，１’−ビフェニル−４，４’ジアミン）、α−ＮＰＤ（４，４’−ビス［Ｎ−（１−ナフチル）−Ｎ−フェニルアミノ］ビフェニル）、ｍ−ＭＴＤＡＴＡ（４、４’，４’’−トリス（３−メチルフェニルフェニルアミノ）トリフェニルアミン）等のトリフェニルアミン誘導体類、ジフェニル類、ナフタレン類、アントラセン類の多環芳香族類、ベンゾキノン、アントラキノン等の芳香族キノン類が挙げられる。また高分子化合物として、前記低分子化合物の重合体以外にポリアニリン、ポリチオフェン、ポリエチレンジオキシチオフェン、ポリピロール、ポリパラフェニレンビニレン及びこれらの誘導体に代表されるｐ型導電性高分子、ポリカルバゾール及び誘導体、ポリシラン及び誘導体、ポリシロキサン及び誘導体等が挙げられる。これらのホール輸送材料は単独でも用いられるが、異なるホール輸送材料と混合または積層して用いてもよい。ホール輸送層の厚さは、ホール輸送層の導電率にもよるので一概に限定はできないが、１０ｎｍ〜１０μｍが好ましく、１０ｎｍ〜３μｍが更に好ましく、１０ｎｍ〜１μｍが特に好ましい。
【００４０】
またこれらのホール輸送材料はそれぞれ単独で各層を形成するほかに、高分子材料をバインダとして各層を形成することもできる。これに使用される高分子材料としては、ポリメチルメタクリレート、ポリカーボネート、ポリエステル、ポリスルホン、ポリフェニレンオキサイドなどを例示できるが、特にこれらに限定されるものではない。
【００４１】
前記のホール輸送材料の成膜方法は、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、コーティング法などを用いることが可能で、これらに特に限定されることはないが、低分子化合物に場合は主として抵抗加熱蒸着および電子ビーム蒸着が用いられ、高分子材料の場合は主に溶液塗布法が用いられる。
【００４２】
３−４．陽極材料
本発明に係る発光素子の陽極材料としては、ＩＴＯ（酸化インジウムスズ）、酸化錫、酸化亜鉛、ポリチオフェン、ポリピロール、ポリアニリンなどの導電性高分子などの既知の透明導電材料が使用できるが、特にこれらに限定されることはない。この透明導電材料による電極の表面抵抗は１〜５０Ω／□（オーム／スクエアー）であることが好ましい。これらの陽極材料の成膜方法としては、電子ビーム蒸着法、スパッタリング法、化学反応法、コーティング法などを用いることができるが、これらに特に限定されることはない。陽極の厚さは５０〜３００ｎｍが好ましい。
【００４３】
また、陽極とホール輸送層または陽極に隣接して積層される有機層の間に、ホール注入に対する注入障壁を緩和する目的でバッファ層が挿入されていてもよい。これには銅フタロシアニンなどの既知の材料が用いられるが、特にこれに限定されることはない。
【００４４】
３−５．陰極材料
本発明に係る発光素子の陰極材料としては、Ａｌ、ＭｇＡｇ合金、Ｃａなどのアルカリ土類金属、ＡｌＣａなどのＡｌとアルカリ土類金属の合金などの既知の陰極材料が使用できるが、特にこれらに限定されることはない。これらの陰極材料の成膜方法としては、抵抗加熱蒸着法、電子ビーム蒸着法、スパッタリング法、イオンプレーティング法などを用いることができるが、これらに特に限定されることはない。陰極の厚さは１０ｎｍ〜１μｍが好ましく、３０〜７００ｎｍが更に好ましく、５０〜５００ｎｍが特に好ましい。
【００４５】
また、陰極と、電子輸送層または陰極に隣接して積層される有機層との間に、電子注入効率を向上させる目的で、厚さ０．１〜１０ｎｍの絶縁層が挿入されていてもよい。この絶縁層としては、フッ化リチウム、フッ化マグネシウム、酸化マグネシウム、アルミナなどの既知の陰極材料が使用できるが、特にこれらに限定されることはない。
【００４６】
３−６．基板、応用例
本発明に係る発光素子の基板としては、発光材料の発光波長に対して透明な絶縁性基板が使用でき、ガラスのほか、ＰＥＴ（ポリエチレンテレフタレート）やポリカーボネートを始めとする透明プラスチックなどの既知の材料が使用できるが、特にこれらに限定されることはない。
【００４７】
本発明の発光素子は、マトリックス方式、セグメント方式などの既知の方法で画素を構成することができ、例えば、画像表示装置として用いることができる。また、例えば、画素を形成せずにバックライト等の照明装置として用いることもできる。
【００４８】
【実施例】
以下に本発明について代表的な例を示し具体的に説明する。尚これらは説明のための例示であって、本発明はこれらに何ら制限されるものではない。
【００４９】
＜測定装置及び測定条件＞
１）1Ｈ−ＮＭＲ
日本電子（ＪＥＯＬ）製 ＪＮＭ ＥＸ２７０
２７０Ｍｚ 溶媒：重クロロホルムまたは重ジメチルスルホシキド
【００５０】
２）ＧＰＣ測定（分子量測定）
カラム：Ｓｈｏｄｅｘ ＫＦ−Ｇ＋ＫＦ８０４Ｌ＋ＫＦ８０２＋ＫＦ８０１
溶離液：ヘキサフルオロイソプロパノール（ＨＦＩＰ）
温度 ：４０℃
検出器：ＲＩ（Ｓｈｏｄｅｘ ＲＩ−７１）
【００５１】
３）元素分析装置
ＲＥＣ０社製 ＣＨＮＳ−９３２型
【００５２】
４）ポリマー塗膜評価
実施例１〜３、比較例１で製造したＰＮＰｙ、ＰＭＮＰｙ、ＰＭＴＮＰｙ、ＰＰｙの３質量％ＨＦＩＰ溶液を調製した。これらをスピンコータで１×１ｃｍの白金箔上に塗布後、ＨＦＩＰを蒸発除去させることにより、厚さ約２００ｎｍの各ポリマー塗膜を白金箔上に成膜した。これらポリマー／白金電極を作用極とし、対極を白金箔（２×２ｃｍ）、銀電極を参照極として、０．５ＭテトラエチルアンモニウムＢＦ4／アセトニトリル溶液中で、１ｍＶ／ｓｅｃの走査速度で、サイクリックボルタモグラムを行った。
【００５３】
実施例１：ポリ（３−ニトロ−ピリジン−２，５−ジイル）（ＰＮＰｙ）の合成反応は下記スキームに従って実施した。
【化８】
【００５４】
即ち、ＤＭＦ（含水量２００ｐｐｍ）６００ｃｃを加えた１Ｌのガラス製四口フラスコ（長さ４ｃｍの撹拌はね及び冷却管付き）に、３−ニトロ−２，５−ジブロモ−ピリジン（Ｍｗ２８０）２３．０ｇを溶解し、Ｃｕ粉３７．０ｇを添加し、窒素雰囲気下、還流・攪拌しながら１０時間反応させた。反応後の反応液を２Lの冷水中に加えることにより得られた黄褐色沈殿を濾過、塩酸洗浄、水洗浄、メタノール洗浄、乾燥後１２０℃で１２時間、真空乾燥することにより、ポリ（３−ニトロ−ピリジン−２，５−ジイル）（ＰＮＰｙ）７．０ｇの粉末を得た。
【００５５】
この粉末の元素分析値及びＩＲスペクトルから目的通りの構造と推定された。またヘキサフルオロイソプロパノール（ＨＦＩＰ）を溶離液としたＧＰＣからの質量平均分子量（質量平均）は１１０００であった。ポリマー塗膜評価結果を表１示した。
【００５６】
実施例２：ポリ（４−メチル−３−ニトロ−ピリジン−２，６−ジイル） （ＰＭＮＰｙ）の合成
反応は下記スキームに従って実施した。
【化９】
【００５７】
即ち、ＤＭＦ（含水量２００ｐｐｍ）６００ｃｃを加えた１Ｌのガラス製四口フラスコ（長さ４ｃｍの撹拌はね及び冷却管付き）に、４−メチル−３−ニトロ−２，６−ジブロモ−ピリジン（Ｍｗ２９４）２１．９ｇを溶解し、Ｃｕ粉３７．０ｇを添加し、窒素雰囲気下、還流・攪拌しながら１５時間反応させた。反応後の反応液を２Ｌの冷水中に加えることにより得られた赤褐色沈殿を濾過、塩酸洗浄、水洗浄、メタノール洗浄、乾燥後１２０℃で１２時間、真空乾燥することにより、ポリ（４−メチル−３−ニトロ−ピリジン−２，５−ジイル）（ＰＭＮＰｙ）６．３ｇの粉末を得た。
【００５８】
この粉末の元素分析値及びＩＲスペクトルから目的通りの構造と推定された。またヘキサフルオロイソプロパノール（ＨＦＩＰ）を溶離液としたＧＰＣからの質量平均分子量（質量平均）は９８００であった。ポリマー塗膜評価結果を表１示した。
【００５９】
実施例３：ポリ（４−メチル−６−トリフルオロメチル−３−ニトロ−ピリジン−２，５−ジイル）（ＰＭＦＮＰｙ）の合成
反応は下記スキームに従って実施した。
【化１０】
【００６０】
即ち、ＤＭＦ（含水量２００ｐｐｍ）６００ｃｃを加えた１Ｌのガラス製四口フラスコ（長さ４ｃｍの撹拌はね及び冷却管付き）に、４−メチル−６−トリフルオロメチル−３−ニトロ−２，５−ジブロモ−ピリジン（Ｍｗ３３２）１４．８ｇを溶解し、Ｃｕ粉３７．０ｇを添加し、窒素雰囲気下、還流・攪拌しながら２０時間反応させることにより沈殿が得られた。この沈殿を含む反応液を２Ｌの冷水中に加えることにより得られた茶褐色沈殿を濾過、塩酸洗浄、水洗浄、メタノール洗浄、乾燥後１２０℃で１２時間、真空乾燥することにより、ポリ（４−メチル−６−トリフルオロメチル−３−ニトロ−ピリジン−２，５−ジイル）（ＰＭＦＮＰｙ）３．８ｇの粉末を得た。
【００６１】
この粉末の元素分析値及びＩＲスペクトルから目的通りの構造と推定された。またヘキサフルオロイソプロパノール（ＨＦＩＰ）を溶離液としたＧＰＣからの質量平均分子量（質量平均）は８７００であった。ポリマー塗膜評価結果を表１示した。
【００６２】
比較例１：ポリ（ピリジン−２，５−ジイル）（ＰＰｙ）の合成
反応は下記スキームに従って、Ｃｈｅｍ． Ｌｅｔｔ．，ｐｐ１５３（１９８８）と同様の方法で実施した。
【化１１】
【００６３】
即ち、ＤＭＦ（含水量２００ｐｐｍ）６００ｃｃを加えた１Ｌのガラス製四口フラスコ（長さ４ｃｍの撹拌はね及び冷却管付き）に、２，５−ジブロモ−ピリジン（Ｍｗ２３５）５．０ｇを溶解し、ビスシクロオクタジエニルＮｉ（０価）錯体２０ｇ、２，２−ビピリジン１ｇを添加し、窒素雰囲気下、６０℃で攪拌しながら２０時間反応させた。得られた黄色沈殿を濾過、塩酸洗浄、水洗浄、メタノール洗浄、乾燥後１２０℃で１２時間、真空乾燥することにより、ポリ（ピリジン−２，５−ジイル）１．２ｇの粉末を得た。
【００６４】
この粉末の元素分析値及びＩＲスペクトルから目的通りの構造と推定された。またヘキサフルオロイソプロパノール（ＨＦＩＰ）を溶離液としたＧＰＣからの質量平均分子量（質量平均）は１５０００であった。ポリマー塗膜評価結果を表１示した。
【００６５】
【表１】
表１に示すごとく、各ポリマーのＮ型ドーピングによる酸化還元ピークがみられた。
【００６６】
以上、本発明のニトロピリジン系ポリマーは比較例の非ニトロ系ＰＰｙに比較してＮ型ドーピングでの酸化還元ピークが高く、Ｎ型になりやすいことが証明された。
【００６７】
実施例４：燐光高分子用重合性化合物：Ｉｒ（４−ＭＡ−ＰＰｙ）2（ＰＰｙ）の合成
常法に従い４−メトキシフェニルピリジン（４−ＭｅＯ−ＰＰｙ）を合成した。即ち、下記スキーム３Ａに示すように、常法によりアルゴン気流下において４−ブロモアニソール２２．４ｇ（１２０ｍｍｏｌ）から脱水テトラヒドロフラン（ＴＨＦ）中でマグネシウム（Ｍｇ）３．４ｇを用いて（４−メトキシフェニル）マグネシウムブロマイドを合成し、これを２−ブロモピリジン１５．８ｇ（１００ｍｍｏｌ）と（１，２−ビス（ジフェニルホスフィノ）エタン）ジクロロニッケル（ＩＩ）（Ｎｉ（ｄｐｐｅ）Ｃｌ2） １．８ｇの脱水ＴＨＦ溶液に徐々に添加し、１時間還流した。反応液に５％塩酸水溶液２５０ｍｌを加えた後、クロロホルムで洗浄した。水層を炭酸水素ナトリウムで中和した後、クロロホルムで目的物を抽出し、有機層を減圧下に蒸留した。蒸留物は室温で直ちに固化し、白色固体として２−（４−メトキシフェニル）ピリジン（４−ＭｅＯ−ＰＰｙ）を１５．１ｇ（８１．５ｍｍｏｌ）得た。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。
【化１２】
【００６８】
次いでこの４−ＭｅＯ−ＰＰｙのメトキシ基を常法に従い加水分解した。即ち、下記スキームに示すように、４−ＭｅＯ−ＰＰｙ １５．０ｇ（８０．１ｍｍｏｌ）を濃塩酸中に溶解させ密閉容器中１３０℃で４時間攪拌した。反応後、反応液を炭酸水素ナトリウム水溶液で中和し、目的物をクロロホルムで抽出し、抽出物をクロロホルム／ヘキサン溶液より結晶化させ、無色の結晶として２−（４−ヒドロキシフェニル）ピリジン（４−ＨＯ−ＰＰｙ）１０．０ｇ（５８．５ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。
【化１３】
次いでこの４−ＨＯ−ＰＰｙを常法に従いヘキサクロロイリジウム酸ナトリウムｎ水和物（Ｎａ3ＩｒＣｌ6・ｎＨ2Ｏ）と反応させてビス（μ−クロロ）テトラキス（２−（４−ヒドロキシフェニル）ピリジン）ジイリジウム（ＩＩＩ）（［Ｉｒ（４−ＨＯ−ＰＰｙ）2Ｃｌ］2）を合成した。即ち、下記スキームに示すように、Ｎａ3ＩｒＣｌ6・ｎＨ2Ｏ １０．０ｇを２−エトキシエタノールと水の３：１の混合溶媒４００ｍｌ中に溶解させ、アルゴンガスを３０分間吹き込んだ後に、アルゴン気流下で４−ＨＯ−ＰＰｙ ８．６ｇ（５０．２ｍｍｏｌ）を加えて溶解させ、５時間還流した。反応後、溶媒を留去し、エタノールより再結晶させ、赤橙色の結晶として［Ｉｒ（４−ＨＯ−ＰＰｙ）2Ｃｌ］2 ５．８８ｇ（５．１８ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。
【化１４】
【００６９】
次いでこの［Ｉｒ（４−ＨＯ−ＰＰｙ）2Ｃｌ］2を、常法に従いトリフルオロメチルスルホン酸銀（Ｉ）（ＡｇＣＦ3ＳＯ3）の存在下に２−フェニルピリジン（ＰＰｙ）と反応させた。即ち、下記スキームに示すように、アルゴン気流下にて［Ｉｒ（４−ＨＯ−ＰＰｙ）2Ｃｌ］2 ３．９８ｇ（３．５ｍｍｏｌ）とＰＰｙ １５．５ｇ（１０．０ｍｍｏｌ）の脱水トルエン懸濁液にＡｇＣＦ3ＳＯ3を１．９８ｇ加え、６時間還流した。反応液をシリカゲルカラムで精製した後、溶媒を留去し、黄色粉末としてビス（２−（４−ヒドロキシフェニル）ピリジン）（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（４−ＨＯ−ＰＰｙ）2（ＰＰｙ））２．２０ｇ（３．２ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。
【化１５】
次いで、下記スキームに示すように、アルゴン気流下にて、Ｉｒ（４−ＨＯ−ＰＰｙ）2（ＰＰｙ） １．３７ｇ（２．０ｍｍｏｌ）、脱酸剤としてのトリエチルアミン０．８１ｇ（８．０ｍｍｏｌ）の脱水ＴＨＦ溶液にメタクリル酸クロライド０．５０ｇ（４．８ｍｍｏｌ）を加えて２０℃で５時間反応させた。反応液からトリエチルアミンの塩酸塩を濾別し、濾液をシリカゲルカラムで精製した後、溶媒を留去し、ビス（（２−（４−（２−メタクリロイルオキシ）フェニル）ピリジン）（２−フェニルピリジン）イリジウム（ＩＩＩ）（Ｉｒ（４−ＭＡ−ＰＰｙ）2（ＰＰｙ））１．５５ｇ（１．８８ｍｍｏｌ）を得た。同定はＣＨＮ元素分析、1Ｈ−ＮＭＲで行った。
【化１６】
実施例５〜７、比較例２〜４： 発光素子の作製、評価
実施例４で合成した燐光高分子用重合性化合物、Ｉｒ（４−ＭＡ−ＰＰｙ）2（ＰＰｙ）のヘキサフルオロイソプロパノール（ＨＦＩＰ）の５ｗｔ％溶液をポリエチレンジオキシチオフェン（ＰＥＤＯＴ、バイエル社製）が５０ｎｍの厚さで予め塗布成膜されたＩＴＯ陽極（ガラス基板上にＩＴＯが塗布されたもの）上にスピンコート法により５ｍｍ×５ｍｍの大きさに塗布後、窒素雰囲気で６０℃加熱２時間行い、燐光高分子用重合性化合物を架橋重合／６０℃３時間真空乾燥することにより、厚さ約１００ｎｍの燐光性高分子層（Ｉｒ（４−ＭＡ−ＰＰｙ）2（ＰＰｙ）架橋重合体）をＰＥＤＯＴ／ＩＴＯ陽極上に１２個成膜し、発光層を形成した。これらのうち８個の燐光性高分子／ＰＥＤＯＴ／ＩＴＯ電極上に電子輸送材料として実施例１〜３及び比較例１で合成したＰＮＰｙ、ＰＭＮＰｙ、ＰＭＦＰｙ、ＰＰｙの３ｗｔ％溶液をスピンコ−トにより成膜後、６０℃３時間真空乾燥することにより、各厚さ約５０ｎｍの電子輸送層を各２個ずつ形成させた。また残り４個の燐光性高分子／ＰＥＤＯＴ／ＩＴＯ電極のうち、電子輸送層を形成させないものを２個、電子輸送層としてＰＢＤ（２−（４−ｂｉｐｈｅｎｙｌｙｌ）−５−（４−ｔｅｒｔ−ｂｕｔｙｌｐｈｅｎｙｌ）−１，３，４−ｏｘａｄｉａｚｏｌ）を約５０ｎｍの厚さに真空蒸着により成膜したものを２個、作成した。
ついでこれら１０個の電子輸送層／燐光性高分子／ＰＥＤＯＴ／ＩＴＯ電極及び２個の燐光性高分子／ＰＥＤＯＴ／ＩＴＯ電極の電子輸送層上（ない場合は燐光性高分子上）に陰極としてＡｇ／Ｍｇを質量比９／１で約１００ｎｍの厚さに成膜し、発光層、電子輸送層のことなる６種の発光素子を各２個ずつ作製した。これら素子をアルゴン雰囲気のグローブボックス中でリード線をつけガラス容器内にアルゴン雰囲気で密閉し、発光評価に用いた。
【００７０】
発光輝度は電源として、（株）アドバンテスト社製 プログラマブル直流電圧／電流源 ＴＲ６１４３を用い、実施例において得られた発光素子に電圧を印加し、発光輝度を（株）トプコン社製 輝度計 ＢＭ−８を用いて測定した。
【００７１】
前記発光素子に直流電源を引加したところ、発光開始電圧、１０Ｖでの初期輝度、その後１０Ｖで固定し連続発光させた場合の２４０時間後の輝度は表２及び３の如くなった（各測定値は２個の平均値）。
【００７２】
【表２】
【００７３】
【表３】
【発明の効果】
本発明のニトロピリジン骨格の二価基を主鎖に含む高分子からなる電子輸送材料を用いることにより、高輝度で耐久性のある発光素子及び有機光導電体を提供することが可能となる。
【図面の簡単な説明】
【図１】本発明の発光素子の断面図の例である。
【符号の説明】
１ ガラス基板
２ 陽極
３ ホール輸送層
４ 発光層
５ 電子輸送層
６ 陰極[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electron transporting material made of a polymer having a large electron affinity and easily becoming an N-type semiconductor.
The present invention also relates to an effective production method for obtaining the electron transport material.
Furthermore, the present invention relates to a light emitting element using the electron transporting material with high luminous efficiency and capable of emitting light for a long time, and a method for manufacturing the same.
Furthermore, the present invention relates to an organic photoconductive material having high efficiency, excellent durability, less ozone generation, and less environmental impact using the electron transport material.
[0002]
[Prior art]
A π-conjugated polymer having a π-conjugated double bond in the main chain is oxidized by addition of an electron-donating substance and holes are reduced by addition of an electron-accepting substance and a P-type organic conductor that plays the main role in electrical conduction. There are N-type organic conductors that play the main role of electrical conduction. There are many examples of the former, such as poly (2,5-thienylene), poly (2,5-pyrrolylene), and polyparaphenylene vinylene, but the latter is extremely rare. An n-type organic semiconductor that can be an electron conductor can be used for an electron transport layer such as an organic EL element and an organic photoconductor electrode, and for a wide variety of other uses, and its development is eagerly desired.
Poly (2,5-pyridinediyl) described in Synthetic Metals, 25, 103-107 (1988) is one of the few n-types having an electron-withdrawing pyridine skeleton as a pi-electron conjugated polymer. One of the organic conductors. However, pyridine is insufficient as a stable n-type because of its weak electron withdrawing property.
[0003]
Polymer Journal, Vol. 32, no. 11, pp991-994 (2000) reports an example in which a nitro group is introduced into poly (2,5-pyridinediyl), but its electron transport property and application as an electron transport material are not explained at all. Not.
[0004]
[Problems to be solved by the invention]
The present invention provides an electron transporting material composed of a polymer excellent in stability, processability, and electron transporting property, and a method for producing the same, and a light emitting device having high emission intensity and long life using the electron transporting material. Another object of the present invention is to provide an organic photoconductor material with less ozone generation using the electron transport property.
[0005]
[Means for Solving the Problems]
As a result of intensive studies in view of the above problems, the present inventors have found that a pyridine-based polymer having a nitro group introduced into a pyridine skeleton has an increased electron withdrawing property and is likely to be a stable N-type semiconductor. I found it suitable.
[0006]
Furthermore, the present inventors have found that a light-emitting element with high emission intensity and long life can be obtained by using the nitro group-introduced pyridine polymer as an electron transporting material.
[0007]
Furthermore, the present inventors have found that an organic photoconductor material with less ozone generation and less environmental load can be obtained by using the nitro group-introduced pyridine polymer as an electron transporting material.
That is, the present invention
[1] The following general formula (1)
[0008]
[Formula 4]
(Wherein R 1 , R 2 , R Three Represents a substituent, at least one of the substituents is a nitro group, and the remainder is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms which may have a heteroatom; may have a heteroatom An ester group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; or an optionally substituted aryl group; a carboxylic acid having 1 to 20 carbon atoms Represents a group, and may have any of a linear, branched or cyclic structure. n is an integer of 1 or more. An electron transporting material comprising a polymer containing a divalent group of a nitropyridine skeleton represented by formula (II) in the main chain.
[2] The electron transporting material according to item 1 above, wherein the electron transporting material contains an electron accepting substance.
[0009]
[3] The following general formula (2)
[Chemical formula 5]
(Wherein R 1 , R 2 , R Three Represents a substituent, at least one of the substituents is a nitro group, and the remainder is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms which may have a heteroatom; may have a heteroatom An ester group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; or an optionally substituted aryl group; a carboxylic acid having 1 to 20 carbon atoms Represents a group, and may have any of a linear, branched or cyclic structure. X represents hydrogen or halogen. 3. The method for producing an electron transporting material according to item 1 or 2, wherein the nitropyridine compound represented by formula (1) is polymerized using a reducing catalyst.
[4] The following general formula (3)
[Chemical 6]
(Wherein R Four ~ R 9 Represents a substituent, at least one of the substituents is a nitro group, and the remainder is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms which may have a heteroatom; may have a heteroatom An ester group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; or an optionally substituted aryl group; a carboxylic acid having 1 to 20 carbon atoms Represents a group, and may have any of a linear, branched or cyclic structure. Y represents hydrogen or halogen. The method for producing an electron transporting material according to item 1 above, wherein the nitrobipyridine compound represented by formula (1) is polymerized using a reducing catalyst.
[0010]
[5] A light emitting device using the electron transporting material described in the above item 1 or 2.
[6] A photoconductor material using the electron transporting material described in the above item 1 or 2.
[0011]
[7] The electron transport material described in the above item 1 or 2 in a solution with a light emitting material is polymerized on the electrode or the hole transport layer, the solvent is removed, and a film is formed. Manufacturing method of light emitting element.
[0012]
[8] An image display device comprising a pixel using the light-emitting element according to item 5 above.
[9] An illumination device using the light-emitting element according to item 5 above.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in more detail.
1. Polymer containing divalent group of nitropyridine skeleton in main chain
The electron transport material of the present invention is characterized by comprising a polymer containing a divalent group of a nitropyridine skeleton represented by the general formula (1) in the main chain.
[0014]
[Chemical 7]
(Wherein R 1 , R 2 , R Three Represents a substituent, at least one of the substituents is a nitro group, and the remainder is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms which may have a heteroatom; may have a heteroatom An ester group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; or an aryl group which may have a substituent; a carbon atom having 1 to 20 carbon atoms It represents an acid group and may have any of a linear, branched or cyclic structure. n is an integer of 1 or more. )
[0015]
The “polymer containing a divalent group of a nitropyridine skeleton in the main chain” of the present invention may be any polymer structure as long as it contains a nitropyridine skeleton in at least a part of the polymer main chain. Also good.
[0016]
R represented by the general formula (1) of the present invention 1 , R 2 , R Three Each independently at least one is a nitro group (eg, may be a trinitro substituent), and the rest is a hydrogen atom; an alkyl group having 1 to 20 carbon atoms that may have a heteroatom; May be an ester group having 1 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkynyl group having 2 to 20 carbon atoms; or an aryl group which may have a substituent; The following carboxylic acid groups are represented. These substituents may have any of a linear, branched or cyclic structure. Here, “independently” means R 1 , R 2 , R Three These are not only independent of each other, but are also independent in the independent nitropyridine skeleton of the polymer main chain. That is, for example, any R of the nitropyridine backbone α When (α is 1, 2, 3) is a methyl group, R is a similar position of another nitropyridine skeleton. α Shows that it may be a methyl group or a functional group other than a methyl group. Therefore, when m nitropyridine skeletons exist in one polymer, any R α Indicates that each of m nitropyridine skeletons is an independent functional group.
[0017]
R in the general formula (1) 1 , R 2 , R Three As specific examples other than the nitro group, a hydrogen atom, an alkyl group such as a methyl group, a trifluoromethyl group, an ethyl group, an ethenyl group, a 2-propenyl group, a 1,3-butadienyl group, 4-methoxy-2-butenyl Alkenyl groups such as alkenyl groups, alkynyl groups such as ethynyl groups, 2-propynyl groups, phenyl groups, thienyl groups, pyrrolyl groups, 4-methoxyphenyl groups, 3-trifluoromethylphenyl groups, naphthyl groups, 3-methylthienyl groups, etc. Aryl groups, halogen groups such as fluorine and chlorine, carboxylic acid groups, carboxylic acid ester groups, sulfonic acid groups, and sulfonic acid ester groups. Preferably, a hydrogen atom, a methyl group, a trifluoromethyl group, a phenyl group, a 3-trifluoromethylphenyl group, a naphthyl group, a fluorine, a carboxylic acid group, a carboxylic acid ester group, a sulfonic acid group, and a sulfonic acid ester group, More preferred are hydrogen atom, methyl group, trifluoromethyl group, phenyl group, naphthyl group, fluorine, sulfonic acid group, and sulfonic acid ester group.
[0018]
Specific examples of the polymer containing a divalent group of the nitropyridine skeleton represented by the general formula (1) of the present invention in the main chain include Polymer Journal, Vol. 32, no. 11, pp991-994 (2000) as well as poly (3-nitro-pyridine-2,5-diyl), poly (4-methyl-3-nitro-pyridine-2,6-diyl), poly (4 -Methyl-6-trifluoromethyl-3-nitro-pyridine-2,5-diyl) and the like, but is not limited thereto. When an alkyl such as methyl is introduced into the side chain, the electron withdrawing property of the polymer containing the divalent group of the nitropyridine skeleton in the main chain is slightly lowered, but the solubility in a solvent is increased and the processability is improved. Further, when fluoroalkyl such as trifluoromethyl is introduced into the side chain, the polymer having a divalent group of the nitropyridine skeleton in the main chain becomes more electron withdrawing and soluble in a solvent, and the processability is also improved.
[0019]
The nitropyridine skeleton of a polymer containing the divalent group of the nitropyridine skeleton represented by the general formula (1) of the present invention in the main chain has a nuclear magnetic resonance spectrum (hereinafter abbreviated as NMR) and an infrared spectrum (hereinafter referred to as NMR). , IR abbreviation), elemental analysis, mass spectrometry (hereinafter abbreviated as MS), and the like.
[0020]
From the light emitting device of the present invention, a polymer containing a divalent group of the nitropyridine skeleton represented by the general formula (1) in the main chain is separated by a method such as washing, and further, thermogravimetric analysis-mass spectrometry (hereinafter, It is possible to identify the nitropyridine skeleton by methods such as identifying the nitropyridine skeleton from the structure of the decomposed product by TG-MS), quantifying the composition ratio of elements by elemental analysis, and identifying the binding state by NMR and IR. (Polymer Journal, Vol. 32, No. 11, pp991-994 (2000)).
[0021]
The molecular weight of the polymer containing the divalent group of the nitropyridine skeleton represented by the general formula (1) of the present invention in the main chain is determined by liquid chromatography such as gel permeation chromatography (hereinafter abbreviated as GPC). Can be measured. Specifically, for example, it can be dissolved in a solvent such as dimethylformamide and measured by GPC (Polymer Journal, Vol. 32, No. 11, pp991-994 (2000)).
[0022]
There is no restriction | limiting in particular as molecular weight of the polymer | macromolecule which contains the bivalent group of the nitropyridine skeleton represented by General formula (1) of this invention in a principal chain. If the number of repeating monomer units is 2 or more, it can be used. In the case where a polymer containing a divalent group of the nitropyridine skeleton represented by the general formula (1) of the present invention in the main chain is formed as an electron transport layer, it is applied by dissolving it in a solvent or by vacuum deposition. In this case, if the molecular weight is too high, it may be difficult to dissolve in a solvent or vapor deposition may not be possible. On the other hand, the higher the molecular weight, the better the film strength and uniformity after film formation, and the molecular weight is preferably selected depending on the processability, application, etc. Generally, those having a mass average molecular weight of 1000 or more as measured by GPC molecular weight are used.
[0023]
2. Synthesis method of polymer containing divalent group of nitropyridine skeleton in main chain and its raw material
2-1. Synthesis method
The method for synthesizing the polymer containing the divalent group of the nitropyridine skeleton represented by the general formula (1) of the present invention in the main chain is not particularly limited.
For example, as a synthesis method, a compound having a nitropyridine structure represented by the general formula (2), in which two Xs are hydrogen, or a halogen such as bromine alone or other two or more hydrogens, or Examples thereof include polymerization or copolymerization with a catalyst containing a metal such as Cu or Ni in the presence of a halogen-containing compound. Compounds having such a nitropyridine structure include 3-nitropyridine, 3-nitro-2,5-dibromo-pyridine, 4-ethyl-3-nitro-2,5-dichloropyridine, 4-trifluoromethyl. -Nitro-2,6-iodo-pyridine and the like.
[0024]
Examples of the catalyst include reducing catalysts such as copper powder, Cu monovalent complex, and Ni0 valent complex. Among these, copper powder is preferable in terms of cost.
As another example of the synthesis method, a compound having a nitrobipyridine structure represented by the general formula (3), wherein two Ys are hydrogen or a halogen such as a bromo group, alone or the other two Examples thereof include a method of polymerizing or copolymerizing with a catalyst containing a metal such as Cu or Ni in the presence of the above-described compound having hydrogen or halogen. Examples of the compound having such a nitrobipyridine structure include 5-nitro-bipyridine, 5,8-dinitro-3,10-dibromo-bipyridine, 4-ethyl-5,8-dinitro-3,11-diiodo-bipyridine, 4-trifluoromethyl-5,8 dinitro-3,10-diiodo-pyridine and the like can be mentioned.
[0025]
Examples of the catalyst include reducing catalysts such as copper powder, Cu monovalent complex, and Ni0 valent complex. Among these, copper powder is preferable in terms of cost.
[0026]
3. Light emitting element
Next, the light emitting device of the present invention using a polymer containing a divalent group of the nitropyridine skeleton represented by the general formula (1) in the main chain will be described.
FIG. 1 is a cross-sectional view showing an example of the structure of a light-emitting element according to the present invention, in which a hole transport layer, a light-emitting layer, and an electron transport layer are sequentially provided between an anode and a cathode provided on a transparent substrate. In addition, the structure of the light-emitting element of the present invention is not limited to the example of FIG. 1, and any one of 1) hole transport layer / light-emitting layer and 2) light-emitting layer / electron transport layer is sequentially provided between the anode and the cathode. 3) hole transport material, light emitting material, layer containing electron transport material, 4) hole transport material, layer containing light emitting material, 5) light emitting material, layer containing electron transport material, 6) light emission Only one layer of a single layer of material may be provided. Further, although the light emitting layer shown in FIG. 1 is one layer, two or more light emitting layers may be laminated directly or with another layer interposed therebetween.
[0027]
3-1. Electron transport material
In the light emitting device of the present invention, a polymer containing a divalent group of a nitropyridine skeleton represented by the general formula (1) in the main chain is used as the electron transport material. There is no particular limitation on the method for forming a polymer containing a divalent group of the nitropyridine skeleton represented by the general formula (1) in the main chain. For example, (A) a method of applying a polymer solution containing a nitropyridine skeleton on the phosphor layer and removing the solvent by volatilization, or (B) a nitro represented by the general formula (1) on the phosphor layer. A method of forming a film of a polymer containing a divalent group of a pyridine skeleton in the main chain by vacuum deposition such as resistance heating, (C) a divalent nitropyridine skeleton represented by the general formula (1) on the phosphor layer Examples include a method of polymerizing a monomer after coating a polymer monomer containing a group in the main chain and forming a film. These methods are suitable for producing a multilayer structure element. In addition, a method for producing a mixed single layer element of a light emitting material, an electron transport material, and a hole transport material is also advantageous in terms of process. For example, (D) a solution in which an electron transport material composed of a polymer containing a divalent group of a nitropyridine skeleton represented by the general formula (1) in the main chain, a light emitting material, and a hole transport material is prepared, (E) A polymer monomer containing a divalent group of a nitropyridine skeleton represented by the general formula (1) in the main chain, a light emitting material, and a hole transport material were mixed. Examples of the method include preparing a solution, applying the solution on an electrode, polymerizing the monomer, and removing the solvent by volatilization. The method for applying the polymer solution or the monomer solution is not particularly limited. For example, various methods, such as a printing method, an inkjet, and a spin coat, are mentioned. Although the thickness of the electron transport layer depends on the conductivity of the electron transport layer and cannot be generally limited, it is preferably 10 nm to 10 μm, more preferably 10 nm to 3 μm, and particularly preferably 10 nm to 1 μm.
[0028]
In the present invention, another electron transport material may be mixed and / or laminated on the polymer containing the divalent group of the nitropyridine skeleton represented by the general formula (1) in the main chain. Other electron transport materials that can be used include Alq. Three Known electron transport materials such as quinolinol derivative metal complexes such as (trisaluminum quinolinol), oxadiazole derivatives, and triazole derivatives can be used, but are not particularly limited thereto.
[0029]
In addition to forming the electron transport layer alone, each of the electron transport materials can also form each layer using a polymer material as a binder. Examples of the polymer material used for this include, but are not limited to, polymethyl methacrylate, polycarbonate, polyester, polysulfone, polyphenylene oxide, and the like.
[0030]
3-2. Luminescent material
Examples of the light emitting material include a compound having a conjugated structure such as a stilbene structure, a light metal complex such as an aluminum quinolium complex, and a transition metal complex. A metal complex is preferable in terms of stability and design freedom. .
[0031]
In the light-emitting material used for the light-emitting element of the present invention, a compound further having light emission from an excited triplet state or light emission via an excited triplet state, that is, a so-called phosphorescent substance is preferable. The phosphorescent substance preferably has a quantum efficiency value in the excited triplet state of 0.1 or more, more preferably 0.3 or more, and even more preferably 0.5 or more. These compounds having high quantum efficiency in the excited triplet state can be selected from, for example, “Handbook of Photochemistry, Second Edition (Steven L. Murov et al., Marcel Dekker Inc., 1993).
[0032]
Examples of phosphorescent sites that emit light from the excited triplet state or pass through the excited triplet state of the preferred light emitting material of the present invention include metal complex structures such as iridium and platinum, and derivatives thereof. A phosphorescent metal complex structure is preferable because the excited triplet state is relatively stable even at high temperatures.
[0033]
As the transition metal used in the phosphorescent metal complex structure, in the periodic table, the first transition element series is Sc of atomic number 21 to Zn of atomic number 30 and the second transition element series is Y of atomic number 39. To Cd of atomic number 48, the third transition element series includes from Hf of atomic number 72 to Hg of atomic number 80. As another specific example of the phosphorescent metal complex structure that emits light via the excited triplet state, a rare earth metal complex structure can be exemplified, but the present invention is not limited thereto. The rare earth metal used in this rare earth metal complex structure includes La of atomic number 57 to Lu of atomic number 71 in the periodic table.
[0034]
Examples of the structure of the ligand used in the above metal complex structure include acetylacetonate, 2,2′-bipyridine, 4,4′-dimethyl-2,2′-bipyridine, 1,10-phenanthroline, 2- Examples thereof include, but are not limited to, phenylpyridine, porphyrin, phthalocyanine, pyrimidine, quinoline and / or derivatives thereof. One or more kinds of these ligands are coordinated with respect to one complex. In addition, a binuclear complex structure or a polynuclear complex structure, or a complex structure of two or more complexes can be used as the complex compound.
[0035]
In addition to forming each of the light emitting materials used for the light emitting layer, each layer can be formed using a polymer material as a binder. Examples of the polymer material used for this include, but are not limited to, polymethyl methacrylate, polycarbonate, polyester, polysulfone, polyphenylene oxide, and the like.
[0036]
The thickness of the light emitting layer cannot be generally limited, but is preferably 10 nm to 10 μm, more preferably 10 nm to 3 μm, and particularly preferably 10 nm to 1 μm.
[0037]
As a film formation method of the light emitting material used for the light emitting layer, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a coating method, or the like can be used. In the case of molecular compounds, resistance heating vapor deposition and electron beam vapor deposition are mainly used, and in the case of polymer materials, a solution coating method is mainly used.
[0038]
3-3. Hall transport material
A hole transport material can also be used in the light emitting device of the present invention. When the light-emitting material does not have a hole transport function, the performance of the element can be improved by improving the light emission efficiency and driving voltage by using a hole transport material. There is no restriction | limiting in particular in the hole transport material to be used, What is necessary is just to select a suitable thing in combination with the electron transport material which consists of a light emitting material and the polymer which has a quinoxaline structure.
[0039]
Examples of the hole transport material include low molecular weight compounds such as phthalocyanines, metal phthalocyanines, naphthalocyanines, metal naphthalocyanines, bisazo compounds, trisazo compounds, TPD (N, N′-dimethyl-N, N ′-( 3-methylphenyl) -1,1′-biphenyl-4,4′diamine), α-NPD (4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl), m-MTDATA Triphenylamine derivatives such as (4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine), diphenyls, naphthalenes, polycyclic aromatics of anthracene, benzoquinone, anthraquinone, etc. Aromatic quinones. Further, as a polymer compound, in addition to the polymer of the low-molecular compound, polyaniline, polythiophene, polyethylenedioxythiophene, polypyrrole, polyparaphenylene vinylene, and p-type conductive polymers represented by these derivatives, polycarbazole and derivatives, Examples include polysilane and derivatives, polysiloxane and derivatives. These hole transport materials may be used alone, but may be mixed or laminated with different hole transport materials. Although the thickness of the hole transport layer depends on the conductivity of the hole transport layer, it cannot be generally limited, but is preferably 10 nm to 10 μm, more preferably 10 nm to 3 μm, and particularly preferably 10 nm to 1 μm.
[0040]
In addition to forming each layer alone, these hole transport materials can also form each layer using a polymer material as a binder. Examples of the polymer material used for this include, but are not limited to, polymethyl methacrylate, polycarbonate, polyester, polysulfone, polyphenylene oxide, and the like.
[0041]
The film formation method of the hole transport material may be a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, a coating method, or the like. In general, resistance heating vapor deposition and electron beam vapor deposition are used, and in the case of a polymer material, a solution coating method is mainly used.
[0042]
3-4. Anode material
As the anode material of the light emitting device according to the present invention, known transparent conductive materials such as conductive polymers such as ITO (indium tin oxide), tin oxide, zinc oxide, polythiophene, polypyrrole, and polyaniline can be used. It is not limited to. The surface resistance of the electrode made of this transparent conductive material is preferably 1 to 50Ω / □ (ohm / square). As a method for forming these anode materials, an electron beam vapor deposition method, a sputtering method, a chemical reaction method, a coating method, and the like can be used, but there is no particular limitation thereto. The thickness of the anode is preferably 50 to 300 nm.
[0043]
Further, a buffer layer may be inserted between the anode and the hole transport layer or the organic layer laminated adjacent to the anode for the purpose of relaxing the injection barrier against hole injection. For this, a known material such as copper phthalocyanine is used, but it is not particularly limited thereto.
[0044]
3-5. Cathode material
As the cathode material of the light emitting device according to the present invention, known cathode materials such as Al, MgAg alloy, alkaline earth metal such as Ca, Al and alkaline earth metal alloy such as AlCa can be used. There is no limit. As a film forming method for these cathode materials, a resistance heating vapor deposition method, an electron beam vapor deposition method, a sputtering method, an ion plating method, or the like can be used, but is not particularly limited thereto. The thickness of the cathode is preferably 10 nm to 1 μm, more preferably 30 to 700 nm, and particularly preferably 50 to 500 nm.
[0045]
An insulating layer having a thickness of 0.1 to 10 nm may be inserted between the cathode and the electron transport layer or the organic layer stacked adjacent to the cathode for the purpose of improving the electron injection efficiency. . As this insulating layer, known cathode materials such as lithium fluoride, magnesium fluoride, magnesium oxide, and alumina can be used, but are not particularly limited thereto.
[0046]
3-6. Substrate, application example
As the substrate of the light emitting device according to the present invention, an insulating substrate transparent to the emission wavelength of the light emitting material can be used. In addition to glass, known materials such as transparent plastics such as PET (polyethylene terephthalate) and polycarbonate are used. Can be used, but is not particularly limited thereto.
[0047]
The light-emitting element of the present invention can form pixels by a known method such as a matrix method or a segment method, and can be used, for example, as an image display device. For example, it can also be used as an illumination device such as a backlight without forming pixels.
[0048]
【Example】
Hereinafter, the present invention will be described in detail by way of typical examples. These are illustrative examples, and the present invention is not limited to these.
[0049]
<Measurement equipment and measurement conditions>
1) 1 H-NMR
JNM EX270 made by JEOL
270Mz Solvent: deuterated chloroform or deuterated dimethyl sulfoxide
[0050]
2) GPC measurement (molecular weight measurement)
Column: Shodex KF-G + KF804L + KF802 + KF801
Eluent: Hexafluoroisopropanol (HFIP)
Temperature: 40 ° C
Detector: RI (Shodex RI-71)
[0051]
3) Elemental analyzer
CHNS-932 type manufactured by REC0
[0052]
4) Polymer coating evaluation
3 mass% HFIP solutions of PNPy, PMNPy, PMTNPy, and PPy produced in Examples 1 to 3 and Comparative Example 1 were prepared. These were coated on a 1 × 1 cm platinum foil with a spin coater, and then HFIP was removed by evaporation to form each polymer coating having a thickness of about 200 nm on the platinum foil. 0.5M tetraethylammonium BF with these polymer / platinum electrodes as the working electrode, the counter electrode as the platinum foil (2 × 2 cm), and the silver electrode as the reference electrode Four A cyclic voltammogram was performed in a / acetonitrile solution at a scan rate of 1 mV / sec.
[0053]
Example 1: The synthesis reaction of poly (3-nitro-pyridine-2,5-diyl) (PNPy) was carried out according to the following scheme.
[Chemical 8]
[0054]
That is, 3-nitro-2,5-dibromo-pyridine (Mw280) 23. was added to a 1 L glass four-necked flask (with a 4 cm long stirring splash and a cooling tube) to which 600 cc of DMF (water content 200 ppm) was added. 0 g was dissolved, 37.0 g of Cu powder was added, and the mixture was reacted for 10 hours under reflux and stirring in a nitrogen atmosphere. The yellowish brown precipitate obtained by adding the reaction solution after the reaction to 2 L of cold water was filtered, washed with hydrochloric acid, washed with water, washed with methanol, dried and then vacuum dried at 120 ° C. for 12 hours to obtain poly (3- A powder of 7.0 g of nitro-pyridine-2,5-diyl) (PNPy) was obtained.
[0055]
It was estimated from the elemental analysis value and IR spectrum of this powder that the structure was as intended. The mass average molecular weight (mass average) from GPC using hexafluoroisopropanol (HFIP) as an eluent was 11,000. The results of polymer coating evaluation are shown in Table 1.
[0056]
Example 2: Synthesis of poly (4-methyl-3-nitro-pyridine-2,6-diyl) (PMNPy)
The reaction was carried out according to the following scheme.
[Chemical 9]
[0057]
That is, to a 1 L glass four-necked flask (with a 4 cm long stirring splash and a cooling tube) to which 600 cc of DMF (water content 200 ppm) was added, 4-methyl-3-nitro-2,6-dibromo-pyridine ( Mw294) 21.9 g was dissolved, Cu powder 37.0 g was added, and the mixture was reacted for 15 hours under reflux and stirring in a nitrogen atmosphere. The reddish brown precipitate obtained by adding the reaction solution after the reaction to 2 L of cold water was filtered, washed with hydrochloric acid, washed with water, washed with methanol, dried and then vacuum dried at 120 ° C. for 12 hours to obtain poly (4-methyl -3-g powder of -3-nitro-pyridine-2,5-diyl) (PMNPy) was obtained.
[0058]
It was estimated from the elemental analysis value and IR spectrum of this powder that the structure was as intended. Further, the mass average molecular weight (mass average) from GPC using hexafluoroisopropanol (HFIP) as an eluent was 9,800. The results of polymer coating evaluation are shown in Table 1.
[0059]
Example 3: Synthesis of poly (4-methyl-6-trifluoromethyl-3-nitro-pyridine-2,5-diyl) (PMFNPy)
The reaction was carried out according to the following scheme.
[Chemical Formula 10]
[0060]
That is, to a 1 L glass four-necked flask (with 4 cm long stirring splash and cooling tube) to which 600 cc of DMF (water content 200 ppm) was added, 4-methyl-6-trifluoromethyl-3-nitro-2, A precipitate was obtained by dissolving 14.8 g of 5-dibromo-pyridine (Mw332), adding 37.0 g of Cu powder, and reacting for 20 hours under reflux and stirring in a nitrogen atmosphere. The brown precipitate obtained by adding the reaction solution containing this precipitate to 2 L of cold water is filtered, washed with hydrochloric acid, washed with water, washed with methanol, dried and then vacuum dried at 120 ° C. for 12 hours to obtain poly (4- Methyl-6-trifluoromethyl-3-nitro-pyridine-2,5-diyl) (PMFNPy) 3.8 g of powder was obtained.
[0061]
It was estimated from the elemental analysis value and IR spectrum of this powder that the structure was as intended. The mass average molecular weight (mass average) from GPC using hexafluoroisopropanol (HFIP) as an eluent was 8,700. The results of polymer coating evaluation are shown in Table 1.
[0062]
Comparative Example 1: Synthesis of poly (pyridine-2,5-diyl) (PPy)
The reaction was carried out according to the following scheme in Chem. Lett. , Pp 153 (1988).
Embedded image
[0063]
That is, 5.0 g of 2,5-dibromo-pyridine (Mw235) was dissolved in a 1 L glass four-necked flask (with a stirring splash of 4 cm in length and a cooling tube) to which 600 cc of DMF (water content 200 ppm) was added. Then, 20 g of a biscyclooctadienyl Ni (zero valent) complex and 1 g of 2,2-bipyridine were added, and the mixture was reacted for 20 hours while stirring at 60 ° C. in a nitrogen atmosphere. The obtained yellow precipitate was filtered, washed with hydrochloric acid, washed with water, washed with methanol, dried and then vacuum dried at 120 ° C. for 12 hours to obtain 1.2 g of poly (pyridine-2,5-diyl).
[0064]
It was estimated from the elemental analysis value and IR spectrum of this powder that the structure was as intended. The mass average molecular weight (mass average) from GPC using hexafluoroisopropanol (HFIP) as an eluent was 15000. The results of polymer coating evaluation are shown in Table 1.
[0065]
[Table 1]
As shown in Table 1, redox peaks due to N-type doping of each polymer were observed.
[0066]
As described above, it has been proved that the nitropyridine-based polymer of the present invention has a higher oxidation-reduction peak in N-type doping than the non-nitro-based PPy of Comparative Example, and is likely to be N-type.
[0067]
Example 4: Polymerizable compound for phosphorescent polymer: Ir (4-MA-PPy) 2 Synthesis of (PPy)
4-Methoxyphenylpyridine (4-MeO-PPy) was synthesized according to a conventional method. That is, as shown in the following scheme 3A, in a conventional manner, 22.4 g (120 mmol) of 4-bromoanisole and 3.4 g of magnesium (Mg) in dehydrated tetrahydrofuran (THF) under an argon stream (4-methoxyphenyl) ) Magnesium bromide was synthesized from 15.8 g (100 mmol) of 2-bromopyridine and (1,2-bis (diphenylphosphino) ethane) dichloronickel (II) (Ni (dppe) Cl 2 ) Slowly added to 1.8 g of dehydrated THF solution and refluxed for 1 hour. 250 ml of 5% aqueous hydrochloric acid solution was added to the reaction solution, and then washed with chloroform. The aqueous layer was neutralized with sodium hydrogen carbonate, the target product was extracted with chloroform, and the organic layer was distilled under reduced pressure. The distillate solidified immediately at room temperature to obtain 15.1 g (81.5 mmol) of 2- (4-methoxyphenyl) pyridine (4-MeO-PPy) as a white solid. Identification is CHN elemental analysis, 1 Performed by 1 H-NMR.
Embedded image
[0068]
Subsequently, the methoxy group of 4-MeO-PPy was hydrolyzed according to a conventional method. That is, as shown in the following scheme, 15.0 g (80.1 mmol) of 4-MeO-PPy was dissolved in concentrated hydrochloric acid and stirred at 130 ° C. for 4 hours in a sealed container. After the reaction, the reaction solution was neutralized with an aqueous sodium hydrogen carbonate solution, the target product was extracted with chloroform, and the extract was crystallized from a chloroform / hexane solution to give 2- (4-hydroxyphenyl) pyridine (4 -HO-PPy) 10.0g (58.5 mmol) was obtained. Identification is CHN elemental analysis, 1 Performed by 1 H-NMR.
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Next, this 4-HO-PPy was converted into sodium hexachloroiridate n hydrate (Na Three IrCl 6 ・ NH 2 O) and bis (μ-chloro) tetrakis (2- (4-hydroxyphenyl) pyridine) diiridium (III) ([Ir (4-HO-PPy) 2 Cl] 2 ) Was synthesized. That is, as shown in the following scheme, Na Three IrCl 6 ・ NH 2 10.0 g of O was dissolved in 400 ml of a 3: 1 mixed solvent of 2-ethoxyethanol and water, and argon gas was blown in for 30 minutes, and then 8.6 g (50.2 mmol) of 4-HO-PPy under an argon stream. Was dissolved and refluxed for 5 hours. After the reaction, the solvent was distilled off and recrystallized from ethanol to give [Ir (4-HO-PPy) as red-orange crystals. 2 Cl] 2 5.88 g (5.18 mmol) were obtained. Identification is CHN elemental analysis, 1 Performed by 1 H-NMR.
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[0069]
This [Ir (4-HO-PPy) 2 Cl] 2 In accordance with a conventional method, silver trifluoromethylsulfonate (I) (AgCF Three SO Three ) In the presence of 2-phenylpyridine (PPy). That is, as shown in the following scheme, [Ir (4-HO-PPy) under an argon stream. 2 Cl] 2 AgCF was added to a dehydrated toluene suspension of 3.98 g (3.5 mmol) and PPy 15.5 g (10.0 mmol). Three SO Three Was added and refluxed for 6 hours. After the reaction solution was purified with a silica gel column, the solvent was distilled off, and bis (2- (4-hydroxyphenyl) pyridine) (2-phenylpyridine) iridium (III) (Ir (4-HO-PPy) was obtained as a yellow powder. 2 (PPy)) 2.20 g (3.2 mmol) was obtained. Identification is CHN elemental analysis, 1 Performed by 1 H-NMR.
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Then, as shown in the following scheme, Ir (4-HO-PPy) under an argon stream 2 (PPy) 0.50 g (4.8 mmol) of methacrylic acid chloride was added to a dehydrated THF solution of 1.37 g (2.0 mmol) and triethylamine 0.81 g (8.0 mmol) as a deoxidizer, and the mixture was stirred at 20 ° C. for 5 hours. Reacted. After the triethylamine hydrochloride was filtered off from the reaction solution and the filtrate was purified with a silica gel column, the solvent was distilled off to give bis ((2- (4- (2-methacryloyloxy) phenyl) pyridine) (2-phenylpyridine). ) Iridium (III) (Ir (4-MA-PPy) 2 (PPy)) 1.55 g (1.88 mmol) was obtained. Identification is CHN elemental analysis, 1 Performed by 1 H-NMR.
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Examples 5 to 7 and Comparative Examples 2 to 4: Production and evaluation of light-emitting elements
Polymerizable compound for phosphorescent polymer synthesized in Example 4, Ir (4-MA-PPy) 2 A 5 wt% solution of (PPy) hexafluoroisopropanol (HFIP) was coated with polyethylene dioxythiophene (PEDOT, manufactured by Bayer) at a thickness of 50 nm, and an ITO anode (ITO was coated on a glass substrate). After coating to a size of 5 mm × 5 mm by a spin coating method, heating is performed at 60 ° C. for 2 hours in a nitrogen atmosphere, and the polymerizable compound for phosphorescent polymer is crosslinked and dried by vacuum drying at 60 ° C. for 3 hours, About 100 nm phosphorescent polymer layer (Ir (4-MA-PPy) 2 Twelve (PPy) cross-linked polymers) were formed on the PEDOT / ITO anode to form a light emitting layer. Among these, a 3 wt% solution of PNPy, PMNPy, PMFPy, PPy synthesized in Examples 1 to 3 and Comparative Example 1 as an electron transport material was formed on 8 phosphorescent polymer / PEDOT / ITO electrodes by spin coating. After the film formation, two electron transport layers each having a thickness of about 50 nm were formed by vacuum drying at 60 ° C. for 3 hours. Of the remaining 4 phosphorescent polymer / PEDOT / ITO electrodes, 2 do not form an electron transport layer, and PBD (2- (4-biphenylyl) -5- (4-tert-butylphenyl) as an electron transport layer. ) -1,3,4-oxadiazol) having a thickness of about 50 nm formed by vacuum deposition.
Next, Ag is used as a cathode on the electron transport layer of these ten electron transport layers / phosphorescent polymer / PEDOT / ITO electrode and two phosphorescent polymer / PEDOT / ITO electrodes (on the phosphorescent polymer if not). / Mg was formed to a thickness of about 100 nm at a mass ratio of 9/1, and two each of six types of light-emitting elements each consisting of a light-emitting layer and an electron transport layer were produced. These devices were attached with lead wires in a glove box in an argon atmosphere, sealed in a glass container in an argon atmosphere, and used for light emission evaluation.
[0070]
Luminance is supplied as a power source using a programmable DC voltage / current source TR6143 manufactured by Advantest Co., Ltd., and voltage is applied to the light-emitting elements obtained in the examples, and the luminance is luminometer BM-8 manufactured by Topcon Corporation. It measured using.
[0071]
When a direct current power source was applied to the light emitting element, the initial luminance at the light emission starting voltage of 10 V, and the luminance after 240 hours when continuously emitting light after fixing at 10 V were as shown in Tables 2 and 3 (each measurement The value is the average of two).
[0072]
[Table 2]
[0073]
[Table 3]
【The invention's effect】
By using an electron transport material comprising a polymer containing a divalent group of the nitropyridine skeleton in the main chain of the present invention, it is possible to provide a light-emitting element and an organic photoconductor having high luminance and durability.
[Brief description of the drawings]
FIG. 1 is an example of a cross-sectional view of a light-emitting element of the present invention.
[Explanation of symbols]
1 Glass substrate
2 Anode
3 Hole transport layer
4 Light emitting layer
5 Electron transport layer
6 Cathode
Claims (7)
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