JP3879372B2 - Organic electronic device, electrophotographic photosensitive member, electrophotographic image forming apparatus and process cartridge - Google Patents

Description

（式中、Ａｒ¹、Ａｒ²、Ａｒ³およびＡｒ⁴はそれぞれ同一でも異なっていてもよく、置換または無置換のアリール基を表し、Ａｒ⁵は置換または無置換の２価の芳香族炭化水素基を表し、ｋは０または１を表し、Ａｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵のうちの１〜４個は上記一般式（１）中の−Ｄ−ＳｉＲ_3-aＱ_aで表される基と結合する結合手を有する）
で表される化合物である。
【００２７】
ここで、上記式（４）中、Ａｒ¹、Ａｒ²、Ａｒ³およびＡｒ⁴で表される置換または無置換のアリール基としては、下記式（５）〜（１１）：
【化２】

【化３】

【化４】

【化５】

【化６】

【化７】

【化８】

（式中、Ｒ¹は水素原子、炭素数１〜４のアルキル基、フェニル基、炭素数７〜１０のアルキルフェニル基、炭素数７〜１０のアルコキシフェニル基または炭素数７〜１０のアラルキル基を表し、Ｒ²およびＲ³はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フェニル基、炭素数７〜１０のアルコキシフェニル基、炭素数７〜１０のアラルキル基またはハロゲン基を表し、Ａｒ⁶は置換または無置換の２価の芳香族炭化水素基を表し、Ｚは２価の官能基を表し、ｓは１〜３の整数を表し、・は上記一般式（１）中の−Ｄ−ＳｉＲ_3-aＱ_aで表される基が結合する場合の結合位置を表す）
で表される構造のうちのいずれかを有するものが好ましい。さらに、上記式（１１）中のＡｒ⁶で表される置換または無置換の２価の芳香族炭化水素基としては、下記一般式（１２）または（１３）：
【化９】

【化１０】

（式中、Ｒ⁴およびＲ⁵はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フェニル基、炭素数７〜１０のアルコキシフェニル基、炭素数７〜１０のアラルキル基またはハロゲン基を表し、ｔは１〜３の整数を表す）
で表される構造を有するものが好ましく；
上記式（１１）中のＺで表される２価の基としては、下記式（１４）〜（２１）：
【化１１】

【化１２】

【化１３】

【化１４】

【化１５】

【化１６】

【化１７】

【化１８】

（式中、Ｒ⁶およびＲ⁷はそれぞれ水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシ基、フェニル基、炭素数７〜１０のアルコキシフェニル基、炭素数７〜１０のアラルキル基またはハロゲン基を表し、Ｚ’は２価の基を表し、ｑおよびｒはそれぞれ１〜１０の整数を表し、ｔは１〜３の整数を表す）
で表される構造のうちのいずれかを有するものが好ましい。さらにまた、上記式（２１）中のＺ’で表される２価の基としては、下記式（２２）〜（３０）：
【化１９】

【化２０】

【化２１】

【化２２】

【化２３】

【化２４】

【化２５】

【化２６】

【化２７】

（式中、ｐは０〜３の整数を表す）
で表される構造のうちのいずれかを有するものが好ましい。
【００２８】
上記式（１）中、Ｄで表される２価の基は、好ましくは、−Ｃ_nＨ_2n−、−Ｃ_nＨ_2n-2−、−Ｃ_nＨ_2n-4−（ｎは１〜１５の整数であり、好ましくは２〜１０の整数である）、−ＣＨ₂−Ｃ₆Ｈ₄−または−Ｃ₆Ｈ₄−Ｃ₆Ｈ₄−で表される２価の炭化水素基、オキシカルボニル基（−ＣＯＯ−）、チオ基（−Ｓ−）、オキシ基（−Ｏ−）、イソシアノ基（−Ｎ＝ＣＨ−）、またはこれら２種以上の組み合わせによる２価の基である。なお、これらの２価の基は側鎖にアルキル基、フェニル基、アルコキシ基、アミノ基などの置換基を有していてもよい。Ｄが上記の好ましい２価の基であると、有機けい素化合物（１）を用いて３次元的な無機ガラス質ネットワークに適度な可とう性が付与されて層の強度が向上する傾向にある。
【００２９】
上記式（１）中、Ｑで表される加水分解性基とは、上記一般式（１）で表される有機ケイ素化合物の硬化反応において、加水分解によりシロキサン結合（Ｏ−Ｓｉ−Ｏ）を形成し得る官能基のことをいう。本発明にかかる加水分解性基の好ましい例としては、具体的には、水酸基、アルコキシ基、メチルエチルケトオキシム基、ジエチルアミノ基、アセトキシ基、プロペノキシ基、クロロ基が挙げられるが、これらの中でも、−ＯＲ’（Ｒ’は炭素数２〜１５のアルキル基または炭素数１〜４のトリメチルシリル基）で表される基がより好ましい。このような加水分解性基を有するけい素化合物を用いると、合成工程における原料化合物（けい素化合物）や目的生成物（光機能性有機けい素化合物）の加水分解性基における加水分解が抑制され、目的化合物の純度および収率がより向上する傾向にある。特に、Ｒ’が炭素数３〜１０の分岐鎖状アルキル基である−ＯＲ’基は、より安価に製造することができる点で特に好ましい。
【００３０】
このような構成を有する有機けい素化合物（１）のうち、Ｗが上記一般式（４）で表される置換または無置換のアリール基である化合物におけるＡｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴、Ａｒ⁵、Ｄ−ＳｉＲ_3-aＱ_aで表される基および整数ｋの好ましい組み合わせを下記表１〜３に示す。なお、表中、ＳはＡｒ¹、Ａｒ²、Ａｒ³、Ａｒ⁴またはＡｒ⁵の所定の結合位置に−Ｄ−ＳｉＲ_3-aＱ_aが結合していることを表す。
【００３１】
【表１】

【００３２】
【表２】

【００３３】
【表３】

【００３４】
本発明の有機電子デバイスは、従来の技術では達成されなかった十分に高い光電特性と十分に高い耐久性とを有し、しかも確実且つ容易に製造されるものであるが、これらの特性は、上記一般式（１）で表される有機けい素化合物を含有する層の²⁹Ｓ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）が上記関係式（２）で表される条件、好ましくは下記関係式（３１）：
０．６≦Ｓ₁／（Ｓ₁＋Ｓ₂） （３１）
（式中、Ｓ₁は−３５〜０ｐｐｍのピーク面積を表し、Ｓ₂は−１００〜−４０ｐｐｍのピーク面積を表す）
で表される条件を満たすように、層中の三官能性または四官能性のアルコキシシランの形成を抑制することによって初めて達成されるものである。そして、このような特性を有する本発明の有機電子デバイスは、上記一般式（１）で表される有機けい素化合物を含む原料に、下記（ａ）〜（ｃ）：
（ａ）下記一般式（３）：
Ａ−［Ｄ’−ＳｉＲ’_3-cＱ’_c］_n （３）
（式中、Ａは直鎖または分岐鎖のｎ価の脂肪族炭化水素基、置換または無置換のｎ価の芳香族炭化水素基、イミノ基（−ＮＨ−）またはシロキサン基（−Ｓｉ−Ｏ−）を表し、Ｄ’は２価の官能基を表し、Ｒ’は水素原子、アルキル基または置換あるいは無置換のアリール基を表し、Ｑ’は加水分解性基を表し、ｃは１〜３の整数を表し、ｎは２以上の整数を表す）
で表される有機けい素化合物
（ｂ）シランカップリング剤
（ｃ）ハードコート剤
からなる群より選ばれる少なくとも一種を、上記一般式（１）で表される有機けい素化合物１重量部に対して好ましくは０．０１〜１０重量部（より好ましくは０．１〜１重量部）配合することによって好適に製造される。
【００３５】
ここで、上記一般式（３）中、Ａで表される直鎖または分岐鎖のｎ価の脂肪族炭化水素基としては、メチレン基、エチレン基、プロピレン基、ブチレン基、ペンチレン基、へキシレン基、オクチル基など；
置換または無置換のｎ価の芳香族炭化水素基としては、フェニレン基、ジフェニルエチレン基など、が挙げられる。また、上記一般式（３）中、Ｄ’、Ｒ’およびＱで表される基としては、具体的には、それぞれ上記一般式（１）で表される有機けい素化合物の説明において例示されたＤ、Ｒ、およびＱで表される基が挙げられる。このような構成を有する（ａ）有機けい素化合物（３）の好ましい例を下記表４に示す。
【００３６】
【表４】

【００３７】
本発明において使用される（ｂ）シランカップリング剤としては、テトラメトキシシラン、テトラエトキシシランなどの四官能性アルコキシシラン；メチルトリメトキシシラン、メチルトリエトキシシラン、エチルトリメトキシシラン、メチルトリメトキシエトキシシラン、ビニルトリメトキシシラン、ビニルトリエトキシシラン、フェニルトリメトキシシラン、γ−グリシドキシプロピルメチルジエトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−グリシドキシプロピルトリメトキシシラン、γ−アミノプロピルトリエトキシシラン、γ−アミノプロピルトリメトキシシラン、γ−アミノプロピルメチルジメトキシシラン、Ｎ−β（アミノエチル）γ−アミノプロピルトリエトキシシランなどの三官能性アルコキシシラン；ジメチルジメトキシシラン、ジフェニルジメトキシシランなどの二官能性アルコキシシラン；トリメチルメトキシシランなどの一官能アルコキシシランなど、が挙げられる。これらの中でも、三官能性または四官能性のアルコキシシランを用いることは、得られる有機電子デバイスの機械的強度が向上する傾向にあるので好ましく、他方、一官能性または二官能性のアルコキシシランを用いることは、得られる有機電子デバイスの可とう性および成膜性が向上する傾向にあるので好ましい。
【００３８】
本発明において使用される（ｃ）ハードコート剤としては、具体的には、ＫＰ−８５、Ｘ−４０−９７４０、Ｘ−４０−２２３９ （以上、信越シリコーン社製）；ＡＹ４２−４４０、ＡＹ４２−４４１、ＡＹ４９−２０８ （以上、東レダウコーニング社製）、などの市販のハードコート剤が挙げられる。
【００３９】
上記（ａ）〜（ｃ）の中でも、（ａ）上記一般式（３）で表される有機けい素化合物を上記一般式（１）で表される有機けい素化合物と併用すると、層中の三官能性または四官能性のアルコキシシラン量が確実且つ容易に抑制され、得られる有機電子デバイスの光電特性、耐久性および製造性がより向上する傾向にあるので特に好ましい。
【００４０】
さらに、本発明においては、上記一般式（１）で表される有機けい素化合物を含む原料に含フッ素化合物を配合することができる。本発明に使用される含フッ素化合物としては、具体的には、（トリデカフルオロ −１，１，２，２−テトラヒドロオクチル）トリエトキシシラン、（３，３，３−トリフルオロプロピル）トリメトキシシラン、3−(ヘプタフルオロイソプロポキシ)プロピルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロアルキルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロデシルトリエトキシシラン、１Ｈ，１Ｈ，２Ｈ，２Ｈ−パーフルオロオクチルトリエトシキシラン、などが挙げられる。これらの含フッ素化合物を用いると、支持体に積層される層に撥水性が付与される傾向にある。なお、含フッ素化合物の配合量は、フッ素を含まない他の原料化合物に対して重量比で０．５以下であることが好ましい。含フッ素化合物の配合量が前記上限値を越えると成膜性が低下する傾向にある。
【００４１】
上記一般式（１）で表される有機けい素化合物を含有する層は、以下の方法によって支持体上に確実且つ容易に成膜することができる。先ず、上記一般式（１）で表される有機けい素化合物を含む原料化合物を所定の有機溶剤に加えて混合し、これに水およびイオン交換樹脂（アンバーリスト１５Ｅなど）を加えて加水分解を行う。反応終了後、反応混合物中に含まれるイオン交換樹脂などの不溶分を濾過などによって除去して塗工液を得る。次に、得られた塗工液を、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法などの方法によって支持体上に塗布し、乾燥させることによって目的の有機電子デバイスが得られる。ここで、本発明に使用される溶剤としては、具体的には、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、t-ブタノール、シクロヘキサノールなどのアルコール類；ジエチルエーテル、ジブチルエーテル、ジメトキシエタン、ジエトキシエタンなどのエーテル類；キシレン、ｐ-シメンなどの芳香族系溶剤；メチルセルソルブ、エチルセルソルブなどのセルソルブ類、などが挙げられる。また、上記の加水分解において使用される、イオン交換樹脂などの系に不溶な固体触媒としては、
アンバーライト１５、アンバーライト２００Ｃ、アンバーリスト１５（以上、ローム・アンド・ハース社製）、ダウエックスＭＷＣ−１−Ｈ、ダウエックス８８、ダウエックスＨＣＲ−Ｗ２（以上、ダウ・ケミカル社製）、レバチットＳＰＣ−１０８、レバチットＳＰＣ−１１８（以上、バイエル社製）、ダイヤイオンＲＣＰ−１５０Ｈ（三菱化学社製）、スミカイオンＫＣ−４７０、デュオライトＣ２６−Ｃ、デュオライトＣ−４３３、デュオライト４６４（以上、住友化学工業社製）、ナフィオン−Ｈ（デュポン社製）、などの陽イオン交換樹脂；
アンバーライトＩＲＡ−４００、アンバーライトＩＲＡ−４５（以上、ローム・アンド・ハース社製）などの陰イオン交換樹脂；
Ｚｒ（Ｏ₃ＰＣＨ₂ＣＨ₂ＳＯ₃Ｈ）₂、Ｔｈ（Ｏ₃ＰＣＨ₂ＣＨ₂ＣＯＯＨ）₂などのプロトン酸基を含有する基が表面に結合されている無機固体；
スルホン酸基を有するポリオルガノシロキサンなどのプロトン基を含有するポリオルガノシロキサン；
コバルトタングステン酸、リンモリブデン酸などのヘテロポリ酸；
ニオブ酸、タンタル酸、モリブデン酸などのイソポリ酸；
シリカゲル、アルミナ、クロミア、ジルコニア、酸化カルシウム（ＣａＯ）、酸化マグネシウム（ＭｇＯ）などの単元系金属酸化物；
シリカ−アルミナ、シリカ−マグネシア、シリカ−ジルコニア、ゼオライト類などの複合系金属酸化物；
酸性白土、活性白土、モンモリナイト、カオリナイトなどの粘土鉱物；
硫酸リチウム（Ｌｉ₂ＳＯ₄）、硫酸マグネシウム（ＭｇＳＯ₄）などの金属硫酸塩；
リン酸ジルコニア、リン酸ランタンなどの金属リン酸塩；
硝酸リチウム（ＬｉＮＯ₃）、硝酸マンガン（Ｍｎ（ＮＯ₃）₂）などの金属硝酸塩；
シリカゲル上にアミノプロピルトリエトキシシランを反応させて得られた固体などのアミノ基を含有する基が表面に結合されている無機固体；
アミノ変性シリコーン樹脂などのアミノ基を含有するポリオルガノシロキサン、などが挙げられる。また、上記の固体触媒以外にも、
塩酸、酢酸、硫酸、リン酸などの無機酸；
擬酸、プロピオン酸、シュウ酸、パラトルエンスルホン酸、安息香酸、フタル酸、マレイン酸などの有機酸；
水酸化カリウム、水酸化ナトリウム、水酸化カルシウム、アンモニアなどのアルカリ触媒；
有機金属、金属アルコキシド、例えばジブチルスズジラウリラート、ジブチルスズジオクチエート、ジブチルスズジアセテートなどの有機スズ化合物、アルミニウムトリス（アセチルアセトネート）、チタニウムビス（ブトキシ）ビス（アセチルアセトネート）、チタニウムビス（イソプロポキシ）ビス（アセチルアセトネート）、ジルコニウムテトラキス（アセチルアセトネート）、ジルコニウムビス（ブトキシ）ビス（アセチルアセトネート）、ジルコニウムビス（イソプロポキシ）ビス（アセチルアセトネート）などの金属キレート化合物、ホウ素ブトキシド、ホウ酸などのホウ素化合物、
などを触媒として用いることができる。
【００４２】
さらに、上記の加水分解は従来より公知の反応条件下で行うことができるが、その反応温度は通常−３０〜１００℃であり、好ましくは−１０〜４０℃である。また、塗工液の乾燥工程は、通常６０〜２００℃、好ましくは８０〜１５０℃で行われる。
【００４３】
次に、本発明の有機電子デバイスを適用した電子写真感光体の好適な一実施形態について説明する。図１は本発明の電子写真感光体の断面概略図である。電子写真感光体１は、支持体２上に積層される感光層３において電荷発生層４と電荷輸送層５とに機能を分離した積層型感光体であり、感光層３上には上記一般式（１）で表される有機けい素化合物を含有する表面保護層６が、支持体２と感光層３（電荷発生層４）との間には下引き層７が、それぞれ配置されている。そして、表面保護層６の²⁹Ｓｉ−ＮＭＲスペクトルにおける−３５〜０ｐｐｍのピーク面積と−１００〜−４０ｐｐｍのピーク面積とは上記関係式（２）を満たすものである。
【００４４】
ここで、図１中の支持体２としては、上記の本発明の有機電子デバイスに使用される支持体の説明において例示されたものが挙げられる。また、支持体２には、必要に応じて、上記の本発明の有機電子デバイスに使用される支持体の説明において例示された表面処理が施される。さらに、本発明においては、図１に示すように支持体２と感光層３との間に結着樹脂からなる下引き層７を設けることが好ましい。このように下引き層を設けると、感光層３が帯電した場合に支持体２から感光層３への電荷の流入が防止されるとともに、感光層３を支持体２に対して一体的に接着保持され、さらにその材質によっては支持体２の光反射が防止される傾向にある。本発明の下引き層に使用される結着樹脂としては、具体的には、ポリアミド樹脂、塩化ビニル樹脂、酢酸ビニル樹脂、フェノール樹脂、ポリウレタン樹脂、メラミン樹脂、ベンゾグアナミン樹脂、ポリイミド樹脂、ポリエチレン樹脂、ポリプロピレン樹脂、ポリカーボネート樹脂、アクリル樹脂、メタクリル樹脂、塩化ビニリデン樹脂、ポリビニルアセタール樹脂、塩化ビニル−酢酸ビニル共重合体、ポリビニルアルコール樹脂、水溶性ポリエステル樹脂、ニトロセルロース、カゼイン、ゼラチン、ポリグルタミン酸、澱粉、スターチアセテート、アミノ澱粉、ポリアクリル酸、ポリアクリルアミド、ジルコニウムキレート化合物、チタニルキレート化合物、チタニルアルコキシド化合物、有機チタニル化合物、シランカップリング剤などが挙げられ、これらの材料は１種を単独で用いてもよく、２種以上の混合物として用いでもよい。さらに、本発明においては、下引き層７に、酸化チタン、酸化アルミニウム、酸化珪素、酸化ジルコニウム、チタン酸バリウム、シリコーン樹脂などの無機材料からなる微粒子を配合させることができる。
【００４５】
下引き層７の成膜方法としては、従来より公知の方法を用いることができるが、具体的には、結着樹脂および有機溶剤を含む塗工液を調製し、得られた塗工液を、ブレードコーティング法、マイヤーバーコティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法などの方法により支持体２上に塗布し、乾燥させる方法が挙げられる。ここで、下引き層の成膜工程において使用される有機溶剤としては、具体的には、メタノール、エタノール、ｎ−プロパノール、ｎ−ブタノール、ベンジルアルコール、メチルセルソルブ、エチルセルソルブ、アセトン、メチルエチルケトン、シクロヘキサノン、クロロベンゼン、酢酸メチル、酢酸ｎ−ブチル、ジオキサン、テトラヒドロフラン、メチレンクロライド、クロロホルムなどが挙げられ、これらは１種を単独で用いてもよく、2種以上の混合物として用いてもよい。また、このようにして得られる下引層の膜厚は好ましくは０．０１〜１０μｍ、より好ましくは０．０５〜２μｍである。下引き層の膜厚が０．０１μｍ未満であると支持体２から感光層３への電荷の流入防止性あるいは支持体２と感光層３との接着性などの特性が不十分となる傾向にあり、他方、膜厚が１０μｍを超えると電子写真特性が低下する傾向にある。
【００４６】
電荷発生層４は、通常、電荷発生材料および結着樹脂を含むものである。ここで、本発明において使用される電荷発生材料としては、具体的には、アゾ系顔料、キノン系顔料、ペリレン系顔料、インジゴ系顔料、チオインジゴ系顔料、ビスベンゾイミダゾール系顔料、フタロシアニン系顔料、キナクリドン系顔料、キノリン系顔料、レーキ系顔料、アゾレーキ系顔料、アントラキノン系顔料、オキサジン系顔料、ジオキサジン系顔料、トリフェニルメタン系顔料などの有機顔料；アズレニウム系染料、スクウェアリウム系染料、ピリリウム系染料、トリアリルメタン系染料、キサンテン系染料、チアジン系染料、シアニン系染料などの染料；アモルファスシリコン、アモルファスセレン、テルル、セレン−テルル合金、硫化カドミウム、硫化アンチモン、酸化亜鉛、硫化亜鉛などの無機材料、などが挙げられるが、これらの中でも縮環芳香族系顔料、ペリレン系顔料またはアゾ系顔料を用いることは、感度、電気的安定性および光化学的安定性の点で好ましい。
【００４７】
また、電荷発生層４に使用される結着樹脂としては、ポリビニルアセタール系樹脂（ポリビニルブチラール樹脂、ポリビニルホルマール樹脂、ブチラールの一部がホルマールやアセトアセタール等で変性された部分アセタール化ポリビニルアセタール樹脂など）、ポリアミド系樹脂、ポリエステル樹脂、変性エーテル型ポリエステル樹脂、ポリカーボネート樹脂、アクリル樹脂、ポリ塩化ビニル樹脂、ポリ塩化ビニリデン樹脂、ポリスチレン樹脂、ポリビニルアセテート樹脂、塩化ビニルー酢酸ビニル共重合体、シリコーン樹脂、フェノール樹脂、フェノキシ樹脂、メラミン樹脂、ベンゾグアナミン樹脂、尿素樹脂、ポリウレタン樹脂、ポリ−Ｎ−ビニルカルバゾール樹脂、ポリビニルアントラセン樹脂、ポリビニルピレン等が挙げられる。これらの中でもポリビニルアセタール系樹脂、塩化ビニル−酢酸ビニル系共重合体、フェノキシ樹脂または変性エーテル型ポリエステル樹脂を用いると、電荷発生材料の分散性が向上してその凝集が防止され、長期にわたり安定な塗工液が得られる傾向にある。そして、このような塗工液を用いると電荷発生層が均一に成膜されて電気特性が向上し、その結果、画質欠陥の発生が抑制される傾向にある。なお、本発明においては、電荷発生層５にフェノール系化合物、硫黄系化合物、リン系化合物、アミン系化合物などの酸化防止剤、ビス（ジチオベンジル）ニッケル、ジ−ｎ−ブチルチオカルバミン酸ニッケルなどの失活剤、などを配合することもできる。
【００４８】
電荷発生層４の成膜方法としては、従来より公知の方法が使用可能であるが、具体的には、上記の電荷発生材料および結着樹脂を含む塗工液を、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法などの方法によって支持体上に塗布し、乾燥させる方法が挙げられる。ここで、電荷発生層の成膜工程に使用される有機溶剤としては、下引き層７の成膜方法の説明において例示された有機溶剤が挙げられる。また、電荷発生材料と結着樹脂との配合比は、好ましくは５：１〜１：２（体積比）である。さらに、このようにして得られる電荷発生層の膜厚は、好ましくは０．０１〜５μｍであり、より好ましくは０．１〜２μｍである、電荷発生層の膜厚が前記下限値未満であると電荷発生層を均一に成膜しにくくなる傾向にあり、他方、前記上限値を超えると電子写真特性が低下する傾向にある。
【００４９】
電荷輸送層５は、通常、低分子電荷輸送材料と結着樹脂、あるいは電荷輸送性ポリマーを含むものであり、必要に応じて架橋剤、無機微粒子などの添加剤が配合されたものである。本発明に使用される低分子電荷輸送材料としては、具体的には、ピレン系化合物、カルバゾール系化合物、ヒドラゾン系化合物、オキサゾール系化合物、オキサジアゾール系化合物、ピラゾリン系化合物、アリールアミン系化合物、アリールメタン系化合物、ベンジジン系化合物、チアゾール系化合物、スチルベン系化合物、ブタジエン系化合物など；
電荷輸送性ポリマーとしては、具体的には、上記一般式（１）で表される有機けい素化合物からなる硬化物、ポリ−Ｎ−ビニルカルバゾール、ハロゲン化ポリ−Ｎ−ビニルカルバゾール、ポリビニルピレン、ポリビニルアンスラセン、ポリビニルアクリジン、ピレン−ホルムアルデヒド樹脂、エチルカルバゾール−ホルムアルデヒド樹脂、トリフェニルメタンポリマー、ポリシランなど、
が挙げられる。これらの中でも、上記一般式（１）で表される有機けい素化合物からなる硬化物を用いると、電荷輸送層の光電特性を高水準に維持しながら耐久性が向上する傾向にあるので好ましい。また、トリフェニルアミン化合物、トリフェニルメタン化合物、ベンジジン化合物がモビリティーを用いると、安定性、光に対する透明性が向上する傾向にあるので好ましい。
【００５０】
また、電荷輸送層５の材料として使用される結着樹脂としては、電気絶縁性のフィルムが形成可能な高分子重合体が好ましく、具体的には、ポリカーボネート、ポリエステル、メタクリル樹脂、アクリル樹脂、ポリ塩化ビニル、ポリ塩化ビニリデン、ポリスチレン、ポリビニルアセテート、スチレン−ブタジエン共重合体、塩化ビニリデン−アクリロニトリル重合体、塩化ビニル−酢酸ビニル共重合体、塩化ビニル−酢酸ビニル−無水マレイン酸共重合体、シリコン樹脂、シリコン−アルキッド樹脂、フェノール−ホルムアルデヒド樹脂、スチレン−アルキッド樹脂、ポリ−Ｎ−ビニルカルバゾール、ポリビニルブチラール、ポリビニルフォルマール、ポリスルホン、カゼイン、ゼラチン、ポリビニルアルコール、エチルセルロース、フェノール樹脂、ポリアミド、カルボキシ−メチルセルロース、塩化ビニリデン系ポリマーラテックス、ポリウレタンなどが好ましい。これらの中でも、ポリカーボネート、ポリエステル、メタクリル樹脂、アクリル樹脂を用いると、電荷輸送材料との相溶性、溶剤への溶解性および機械的強度が向上する傾向にあるので特に好ましい。なお、これらの結着樹脂は、１種を単独で用いてもよく、２種以上の混合物として用いてもよい。
【００５１】
さらに、本発明においては、電荷輸送層５に可塑剤、表面改質剤、酸化防止剤、光劣化防止剤などの添加剤を配合することができる。本発明に使用される可塑剤としては、具体的には、ビフェニル、塩化ビフェニル、ターフェニル、ジブチルフタレート、ジエチレングリコールフタレート、ジオクチルフタレート、トリフェニル燐酸、メチルナフタレン、ベンゾフェノン、塩素化パラフィン、ポリプロピレン、ポリスチレン、各種フルオロ炭化水素など；
酸化防止剤としては、具体的には、フェノール系化合物、硫黄系化合物、リン系化合物、アミン系化合物など；
光劣化防止剤としては、具体的には、ベンゾトリアゾール系化合物、ベンゾフェノン系化合物、ヒンダードアミン系化合物など、
が挙げられる。
【００５２】
電荷輸送層５の成膜方法としては、従来より公知の方法が使用可能である。電荷輸送材料が低分子化合物である場合は、電荷輸送材料、結着樹脂および有機溶剤を含む塗工液、電荷輸送性ポリマーの場合は電荷輸送性ポリマーおよび有機溶剤を含む塗工液、をそれぞれ調製し、得られた塗工液を、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法などの方法によって支持体上に塗布し、乾燥させる方法が挙げられる。ここで、電荷輸送層５の成膜工程に使用される有機溶剤としては、具体的には、下引き層７の成膜方法の説明において例示された有機溶剤が挙げられる。また、このようにして得られる電荷輸送層の膜厚は好ましくは５〜５０μｍであり、より好ましくは１０〜４０μｍである。電荷輸送層の膜厚が５μｍ未満であると帯電性が不十分となる傾向にあり、他方、膜厚が５０μｍを越えると電子写真特性が著しく低下する傾向がある。
【００５３】
本発明の電子写真感光体においては、図１に示すように感光層２上に上記一般式（１）で表される有機けい素化合物を含有する表面保護層６を設けることが好ましい。このように、有機けい素化合物（１）を含有する表面保護層を設けると、光電特性を高水準に維持しながら感光体表面に十分に高い耐久性が付与される傾向にある。また、表面保護層６に、有機けい素化合物（１）に加えてさらに潤滑剤や無機微粒子などを含有させると、表面保護層６の潤滑性、汚染物付着防止性および機械的強度が向上し、より長寿命の電子写真感光体が得られる傾向にある。ここで、本発明において使用される潤滑剤としてはシリコーンオイル、フッ素系シランカップリング剤などが挙げられ、無機微粒子としてはシリカ微粒子、シリコーン微粒子などのけい素含有微粒子；四フッ化エチレン微粒子、三フッ化エチレン微粒子、六フッ化プロピレン微粒子、フッ化ビニル微粒子などのフッ素含有微粒子；ＺｎＯ−Ａｌ₂Ｏ₃、ＳｎＯ₂−Ｓ₂Ｏ₃、Ｉｎ₂Ｏ₃−ＳｎＯ₂、ＺｎＯ−ＴｉＯ₂、ＭｇＯ−Ａｌ₂Ｏ₃、ＦｅＯ−ＴｉＯ₂、ＴｉＯ₂、ＳｎＯ₂、Ｉｎ₂Ｏ₃、ＺｎＯ、ＭｇＯなどの半導電性金属酸化物からなる微粒子、または水酸基を有する重合性単量体とフッ素系樹脂との共重合により得られる微粒子（第８回ポリマー材料フォーラム講演予稿集、ｐ８９）などが挙げられ、これらの中でもコロイダルシリカまたはシリコーン微粒子を用いることが好ましい。
【００５４】
ここで、本発明にかかるシリカ微粒子を表面保護層６中に配合する場合は市販のコロイダルシリカを使用することができ、中でも、平均粒子径が１〜１００ｎｍ、好ましくは１０〜３０ｎｍのシリカ微粒子を、酸性もしくはアルカリ性の水溶液に分散させた水分散液、あるいはアルコール、ケトン、エステル等の有機溶媒中に分散させたものが好適に使用される。また、表面保護層６中のシリカ微粒子の含有量は、表面保護層６中の固形分全量基準で好ましくは１〜５０重量％、より好ましくは５〜３０重量％である。表面保護層６中のシリカ微粒子の固形分含有量が前記の好適な範囲内であると、成膜性、電気特性および機械的強度が向上する傾向にある。
【００５５】
また、本発明にかかるシリコーン微粒子としては、シリコーン樹脂粒子、シリコーンゴム粒子、シリコーン表面処理シリカ粒子からなる群より選ばれる１種であることが好ましく、その形状は球状で平均粒子径１〜５００ｎｍ、好ましくは１０〜１００ｎｍであることが好ましい。このようなシリコーン微粒子は化学的に不活性で、樹脂への分散性に優れる小径粒子であり、さらに十分な特性を得るために必要とされる含有量が低いため、架橋反応を阻害することなく、電子写真感光体の表面性状を改善することができる。即ち、強固な架橋構造中に均一に分散された状態で、電子写真感光体表面の潤滑性、撥水性を向上させ、長期間にわたって良好な耐摩耗性、耐汚染物付着性を維持することができる。本発明の電子写真感光体における最表面層中のシリコーン微粒子の含有量は、表面保護層の全固形分全量基準で０．１〜２０重量％であることが好ましく、０．５〜１０重量％であることがより好ましい。
【００５６】
表面保護層６の成膜方法としては、従来より公知の方法が使用可能であるが、具体的には、上記一般式（１）で表される有機けい素化合物を含む塗工液を調製し、得られた塗工液を、ブレードコーティング法、マイヤーバーコーティング法、スプレーコーティング法、浸漬コーティング法、ビードコーティング法、エアーナイフコーティング法、カーテンコーティング法などの方法によって支持体上に塗布し、乾燥させる方法が挙げられる。ここで、表面保護層６の成膜工程において使用される有機溶剤としては、表面保護層を構成する原料化合物を十分に溶解することができ、且つ下層である電荷輸送層５に悪影響を及ぼさないものが好ましい。このような有機溶剤としては、具体的には、メタノール、エタノール、プロパノール、イソプロパノール、ブタノール、t-ブタノール、シクロヘキサノール等のアルコール類；ジエチルエーテル、ジブチルエーテル、ジメトキシエタン、ジエトキシエタン等のエーテル類；キシレン、ｐ-シメン等の芳香族系溶剤、メチルセルソルブ、エチルセルソルブ等のセルソルブ類、が好ましく、これらの中でも沸点が６０〜１５０℃のアルコール類が成膜性および塗布液の保存安定性の点で特に好ましい。また、このようにして得られる表面保護層の膜厚は好ましくは０．１〜１０μｍであり、より好ましくは０．５〜７μｍである。表面保護層の膜厚が０．１μｍ未満であると耐久性が不十分となる傾向にあり、他方、膜厚が１０μｍを越えると電子写真特性が低下する傾向がある。
【００５７】
なお、電荷輸送層５が上記一般式（１）で表される有機けい素化合物を電荷輸送材料として含有し、且つ²⁹Ｓｉ−ＮＭＲスペクトルのピーク面積比が上記関係式（２）で表される条件を満たす場合には、表面保護層６を設ける代わりに電荷輸送層５を最表面層としてもよい。また、図１には積層型電子写真感光体の例を示したが、図１における積層型感光層３の代わりに、電荷発生材料と電荷輸送材料とを同一の層に含有する単層型の感光層を積層してもよい。
【００５８】
このように、十分に高い光電特性（電子写真特性）と十分に高い耐久性とを有する本発明の電子写真感光体を用いることによって、帯電、画像入力（露光）、現像、転写、定着、クリーニングなどの工程を含む電子写真画像形成プロセスにおいて、長期にわたって高水準の画像品位を得ることが可能となる。
【００５９】
本発明の電子写真画像形成装置の好適な一実施形態を図２に示す。図２の電子写真画像形成装置は、図１に示した積層構造を有するドラム状の電子写真感光体１が支持体２によって保持されており、感光体１は支持体８を中心として矢印の方向に所定の回転速度で回転駆動される。この回転過程において、電源９から電圧の供給を受けた接触帯電用部材１０により、感光体１はその周面に正又は負の所定電位の均一帯電を受ける。ここで、接触帯電用部材１０には、ＢＣＲ等導電性を付与したゴム状のロールが好適に使用される。また、感光体１を帯電させる他の方法としてはコロナ放電方式等が挙げられるが、接触帯電方式により帯電を行うことはオゾンが発生しにくいという点で好ましい。
【００６０】
次に、感光体１が画像入力装置（露光装置）１１にて光像露光を受けることにより、その周面に露光像に対応した静電潜像が形成される。その後、現像装置１２にて前記静電潜像にトナーを付着させてトナー像が形成され、転写装置１３にて前記トナー像が転写材Ｐに転写される。トナー像が転写された後の転写材Ｐは像定着装置１４にて像定着を受けて複写物としてプリントアウトされる。転写工程後の感光体１はクリーニング装置１５にてその周面に残存したトナーの除去を受けて清浄面化された後、除電器１６により除電されて繰り返して像形成に使用される。
【００６１】
ここで、電子写真感光体１は前述の通り十分に高い光電特性と十分に高い耐久性とをバランスよく有するものであり、このような電子写真感光体を電子写真画像形成装置に使用することによって、長期間にわたって高水準の印字品質を維持することが可能となる。
【００６２】
また、本発明においては、電子写真感光体と、帯電装置、現像装置およびクリーニング装置からなる群より選ばれる１種と、を備えるプロセスカートリッジを使用することは、電子写真画像形成装置における電子写真感光体などの脱着が容易となり、これらの構成部分の交換作業の効率が向上するという点で好ましい。
【００６３】
本発明の有機電子デバイスの好適な一実施形態として、図３および図４に示す有機エレクトロルミネッセンス素子（有機ＥＬ素子）を例示することもできる。
【００６４】
図３においては、透明絶縁性基板１７上に、透明電極１８と、上記一般式（１）で表される有機ケイ素化合物を含むホール輸送層１９と、発光層２０と、背面電極２１と、が順次積層されている。
【００６５】
また、図４においては、透明絶縁性基板１７上に、透明電極１８と、上記一般式（１）で表される有機ケイ素化合物を含むキャリア輸送機能を有する発光層２２と、背面電極２１と、が順次積層されている。
【００６６】
ここで、本発明にかかる透明絶縁性基板は、発光を取り出すため透明であることが好ましく、その材料としては、ガラス、プラスチックフィルムなどが用いられる。
【００６７】
また、本発明にかかる透明電極は、上記の透明絶縁性基板と同様に発光を取り出すため透明であることが好ましく、且つホールの注入を行うための仕事関数が大きなものが好ましい。本発明に係る透明電極としては、酸化スズインジウム（ＩＴＯ）、酸化スズ（ＮＥＳＡ）、酸化インジウム、酸化亜鉛などの酸化膜、および蒸着あるいはスパッタされた金、白金、パラジウムなどを用いることができる。
【００６８】
本発明にかかる上記一般式（１）で表される有機ケイ素化合物を含む層は、図３の有機ＥＬ素子においてはホール輸送層１９として作用し、他方、図４の有機ＥＬ素子においてはキャリア輸送機能を有する発光層２２として作用する。
【００６９】
有機ＥＬ素子が図３に示す層構成を有する場合、ホール輸送層１９は上記一般式（１）で表される有機ケイ素化合物単独で構成されていてもよいが、ホール移動度を調節するためにテトラフェニレンジアミン誘導体を１〜５０重量％の範囲で分散させて形成されていてもよい。また、他の汎用の樹脂を混合してもよい。
【００７０】
図３において、発光層２０の発光材料としては、固体状態で高い蛍光量子収率を示す化合物が用いられる。ここで、前記発光材料が低分子の有機化合物である場合は、真空蒸着法、もしくは発光材料と結着樹脂とを含む溶液または分散液を塗布、乾燥することにより良好な薄膜形成が可能であることが条件である。このような低分子の有機化合物としては、キレート型有機金属錯体、多核または縮合芳香環化合物、ペリレン誘導体、クマリン誘導体、スチリルアリーレン誘導体、シロール誘導体、オキサゾール誘導体、オキサチアゾール誘導体またはオキサジアゾール誘導体を用いることが好ましく、下記式（IV−１）〜（IV−１２）：
【化２８】

【化２９】

【化３０】

【化３１】

【化３２】

【化３３】

【化３４】

【化３５】

【化３６】

【化３７】

【化３８】

【化３９】

で表される化合物を用いることがより好ましい。
【００７１】
また、本発明にかかる発光層２０の発光材料が高分子化合物である場合、発光材料を含む溶液または分散液を塗布、乾燥することにより良好な薄膜形成が可能であることが条件である。このような高分子化合物としては、ポリパラフェニレン誘導体、ポリパラフェニレンビニレン誘導体、ポリチオフェン誘導体またはポリアセチレン誘導体を用いることが好ましく、下記式（IV−１３）〜（IV−１５）：
【化４０】

【化４１】

【化４２】

［上記式（IV−１３）〜（IV−１５）中、ｎは１以上の整数（好ましくは１〜２０、より好ましくは１〜１０）を表し、ｘは１以上の整数（好ましくは５〜１００００、より好ましくは１０〜１０００）を表す］
で表される化合物を用いることがより好ましい。
【００７２】
また、有機ＥＬ素子の耐久性および発光効率の向上を目的として、上記の発光材料中にゲスト材料として発光材料と異なる色素化合物をドーピングしてもよい。色素化合物をドーピングする方法としては、真空蒸着による発光層の形成工程において色素化合物を共蒸着させる方法、溶液または分散液の塗布、乾燥による発光層の形成工程において溶液または分散液に色素化合物を混合する方法、などが挙げられる。ここで、発光層中にドーピングされる色素化合物の割合は通常０．００１〜４０重量％、好ましくは０．００１〜１０重量％である。本発明において使用される色素化合物としては、発光材料との相溶性が良好であり且つ発光層の良好な成膜形成を妨げない有機化合物が好ましく、具体的には、ＤＭＣ誘導体、キナクドリン誘導体、ルブレン誘導体またはポルフィリンを用いることが好ましく、下記式（V−１）〜（V−４）：
【化４３】

【化４４】

【化４５】

【化４６】

で表される化合物を用いることがより好ましい。
【００７３】
さらにまた、発光材料として、真空蒸着あるいは溶液または分散液の塗布、乾燥による発光層の薄膜形成が可能であるが良好な薄膜が得られないものや、明確な電子輸送特性を示さないものを用いる場合には、有機ＥＬ素子の耐久性および発光効率の向上を目的として、発光層２０と背面電極２１との間に電子輸送層を挿入してもよい。このような電子輸送層に用いられる電子輸送材料としては、真空蒸着法により良好な薄膜形成が可能な有機化合物を用いることが好ましく、具体的には、オキサジアゾール誘導体、ニトロ置換フルオレノン誘導体、ジフェノキノン誘導体、チオピラン時オキシド誘導体、フルオレニリデンメタン誘導体を用いることが好ましく、下記式（VI−１）〜（VI−３）：
【化４７】

【化４８】

【化４９】

で表される化合物を用いることがより好ましい。
【００７４】
有機ＥＬ素子が図４に示す層構成を有する場合、発光層２２は少なくとも上記一般式（１）で表される有機ケイ素化合物中に発光材料を５０重量％以下の配合比で分散させた有機化合物層であり、前記発光材料としては上記式（IV−１）〜（IV−１５）で表される化合物が好適に使用される。ここで、有機ＥＬ素子に注入されるホールと電子とのバランスを調節するためにさらに電子輸送材料を１０〜５０重量％分散させてもよく、あるいは発光層２２と背面電極２１との間に電子輸送材料からなる電子輸送層を挿入してもよい。本発明にかかる電子輸送層に使用される電子輸送材料としては、上記一般式（１）で表される有機ケイ素化合物と強い電子相互作用を示さない有機化合物を用いることが好ましく、具体的には、下記式（VII）：
【化５０】

で表される化合物を用いることが好ましい。また、本発明においては、同様に、ホール移動度を調節するためにテトラフェニレンジアミン誘導体を適量同時に分散させて用いてもよい。さらにまた、本発明においては、発光材料と異なる色素化合物を発光層２２にドーピングしてもよい。
【００７５】
背面電極２１としては、真空蒸着が可能であり且つ電子注入を行うための仕事関数の小さな金属を用いることが好ましく、具体的には、マグネシウム、アルミニウム、銀、インジウムまたはこれらの合金を用いることが好ましい。
【００７６】
本発明にかかる有機ＥＬ素子において、ホール輸送層１９あるいは発光層２２は、上記一般式（１）で表される有機ケイ素化合物単独、あるいは上記一般式（１）で表される有機ケイ素化合物と発光材料と、必要に応じて電子輸送材料とホール（正孔）輸送材料と、を有機溶媒中に溶解または分散し、得られた塗布液を用いて前記透明電極上にスピンコーティング法、ディップ法などにより成膜することによって得ることができる。ここで、本発明にかかるホール輸送層および発光層の膜厚は、それぞれ０．０３〜０．２μｍであることが好ましい。また、これらの層中における発光材料の分散状態は分子分散状態、微粒子分散状態のいずれであってもよい。発光材料の分散状態を分子分散状態とする場合は、上記一般式（１）で表される有機ケイ素化合物、発光材料、電子輸送材料およびホール輸送材料の共通溶媒を分散溶媒として使用する必要があり、他方、発光材料の分散状態を微粒子分散状態とする場合は、発光材料の分散性と、上記一般式（１）で表される有機ケイ素化合物、電子輸送材料およびホール輸送材料の溶解性と、を考慮して分散溶媒を選択する必要がある。また、発光材料の分散状態を微粒子分散状態とする場合、ボールミル、サンドミル、ペイントシェイカー、アトライター、ホモジェナイザー、超音波などを使用することができる。
【００７７】
このようにして形成された、上記一般式（１）で表される有機ケイ素化合物を含む層の上に、各有機ＥＬ素子の層構成に応じて、それぞれ発光材料、電子輸送材料または背面電極を真空蒸着法により形成し、本発明にかかる有機ＥＬ素子を得ることができる。ここで、本発明においては、電子輸送能を有する発光層および電子輸送層の膜厚は、それぞれ０．１μｍ以下であることが好ましく、０．０３〜０．０８μｍであることが特に好ましい。また、本発明にかかる有機ＥＬ素子は、一対の電極間に、例えば４〜２０Ｖで、電流密度１〜２００ｍＡ／ｃｍ²の直流電圧を印加することによって発光させることができる。
【００７８】
【実施例】
以下、実施例および比較例に基づいて本発明をより具体的に説明するが、本発明は以下の実施例に限定されるものではない。なお、以下の実施例において、上記一般式（４）で表される有機けい素化合物のうち上記表１〜３に示した官能基の組み合わせを有するものについては相当する化合物番号を付し、「例示化合物［Ｎｏ．２８］」などということとする。同様に、上記一般式（３）で表される有機化合物のうち、上記表４に示した構造を有するものについては相当する化合物番号を付し、「例示化合物［III−６］」などということとする。
【００７９】
（電子写真感光体の作製）
実施例１
以下の手順に従い、電子写真感光体１６本を同時に作製した。
【００８０】
先ず、ホーニング処理を施した外径３０ｍｍの円筒状のアルミニウム基板上にジルコニウム化合物（商品名：オルガチックスＺＣ５４０、マツモト製薬社製）１００重量部、シラン化合物（商品名：Ａ１１００、日本ユニカー社製)１０重量部、イソプロパノール４００重量部およびブタノール２００重量部からなる溶液を浸漬塗布し、１５０℃にて１０分間加熱乾燥し、０．１μｍの下引き層を形成した。
【００８１】
次に、電荷発生材料としてＸ線回析スペクトルにおけるブラッグ角（２θ±０．２°)が７．４°、１６．６°、２５．５°および２８．３°に強い回析ピークを持つクロロガリウムフタロシアニン結晶１０重量部をポリビニルブチラール樹脂（商品名：エスレックＢＭ−Ｓ、積水化学社製)１０重量部および酢酸ブチル１０００重量部と混合し、ガラスビーズとともにペイントシェーカーで１時間の分散処理を行った。このようにして得られた塗布液を上記の下引き層上に浸積塗布し、１００℃にて１０分間加熱乾燥し、膜厚約０．１５μｍの電荷発生層を形成した。
【００８２】
さらに、下記構造式（３２）：
【化５１】

で表されるベンジジン化合物２０重量部およびビスフェノール（Ｚ）ポリカーボネート樹脂（粘度平均分子量：４．４×１０⁴）３０重量部をモノクロロベンゼン１５０重量部とテトラヒドロフラン１５０重量部との混合溶剤に溶解して得られた塗布液を、上記電荷発生層上に浸漬塗布し、１１５℃にて1時間加熱乾燥し、20μmの電荷輸送層を形成した。
【００８３】
さらに、例示化合物［Ｎｏ．２８］２０重量部、例示化合物［III−６］３０重量部、イソプロピルアルコール（ＩＰＡ）２０重量部、メタノール２０重量部をそれぞれ採取しよく混合した。さらに、イオン交換樹脂（アンバーリスト１５Ｅ）２重量部、蒸留水２４重量部を加え、室温にて１０時間攪拌した後、 薄層クロマトグラフィー（ＴＬＣ、展開溶剤：ヘキサン／酢酸エチル＝３／１、吸着剤：シリカゲル）により例示化合物［Ｎｏ．２８］の消失を確認した。その後、反応液中のイオン交換樹脂及び少量の沈殿を濾過により除去し、アルミニウムトリスアセチルアセトネート０．５重量部およびアセチルアセトン1重量部を加えて溶解させることによって塗工液を調製し、得られた塗工液を上記の電荷輸送層上に浸漬塗布し、１２０℃にて1時間加熱乾燥し、５μｍの表面保護層を形成して目的の電子写真感光体を得た。
【００８４】
このようにして作成した電子写真感光体１６本はいずれも表面状態が良好であり、クラックや乾燥むらなどの成膜不良は観測されなかった。
【００８５】
また、このようにして得られた電子写真感光体から、ケイ素を含まない粘着性テープを用いて表面保護層を剥離し、剥離物約１５０ｍｇを乳鉢で細かく粉砕し、ジルコニア製サンプルチューブ（７ｍｍφ）に充填して²⁹Ｓｉ−ＮＭＲスペクトルを測定した。なお、²⁹Ｓｉ−ＮＭＲスペクトルの測定はＶａｒｉａｎ社製ＵＮＩＴＹ−３００を用いて以下の条件：
周波数：５９．５９ＭＨｚ
遅延時間：１０．００秒
接触時間：２．５ミリ秒
積算回数：１００００回
測定温度：２５℃
試料の回転数：４０００±５００ｒｐｍ
で測定した。得られた²⁹Ｓｉ−ＮＭＲスペクトルを図４、得られた²⁹Ｓｉ−ＮＭＲスペクトルに基づいて算出したピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５、にそれぞれ示す。
【００８６】
実施例２
実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部を用い、例示化合物［III−６］の量を２５重量部としたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００８７】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【００８８】
実施例３
実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．３７］２０重量部を用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００８９】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【００９０】
実施例４
実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部、例示化合物［III−６］３０重量部の代わりに例示化合物［III−４］５重量部および例示化合物［III−６］２０重量部、をそれぞれ用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００９１】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【００９２】
実施例５
実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部、例示化合物［III−６］３０重量部の代わりに例示化合物［III−４］１５重量部および例示化合物［III−６］１０重量部、をそれぞれ用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００９３】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【００９４】
実施例６
実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部、例示化合物［III−６］３０重量部の代わりに例示化合物［III−４］１０重量部および例示化合物［III−６］１５重量部、をそれぞれ用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００９５】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【００９６】
実施例７
実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部、例示化合物［III−６］３０重量部の代わりに例示化合物［III−６］１５重量部およびシリコーン系微粒子（ＡＥＲＯＳＩＬ Ｒ８１２）１０重量部、をそれぞれ用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００９７】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【００９８】
比較例１
実施例１における表面保護層を設けなかったこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製し、表面状態の観察および²⁹Ｓｉ−ＮＭＲスペクトルの測定を行った。
【００９９】
得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【０１００】
比較例２
電荷輸送層の作製までは実施例１と同様に行い、表面保護層の形成において実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部、例示化合物［III−６］３０重量部の代わりに例示化合物［III−４］２０重量部および例示化合物［III−６］５重量部、をそれぞれ用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製したところ、特に、乾燥時に用いる熱風噴出し口の近くに配置された感光体２本にしわ状の成膜不良が見られた。
【０１０１】
このようにして得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【０１０２】
比較例３
電荷輸送層の作製までは実施例１と同様に行い、表面保護層の形成において実施例１における例示化合物［Ｎｏ．２８］２０重量部の代わりに例示化合物［Ｎｏ．２９］２５重量部、例示化合物［III−６］３０重量部の代わりに例示化合物［III−４］２５重量部、をそれぞれ用いたこと以外は実施例１と同様にして、電子写真感光体１６本を同時に作製したところ、特に、乾燥時に用いる熱風噴出し口の近くに配置された感光体４本にしわ状の成膜不良が観測された。
【０１０３】
このようにして得られた電子写真感光体の表面状態および²⁹Ｓｉ−ＮＭＲスペクトルにおけるピーク面積比Ｓ₁／（Ｓ₁＋Ｓ₂）を表５に示す。
【０１０４】
（プリント試験）
このようにして得られた実施例１〜７および比較例１〜３の各電子写真感光体を用いて図１に示す構成を有する電子写真画像形成装置（Ｌａｓｅｒ ｐｒｅｓｓ ４１６１IIを改造したもの）を作製し、各装置について常温常湿（約２０℃、４０％ＲＨ）、高温高湿（約２９℃、８５％ＲＨ）の２条件で５万枚のプリント試験（プリント用紙：酸性紙）を行い、複写物の画質および感光体の表面状態を評価した。その結果を表５に示す。なお、画質の評価においては１枚目および５万枚目の複写物について画質欠陥の有無を観察し、感光体の表面状態の評価においては傷や付着物の有無を観察した。
【０１０５】
【表５】

【０１０６】
表５に示すとおり、実施例１〜７において、１６本同時に作製された電子写真感光体はいずれも、シワなどが発生することなく良好な表面状態を有していた。また、これらの電子写真感光体を用いたプリント試験ではいずれも、５万枚目の複写物においても良好な画質を得ることができ、また、試験後の感光体表面には傷や付着物が認められなかった。
【０１０７】
これに対して、比較例１の電子写真感光体を用いた場合には、５万枚目の複写物における画質欠陥および試験後の感光体表面における傷の発生が認められた。また、比較例２および３では、１６本同時に作製された電子写真感光体のうちの一部にシワが発生し、これらの電子写真感光体を用いた場合には、プリント試験初期から複写物に画質欠陥が見られ、試験後の感光体表面には付着物が認められた。
【０１０８】
【発明の効果】
以上説明したとおり、本発明によれば、十分に高い光電特性と十分に高い耐久性とを有し、しかも確実且つ容易に製造することが可能な有機電子デバイスが得られる。そして、本発明の有機電子デバイスを電子写真感光体に適用し、これを電子写真画像形成装置に用いることによって、長期にわたって十分に良好な画像品位を得ることが可能となる。
【図面の簡単な説明】
【図１】本発明の電子写真感光体の好適な一実施形態を示す断面図である。
【図２】本発明の電子写真画像形成装置の好適な一実施形態を示す概略構成図である。
【図３】本発明にかかる有機エレクトロルミネッセンス素子の好適な一実施形態を示す概略構成図である。
【図４】本発明にかかる有機エレクトロルミネッセンス素子の好適な一実施形態を示す概略構成図である。
【図５】実施例１で得られた電子写真感光体の表面保護層の²⁹Ｓｉ−ＮＭＲスペクトルを表すグラフである。
【符号の説明】
１…電子写真感光体、２…導電性支持体、３…感光層、４…電荷発生層、５…電荷輸送層、６…表面保護層、７…下引き層、８…支持体、９…電源、１０…帯電部材、１１…画像入力装置、１２…現像装置、１３…転写装置、１４…像定着装置、１５…クリーニング装置、１６…除電器、１７…透明絶縁性基板、１８…透明電極、１９…ホール輸送層、２０…発光層、２１…背面電極、２２…キャリア輸送能を有する発光層。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an organic electronic device, an electrophotographic photosensitive member, an electrophotographic image forming apparatus, and a process cartridge, and more particularly, an organic electronic device using a silicon-containing compound, and an electrophotographic photosensitive member to which the organic electronic device is applied. The present invention also relates to an electrophotographic image forming apparatus and a process cartridge provided with the electrophotographic photosensitive member.
[0002]
[Prior art]
In recent years, from the viewpoint of productivity, ease of material design, safety, etc., an electrophotographic photosensitive member using an organic photoconductive material, an organic electroluminescence element (organic EL element), an organic memory element, an organic wavelength conversion element, etc. Organic electronic devices are attracting attention.
[0003]
For example, selenium, arsenic-selenium, cadmium sulfide, zinc oxide, a-Si, etc. have been used as materials for electrophotographic image forming apparatuses such as plain paper copiers (PPC), laser printers, LED printers, and liquid crystal printers. Inorganic photoconductors (IPCs) are used, but in recent years, research and development of organic photoconductors (OPCs) that are excellent in terms of manufacturability and discardability and are inexpensive have become active. Among organic photoreceptors, so-called function-separated laminated photoreceptors in which a charge generation layer and a charge transport layer are laminated are excellent in terms of electrophotographic characteristics such as sensitivity, chargeability and repeated stability, and are practically used. It is progressing rapidly.
[0004]
By the way, in the field of electrophotographic image forming apparatuses, copiers and printers using the contact charging method are increasing for reasons such as generation of oxidizing gas and reduction of power supply cost. In such an apparatus, a voltage having an AC component is applied to the photoreceptor in order to stabilize the charging potential of the photoreceptor, but when an organic photoreceptor is used, the voltage between the photoreceptor and the contact charging member is reduced. There is a problem in that the binding of the binder resin contained in the surface layer of the photoconductor is cut by discharge to lower the molecular weight, and as a result, the wear is remarkably increased by mechanical cleaning such as a cleaning blade.
[0005]
In addition, the material used for the organic electroluminescence element is required to have a characteristic that the film does not cause a morphological change due to the generated Joule heat. However, the required level is increasingly higher from the viewpoint of long life and high quality. It has become.
[0006]
Therefore, various researches are underway to achieve chemical stability and durability against stresses such as heat and mechanical external force that could not be obtained using conventional photofunctional organic materials. Studies in the field of electrophotographic photoreceptors have been actively conducted.
[0007]
For example, as one method for preventing the abrasion of the electrophotographic photosensitive member, the charge transport material constituting the photosensitive member surface layer is polymerized. As such a polymer, US Pat. No. 4,806,443 discloses a polycarbonate obtained by polymerization of a specific dihydroxyarylamine and bischloroformate; US Pat. No. 4,806,444 discloses a specific dihydroxyarylamine and phosgene. Polycarbonate obtained by polymerization; U.S. Pat. No. 4,801,517 discloses polycarbonate obtained by polymerization of bishydroxyalkylarylamine and bischloroformate or phosgene; U.S. Pat. No. 4,937,165 and U.S. Pat. No. 4,959,288 include Polycarbonates obtained by polymerization of certain dihydroxyarylamines or bishydroxyalkylarylamines with bischloroformates, and dihydroxyarylamines or Polyester obtained by polymerization of sulphoalkylarylamine and bisacyl halide; US Pat. No. 5,034,296 discloses a polycarbonate or polyester of arylamine having a specific fluorene skeleton; US Pat. No. 4,983,482 has a polyurethane; Japanese Patent Publication No. 59-28903 discloses polyesters each having a specific bisstyryl bisarylamine as a main chain. JP-A-61-20953, JP-A-1-134456, JP-A-1-134457, JP-A-1-134462, JP-A-4-133565, and JP-A-4-13366. Discloses a polymer having a charge-transporting substituent such as hydrazone or triarylamine as a pendant, and an electrophotographic photoreceptor using the polymer is proposed. However, an electrophotographic photosensitive member using the above polymer as a charge transport material is not sufficient in durability, and tends to cause a phenomenon that electrophotographic characteristics such as sensitivity and residual potential are deteriorated. There's a problem.
[0008]
As another method for preventing wear of the electrophotographic photosensitive member, a method of dispersing a low molecular charge transport material in a binder resin or a precursor thereof and then curing the binder resin or the precursor thereof has been proposed. Yes. For example, in Japanese Patent Application Laid-Open Nos. 56-48637 and 56-42863, techniques using acrylic polymers are disclosed in Japanese Patent Publication No. 5-47104, Japanese Patent Publication No. 60-22347, and Japanese Patent Publication No. 7-120051. The publications each disclose a technique using a silicon-based polymer or a precursor thereof. However, in the case of using the above method, the curing reaction of the binder resin does not progress if a low molecular charge transport material having a concentration (usually 30 to 50%) necessary for the electrophotographic photoreceptor to have sufficient characteristics is blended. It will be enough. As a result, with the use of the electrophotographic photosensitive member, the low molecular charge transporting material comes out from between the binder resins and wear occurs.
[0009]
Furthermore, as another method for preventing wear of the photoconductor, a method of providing a surface protective layer with high mechanical strength on the surface of the electrophotographic photoconductor has been proposed, and a cross-linkable curable resin has been studied as the material thereof. . Here, when the surface protective layer is composed only of the cross-linking curable resin, the outermost surface layer of the photoreceptor becomes an insulating layer, and the development potential margin becomes narrower due to the increase of the bright portion potential during exposure. The photoelectric characteristics as a photosensitive member must be sacrificed, for example, when the residual potential is increased, the image density is lowered particularly when long-term repetitive printing is performed.
[0010]
As a method for imparting photoelectric characteristics to the surface protective layer of the electrophotographic photosensitive member, a method of dispersing a conductive metal oxide fine powder in the surface protective layer as a resistance control material has been proposed (Japanese Patent Laid-Open No. 57-57). 128344). However, since the resistance value of the conductive metal oxide fine powder generally has a high humidity dependency, the electrophotographic photoreceptor obtained by such a method is used on the surface of the photoreceptor when it is used under high temperature and high humidity conditions. The resistance is lowered, and as a result, the electrostatic latent image is blurred and the image quality is significantly lowered.
[0011]
As another method for imparting photoelectric characteristics to the surface protective layer of the electrophotographic photoreceptor, a low molecular charge transport material is dispersed in the binder resin, and then the binder resin is cured to form a surface protective layer. Has been proposed (JP-A-4-15659, etc.). According to this method, it is possible to avoid the phenomenon that the image quality deteriorates under high-temperature and high-humidity conditions because the resistance of the photoreceptor surface does not show humidity dependence. Since the reaction is hindered and the mechanical strength of the surface protective layer is lowered, even when a cross-linking curable resin having a sufficiently high mechanical strength is used alone, an electrophotographic photosensitive material having a sufficiently high mechanical strength is used. It was difficult to get a body.
[0012]
Furthermore, as a method for imparting photoelectric characteristics and mechanical strength to the surface protective layer of the electrophotographic photosensitive member, the surface layer is mechanically reacted by reacting a charge transport material having a reactive functional group with a thermoplastic binder resin. A proposal has been made to improve the mechanical strength (JP-A-6-202354, JP-A-5-323630, etc.). However, when an electrophotographic photosensitive member having a surface layer having such a structure is used for a long time in an apparatus to which a contact charging method is applied, the mechanical strength of the surface layer rapidly decreases after a predetermined period of time, and the cleaning blade When mechanical cleaning such as is performed, the wear is greatly increased. This cause is considered to be due to a strong external stress such as breakage of the bond of the thermoplastic binder resin by application of an alternating voltage in contact charging.
[0013]
Furthermore, in JP-A-11-38656, JP-A-11-184106, JP-A-11-316468, etc., an organic material such as an electrophotographic photoreceptor using a charge transporting material having a hydrolyzable silyl group is disclosed. A technique for imparting photoelectric characteristics and durability to an electronic device is disclosed. However, even when these methods are used, a large-area thin film is formed when a surface protective layer is simultaneously formed on a number of photoconductors in the manufacturing process of an electrophotographic photosensitive member or in a manufacturing process of an organic electroluminescence element. However, there are problems such as film formation defects such as cracks and image defects.
[0014]
[Problems to be solved by the invention]
The present invention has been made in view of the above-described problems of the prior art, has an organic electronic device having sufficiently high photoelectric characteristics and sufficiently high durability, and capable of being reliably and easily manufactured, An object is to provide an electrophotographic photosensitive member to which an organic electronic device is applied, and an electrophotographic image forming apparatus and a process cartridge including the electrophotographic photosensitive member and capable of obtaining sufficiently good image quality over a long period of time. To do.
[0015]
[Means for Solving the Problems]
As a result of intensive studies to achieve the above object, the present inventors have found that in an organic electronic device having a layer containing a specific organosilicon compound, a monofunctional or difunctional alkoxysilane contained in the layer And the trifunctional or tetrafunctional alkoxysilanes have been found to affect the photoelectric properties, durability and manufacturability of organic electronic devices. And as a result of further research based on this knowledge,²⁹In the Si-NMR spectrum, a peak of −35 to 0 ppm attributed to the amount of monofunctional or difunctional alkoxysilane, and −100 to −40 ppm attributed to the amount of trifunctional or tetrafunctional alkoxysilane. When the area ratio of the peak satisfies a specific condition, sufficiently high photoelectric characteristics and sufficiently high durability can be achieved in a well-balanced manner, and the film formability of the layer is improved, thereby producing an organic device. Has been found to be reliable and easy, and the present invention has been completed.
[0016]
That is, the organic electronic device of the present invention is laminated on a support, and the following general formula (1):
W- [D-SiR_3-aQ_a]_b    (1)
Wherein W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4).
An organic electronic device comprising: a layer containing an organosilicon compound represented by:
Of the layer²⁹The peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the Si-NMR spectrum are expressed by the following relational expression (2):
0.5 ≦ S₁/ (S₁+ S₂(2)
(Where S₁Represents a peak area of −35 to 0 ppm, and S₂Represents a peak area of -100 to -40 ppm)
It is characterized by satisfying the condition represented by
[0017]
In addition, the electrophotographic photosensitive member of the present invention is laminated on the support and the following general formula (1):
W- [D-SiR_3-aQ_a]_b    (1)
Wherein W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4).
An electrophotographic photoreceptor comprising a layer containing an organosilicon compound represented by:
Of the layer²⁹The peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the Si-NMR spectrum are expressed by the following relational expression (2):
0.5 ≦ S₁/ (S₁+ S₂(2)
(Where S₁Represents a peak area of −35 to 0 ppm, and S₂Represents a peak area of -100 to -40 ppm)
It is characterized by satisfying the condition represented by
[0018]
Furthermore, the electrophotographic image forming apparatus of the present invention includes the electrophotographic photoreceptor of the present invention described above,
A charging device for charging the electrophotographic photoreceptor;
An exposure apparatus for forming an electrostatic latent image on the electrophotographic photosensitive member;
A developing device for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image;
A transfer device for transferring the toner image to a transfer material;
A cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member;
It is characterized by providing.
[0019]
Furthermore, the process cartridge of the present invention comprises a charging device for charging the electrophotographic photosensitive member,
A developing device for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image; and
Cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member
At least one selected from the group consisting of:
The electrophotographic photosensitive member of the present invention,
It is characterized by providing.
[0020]
According to the present invention, in an organic electronic device comprising a layer containing a specific organosilicon compound,²⁹Trifunctional or tetrafunctional alkoxy in the layer so that the peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the Si-NMR spectrum satisfy the condition represented by the above formula (2). By controlling the formation of silane, sufficiently high photoelectric characteristics and sufficiently high durability can be achieved in a balanced manner, and the layer can be reliably and easily formed in the manufacturing process. Therefore, when the organic electronic device of the present invention is applied to an electrophotographic photoreceptor of an electrophotographic image forming apparatus, a sufficiently high image quality can be obtained over a long period of time.
[0021]
In addition, here²⁹The peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the Si-NMR spectrum are respectively measured in accordance with the CP-MAS method described in the VarianUNITY-300 instruction manual. Yes, pulverize about 150 mg of sample using a mortar, etc., fill in a zirconia sample tube (7 mmφ), and measure under conditions of frequency 59.59 MHz, delay time 10.00 seconds, contact time 2.5 milliseconds. Solid obtained by²⁹It refers to a peak area of −35 to 0 ppm and a peak area of −100 to −40 ppm in the Si-NMR spectrum.
[0022]
In the present invention, the layer containing the organosilicon compound represented by the general formula (1) further includes the following general formula (3):
A- [D'-SiR '_3-cQ ’_c]_n      (3)
(In the formula, A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group or a siloxane group, and D ′ represents a divalent functional group. R ′ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q ′ represents a hydrolyzable group, c represents an integer of 1 to 3, and n represents an integer of 2 or more. To express)
It is preferable to contain 0.1-10 weight part of organosilicon compounds represented by these with respect to 1 weight part of organosilicon compounds represented by the said General formula (1).
[0023]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the drawings as the case may be. In the drawings, the same or corresponding parts are denoted by the same reference numerals.
[0024]
The organic electronic device of the present invention comprises a support and the following general formula (1):
W- [D-SiR_3-aQ_a]_b    (1)
Wherein W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4).
A layer containing an organosilicon compound represented by the formula:²⁹In the Si-NMR spectrum, the peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm are expressed by the following relational expression (2):
0.5 ≦ S₁/ (S₁+ S₂(2)
(Where S₁Represents a peak area of −35 to 0 ppm, and S₂Represents a peak area of -100 to -40 ppm)
It satisfies the condition represented by
[0025]
Here, as the support used in the present invention, specifically, a metal such as aluminum, copper, zinc, stainless steel, chromium, nickel, molybdenum, vanadium, indium, gold, platinum, or an alloy containing these metals. Coating, vapor deposition or laminating a plate-like, drum-like or belt-like material using a conductive polymer, a conductive compound such as indium oxide, a metal such as aluminum, palladium or gold or an alloy containing these metals Examples include paper, plastic film, and belt. In these conductive supports, surface treatment such as anodic oxide coating treatment, thermal hydroxylation treatment, chemical treatment, coloring treatment, and irregular reflection treatment (graining, etc.) may be applied as necessary. Applied.
[0026]
In the present invention, as described above, a layer containing the organosilicon compound represented by the above formula (1) is laminated on the above support. Here, in the above formula (1), the photofunctional organic group represented by W is a physical change such as photoisomerization, photochromism, photoionization, light emission, nonlinear optical effect, and photoelectrochemical effect due to absorption of light energy. Or an organic group exhibiting a physicochemical change, preferably having an aromatic ring, more preferably W is a phthalocyanine structure, porphyrin structure, azobenzene structure, stilbene structure, tris (bipyridyl) -rhodium structure, azulene structure, polyene It has one selected from the group consisting of a structure, a nitroaniline structure, a triarylamine structure, a benzidine structure, an arylalkane structure, an aryl-substituted ethylene structure, an anthracene structure, a hydrazone structure, a quinone structure, and a fluorenone structure. Among the organosilicon compounds having such a structure, those having photocarrier transport properties are preferably triarylamine compounds, benzidine compounds, arylalkane compounds, aryl-substituted ethylene compounds, stilbene compounds, anthracene. And at least one selected from the group consisting of a quinone compound, a hydrazone compound, a quinone compound, and a fluorenone compound;
Particularly preferably, W is represented by the following general formula (4):
[Chemical 1]

(Wherein Ar¹, Ar², Ar^ThreeAnd Ar^FourEach may be the same or different and each represents a substituted or unsubstituted aryl group, Ar^FiveRepresents a substituted or unsubstituted divalent aromatic hydrocarbon group, k represents 0 or 1, Ar¹, Ar², Ar^Three, Ar^Four, Ar^Five1-4 of them are -D-SiR in the above general formula (1)_3-aQ_aHaving a bond to bond with the group represented by
It is a compound represented by these.
[0027]
Here, in the above formula (4), Ar¹, Ar², Ar^ThreeAnd Ar^FourAs the substituted or unsubstituted aryl group represented by the following formulas (5) to (11):
[Chemical 2]

[Chemical Formula 3]

[Formula 4]

[Chemical formula 5]

[Chemical 6]

[Chemical 7]

[Chemical 8]

(Wherein R¹Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, an alkylphenyl group having 7 to 10 carbon atoms, an alkoxyphenyl group having 7 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms;²And R^ThreeRepresents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogen group, Ar⁶Represents a substituted or unsubstituted divalent aromatic hydrocarbon group, Z represents a divalent functional group, s represents an integer of 1 to 3, and-represents -D- in the general formula (1). SiR_3-aQ_aRepresents the bonding position when the group represented by
What has either of the structures represented by these is preferable. Furthermore, Ar in the above formula (11)⁶The substituted or unsubstituted divalent aromatic hydrocarbon group represented by the following general formula (12) or (13):
[Chemical 9]

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(Wherein R^FourAnd R^FiveRepresents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogen group, t represents an integer of 1 to 3)
Those having a structure represented by:
Examples of the divalent group represented by Z in the above formula (11) include the following formulas (14) to (21):
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(Wherein R⁶And R⁷Represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, a phenyl group, an alkoxyphenyl group having 7 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or a halogen group, Z ′ represents a divalent group, q and r each represents an integer of 1 to 10, and t represents an integer of 1 to 3)
What has either of the structures represented by these is preferable. Furthermore, examples of the divalent group represented by Z ′ in the formula (21) include the following formulas (22) to (30):
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(Wherein p represents an integer of 0 to 3)
What has either of the structures represented by these is preferable.
[0028]
In the above formula (1), the divalent group represented by D is preferably —C_nH_2n-, -C_nH_2n-2-, -C_nH_2n-4-(N is an integer of 1-15, preferably an integer of 2-10), -CH₂-C₆H_Four-Or-C₆H_Four-C₆H_FourA divalent hydrocarbon group represented by-, an oxycarbonyl group (-COO-), a thio group (-S-), an oxy group (-O-), an isocyano group (-N = CH-), or these 2 It is a divalent group by a combination of species or more. Note that these divalent groups may have a substituent such as an alkyl group, a phenyl group, an alkoxy group, or an amino group in the side chain. When D is a preferable divalent group, moderate flexibility is imparted to the three-dimensional inorganic glassy network using the organosilicon compound (1), and the strength of the layer tends to be improved. .
[0029]
In the formula (1), the hydrolyzable group represented by Q is a siloxane bond (O—Si—O) formed by hydrolysis in the curing reaction of the organosilicon compound represented by the general formula (1). It refers to a functional group that can be formed. Specific preferred examples of the hydrolyzable group according to the present invention include a hydroxyl group, an alkoxy group, a methyl ethyl ketoxime group, a diethylamino group, an acetoxy group, a propenoxy group, and a chloro group. Among these, —OR A group represented by '(R' is an alkyl group having 2 to 15 carbon atoms or a trimethylsilyl group having 1 to 4 carbon atoms) is more preferable. When such a silicon compound having a hydrolyzable group is used, hydrolysis in the hydrolyzable group of the raw material compound (silicon compound) and the target product (photofunctional organosilicon compound) in the synthesis process is suppressed. The purity and yield of the target compound tend to be further improved. In particular, the —OR ′ group, in which R ′ is a branched alkyl group having 3 to 10 carbon atoms, is particularly preferable because it can be produced at a lower cost.
[0030]
Ar in the organosilicon compound (1) having such a structure, wherein W is a substituted or unsubstituted aryl group represented by the general formula (4)¹, Ar², Ar^Three, Ar^Four, Ar^Five, D-SiR_3-aQ_aTables 1 to 3 below show preferred combinations of the group represented by and integer k. In the table, S is Ar.¹, Ar², Ar^Three, Ar^FourOr Ar^Five-D-SiR at a predetermined bonding position of_3-aQ_aIndicates that they are linked.
[0031]
[Table 1]

[0032]
[Table 2]

[0033]
[Table 3]

[0034]
The organic electronic device of the present invention has sufficiently high photoelectric characteristics and sufficiently high durability that have not been achieved by the prior art, and is reliably and easily manufactured. Of the layer containing the organosilicon compound represented by the general formula (1)²⁹Peak area ratio S in S-NMR spectrum₁/ (S₁+ S₂) Is represented by the above relational expression (2), preferably the following relational expression (31):
0.6 ≦ S₁/ (S₁+ S₂(31)
(Where S₁Represents a peak area of −35 to 0 ppm, and S₂Represents a peak area of -100 to -40 ppm)
This is achieved for the first time by suppressing the formation of trifunctional or tetrafunctional alkoxysilane in the layer so as to satisfy the condition represented by: And the organic electronic device of this invention which has such a characteristic is made into the raw material containing the organosilicon compound represented by the said General formula (1) to following (a)-(c):
(A) The following general formula (3):
A- [D'-SiR '_3-cQ ’_c]_n      (3)
(In the formula, A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group (—NH—) or a siloxane group (—Si—O -), D 'represents a divalent functional group, R' represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q 'represents a hydrolyzable group, and c represents 1 to 3 And n represents an integer of 2 or more)
Organosilicon compounds represented by
(B) Silane coupling agent
(C) Hard coat agent
Preferably at least one selected from the group consisting of 0.01 to 10 parts by weight (more preferably 0.1 to 1 part by weight) with respect to 1 part by weight of the organosilicon compound represented by the general formula (1). ) It is preferably manufactured by blending.
[0035]
Here, in the general formula (3), the linear or branched n-valent aliphatic hydrocarbon group represented by A includes a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and hexylene. Group, octyl group, etc .;
Examples of the substituted or unsubstituted n-valent aromatic hydrocarbon group include a phenylene group and a diphenylethylene group. In the general formula (3), the groups represented by D ′, R ′ and Q are specifically exemplified in the description of the organosilicon compound represented by the general formula (1). And groups represented by D, R, and Q. Preferred examples of (a) organosilicon compound (3) having such a structure are shown in Table 4 below.
[0036]
[Table 4]

[0037]
Examples of the (b) silane coupling agent used in the present invention include tetrafunctional alkoxysilanes such as tetramethoxysilane and tetraethoxysilane; methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, methyltrimethoxyethoxy Silane, vinyltrimethoxysilane, vinyltriethoxysilane, phenyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Trifunctional alkoxysilanes such as aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane; And bifunctional alkoxysilanes such as methyldimethoxysilane and diphenyldimethoxysilane; monofunctional alkoxysilanes such as trimethylmethoxysilane, and the like. Among these, it is preferable to use a trifunctional or tetrafunctional alkoxysilane because the mechanical strength of the obtained organic electronic device tends to be improved. On the other hand, a monofunctional or bifunctional alkoxysilane is used. The use is preferable because the flexibility and film-forming property of the obtained organic electronic device tend to be improved.
[0038]
Specific examples of the (c) hard coat agent used in the present invention include KP-85, X-40-9740, X-40-2239 (manufactured by Shin-Etsu Silicone); AY42-440, AY42- 441, AY49-208 (above, manufactured by Toray Dow Corning Co., Ltd.), and the like.
[0039]
Among the above (a) to (c), when (a) the organosilicon compound represented by the above general formula (3) is used in combination with the organosilicon compound represented by the above general formula (1), The amount of trifunctional or tetrafunctional alkoxysilane is surely and easily suppressed, and the photoelectric characteristics, durability and manufacturability of the resulting organic electronic device tend to be further improved, which is particularly preferable.
[0040]
Furthermore, in this invention, a fluorine-containing compound can be mix | blended with the raw material containing the organosilicon compound represented by the said General formula (1). Specific examples of the fluorine-containing compound used in the present invention include (tridecafluoro-1,1,2,2-tetrahydrooctyl) triethoxysilane and (3,3,3-trifluoropropyl) trimethoxy. Silane, 3- (heptafluoroisopropoxy) propyltriethoxysilane, 1H, 1H, 2H, 2H-perfluoroalkyltriethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, 1H, 1H, 2H , 2H-perfluorooctyltriethoxysilane. When these fluorine-containing compounds are used, water repellency tends to be imparted to the layer laminated on the support. In addition, it is preferable that the compounding quantity of a fluorine-containing compound is 0.5 or less by weight ratio with respect to the other raw material compound which does not contain a fluorine. When the blending amount of the fluorine-containing compound exceeds the above upper limit value, the film formability tends to decrease.
[0041]
The layer containing the organosilicon compound represented by the general formula (1) can be reliably and easily formed on the support by the following method. First, a raw material compound containing an organosilicon compound represented by the above general formula (1) is added to and mixed with a predetermined organic solvent, and water and an ion exchange resin (such as Amberlyst 15E) are added thereto for hydrolysis. Do. After completion of the reaction, an insoluble component such as an ion exchange resin contained in the reaction mixture is removed by filtration or the like to obtain a coating solution. Next, the obtained coating solution is applied onto a support by a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, or the like. The desired organic electronic device is obtained by drying. Here, as the solvent used in the present invention, specifically, alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, cyclohexanol; diethyl ether, dibutyl ether, dimethoxyethane, diethoxy And ethers such as ethane; aromatic solvents such as xylene and p-cymene; and cell solves such as methyl cellosolve and ethyl cellosolve. In addition, as a solid catalyst insoluble in a system such as an ion exchange resin used in the above hydrolysis,
Amberlite 15, Amberlite 200C, Amberlist 15 (above, manufactured by Rohm and Haas), Dowex MWC-1-H, Dowex 88, Dowex HCR-W2 (above, Dow Chemical Co.), Levacit SPC-108, Levacit SPC-118 (manufactured by Bayer), Diaion RCP-150H (Mitsubishi Chemical), Sumikaion KC-470, Duolite C26-C, Duolite C-433, Duolite 464 ( As described above, cation exchange resins such as Sumitomo Chemical Co., Ltd.) and Nafion-H (manufactured by DuPont);
Anion exchange resins such as Amberlite IRA-400 and Amberlite IRA-45 (above, manufactured by Rohm and Haas);
Zr (O_ThreePCH₂CH₂SO_ThreeH)₂, Th (O_ThreePCH₂CH₂COOH)₂An inorganic solid having a group containing a protonic acid group such as bonded to the surface;
Polyorganosiloxanes containing proton groups such as polyorganosiloxanes having sulfonic acid groups;
Heteropolyacids such as cobalt tungstic acid and phosphomolybdic acid;
Isopolyacids such as niobic acid, tantalum acid, molybdic acid;
Unitary metal oxides such as silica gel, alumina, chromia, zirconia, calcium oxide (CaO), magnesium oxide (MgO);
Composite metal oxides such as silica-alumina, silica-magnesia, silica-zirconia, zeolites;
Clay minerals such as acid clay, activated clay, montmorillonite and kaolinite;
Lithium sulfate (Li₂SO_Four), Magnesium sulfate (MgSO_FourMetal sulfates such as
Metal phosphates such as zirconia phosphate and lanthanum phosphate;
Lithium nitrate (LiNO_Three), Manganese nitrate (Mn (NO_Three)₂) And other metal nitrates;
An inorganic solid in which a group containing an amino group such as a solid obtained by reacting aminopropyltriethoxysilane on silica gel is bonded to the surface;
Examples thereof include polyorganosiloxanes containing amino groups such as amino-modified silicone resins. In addition to the above solid catalyst,
Inorganic acids such as hydrochloric acid, acetic acid, sulfuric acid, phosphoric acid;
Organic acids such as pseudoacids, propionic acid, oxalic acid, p-toluenesulfonic acid, benzoic acid, phthalic acid, maleic acid;
Alkaline catalysts such as potassium hydroxide, sodium hydroxide, calcium hydroxide, ammonia;
Organometallics, metal alkoxides, eg organotin compounds such as dibutyltin dilaurate, dibutyltin dioctiate, dibutyltin diacetate, aluminum tris (acetylacetonate), titanium bis (butoxy) bis (acetylacetonate), titanium bis (iso Metal chelate compounds such as propoxy) bis (acetylacetonate), zirconium tetrakis (acetylacetonate), zirconium bis (butoxy) bis (acetylacetonate), zirconium bis (isopropoxy) bis (acetylacetonate), boron butoxide, Boron compounds such as boric acid,
Etc. can be used as a catalyst.
[0042]
Further, the above hydrolysis can be carried out under conventionally known reaction conditions, and the reaction temperature is usually −30 to 100 ° C., preferably −10 to 40 ° C. Moreover, the drying process of a coating liquid is normally performed at 60-200 degreeC, Preferably it is 80-150 degreeC.
[0043]
Next, a preferred embodiment of an electrophotographic photoreceptor to which the organic electronic device of the present invention is applied will be described. FIG. 1 is a schematic cross-sectional view of the electrophotographic photosensitive member of the present invention. The electrophotographic photoreceptor 1 is a laminated photoreceptor in which functions are separated into a charge generation layer 4 and a charge transport layer 5 in a photosensitive layer 3 laminated on a support 2. The surface protective layer 6 containing the organosilicon compound represented by (1) is provided with an undercoat layer 7 between the support 2 and the photosensitive layer 3 (charge generation layer 4). And the surface protective layer 6²⁹The peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the Si-NMR spectrum satisfy the relational expression (2).
[0044]
Here, examples of the support 2 in FIG. 1 include those exemplified in the description of the support used in the organic electronic device of the present invention. Moreover, the surface treatment illustrated in description of the support body used for the said organic electronic device of this invention is given to the support body 2 as needed. Furthermore, in the present invention, it is preferable to provide an undercoat layer 7 made of a binder resin between the support 2 and the photosensitive layer 3 as shown in FIG. When the undercoat layer is provided in this manner, inflow of charges from the support 2 to the photosensitive layer 3 is prevented when the photosensitive layer 3 is charged, and the photosensitive layer 3 is integrally bonded to the support 2. In addition, depending on the material, the light reflection of the support 2 tends to be prevented. Specific examples of the binder resin used in the undercoat layer of the present invention include polyamide resin, vinyl chloride resin, vinyl acetate resin, phenol resin, polyurethane resin, melamine resin, benzoguanamine resin, polyimide resin, polyethylene resin, Polypropylene resin, polycarbonate resin, acrylic resin, methacrylic resin, vinylidene chloride resin, polyvinyl acetal resin, vinyl chloride-vinyl acetate copolymer, polyvinyl alcohol resin, water-soluble polyester resin, nitrocellulose, casein, gelatin, polyglutamic acid, starch, Starch acetate, amino starch, polyacrylic acid, polyacrylamide, zirconium chelate compound, titanyl chelate compound, titanyl alkoxide compound, organic titanyl compound, silane coupling agent, etc. Gerare, these materials may be used singly or may be used as a mixture of two or more. Furthermore, in the present invention, the undercoat layer 7 can be blended with fine particles made of an inorganic material such as titanium oxide, aluminum oxide, silicon oxide, zirconium oxide, barium titanate, and silicone resin.
[0045]
As a method for forming the undercoat layer 7, a conventionally known method can be used. Specifically, a coating liquid containing a binder resin and an organic solvent is prepared, and the obtained coating liquid is used. , Blade coating method, Mayer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method, and the like, and a method of drying on the support 2. Here, as an organic solvent used in the film forming step of the undercoat layer, specifically, methanol, ethanol, n-propanol, n-butanol, benzyl alcohol, methyl cellosolve, ethyl cellosolve, acetone, methyl ethyl ketone , Cyclohexanone, chlorobenzene, methyl acetate, n-butyl acetate, dioxane, tetrahydrofuran, methylene chloride, chloroform, and the like. These may be used alone or as a mixture of two or more. The thickness of the undercoat layer thus obtained is preferably 0.01 to 10 μm, more preferably 0.05 to 2 μm. If the thickness of the undercoat layer is less than 0.01 μm, characteristics such as prevention of inflow of charge from the support 2 to the photosensitive layer 3 or adhesion between the support 2 and the photosensitive layer 3 tend to be insufficient. On the other hand, when the film thickness exceeds 10 μm, the electrophotographic characteristics tend to deteriorate.
[0046]
The charge generation layer 4 usually contains a charge generation material and a binder resin. Here, as the charge generation material used in the present invention, specifically, an azo pigment, a quinone pigment, a perylene pigment, an indigo pigment, a thioindigo pigment, a bisbenzimidazole pigment, a phthalocyanine pigment, Organic pigments such as quinacridone pigments, quinoline pigments, lake pigments, azo lake pigments, anthraquinone pigments, oxazine pigments, dioxazine pigments, triphenylmethane pigments; azurenium dyes, squalium dyes, pyrylium dyes , Dyes such as triallylmethane dyes, xanthene dyes, thiazine dyes, cyanine dyes; inorganic materials such as amorphous silicon, amorphous selenium, tellurium, selenium-tellurium alloys, cadmium sulfide, antimony sulfide, zinc oxide, zinc sulfide , Etc. It is, sensitivity, preferable from the viewpoint of electric stability and photochemical stability using condensed aromatic pigments among these, a perylene pigment or azo pigment.
[0047]
The binder resin used for the charge generation layer 4 includes polyvinyl acetal resins (polyvinyl butyral resin, polyvinyl formal resin, partially acetalized polyvinyl acetal resin in which a part of butyral is modified with formal, acetoacetal, etc. ), Polyamide resin, polyester resin, modified ether type polyester resin, polycarbonate resin, acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl acetate resin, vinyl chloride-vinyl acetate copolymer, silicone resin, phenol Examples thereof include resins, phenoxy resins, melamine resins, benzoguanamine resins, urea resins, polyurethane resins, poly-N-vinylcarbazole resins, polyvinylanthracene resins, and polyvinylpyrene. Among these, when a polyvinyl acetal resin, a vinyl chloride-vinyl acetate copolymer, a phenoxy resin or a modified ether type polyester resin is used, the dispersibility of the charge generating material is improved and the aggregation thereof is prevented, and it is stable for a long time. There is a tendency to obtain a coating solution. When such a coating solution is used, the charge generation layer is uniformly formed and the electrical characteristics are improved, and as a result, the occurrence of image quality defects tends to be suppressed. In the present invention, the charge generation layer 5 is provided with an antioxidant such as a phenol compound, a sulfur compound, a phosphorus compound, or an amine compound, bis (dithiobenzyl) nickel, nickel di-n-butylthiocarbamate, or the like. It is also possible to add a deactivator.
[0048]
As a method for forming the charge generation layer 4, a conventionally known method can be used. Specifically, a coating liquid containing the above charge generation material and a binder resin is used as a blade coating method, a Meyer bar, or the like. Examples of the method include coating on a support by a coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, and the like, followed by drying. Here, examples of the organic solvent used in the charge generation layer forming step include the organic solvents exemplified in the description of the method for forming the undercoat layer 7. The mixing ratio of the charge generation material and the binder resin is preferably 5: 1 to 1: 2 (volume ratio). Further, the film thickness of the charge generation layer thus obtained is preferably 0.01 to 5 μm, more preferably 0.1 to 2 μm. The film thickness of the charge generation layer is less than the lower limit value. And the charge generation layer tends to be difficult to form uniformly, and on the other hand, when the upper limit is exceeded, the electrophotographic characteristics tend to be deteriorated.
[0049]
The charge transport layer 5 usually contains a low molecular charge transport material and a binder resin, or a charge transport polymer, and is blended with additives such as a crosslinking agent and inorganic fine particles as necessary. Specific examples of low molecular charge transport materials used in the present invention include pyrene compounds, carbazole compounds, hydrazone compounds, oxazole compounds, oxadiazole compounds, pyrazoline compounds, arylamine compounds, Arylmethane compounds, benzidine compounds, thiazole compounds, stilbene compounds, butadiene compounds, etc .;
Specific examples of the charge transporting polymer include a cured product composed of an organosilicon compound represented by the above general formula (1), poly-N-vinylcarbazole, halogenated poly-N-vinylcarbazole, polyvinylpyrene, Polyvinyl anthracene, polyvinyl acridine, pyrene-formaldehyde resin, ethylcarbazole-formaldehyde resin, triphenylmethane polymer, polysilane, etc.
Is mentioned. Among these, it is preferable to use a cured product composed of the organosilicon compound represented by the general formula (1) because durability tends to be improved while maintaining the photoelectric characteristics of the charge transport layer at a high level. Further, it is preferable to use mobility for a triphenylamine compound, a triphenylmethane compound, or a benzidine compound because stability and transparency to light tend to be improved.
[0050]
The binder resin used as the material for the charge transport layer 5 is preferably a polymer capable of forming an electrically insulating film. Specifically, polycarbonate, polyester, methacrylic resin, acrylic resin, Vinyl chloride, polyvinylidene chloride, polystyrene, polyvinyl acetate, styrene-butadiene copolymer, vinylidene chloride-acrylonitrile polymer, vinyl chloride-vinyl acetate copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer, silicone resin , Silicone-alkyd resin, phenol-formaldehyde resin, styrene-alkyd resin, poly-N-vinylcarbazole, polyvinyl butyral, polyvinyl formal, polysulfone, casein, gelatin, polyvinyl alcohol, ethyl cellulose, pheno Le resin, polyamide, carboxy - methyl cellulose, vinylidene polymer latexes chloride, and polyurethane are preferable. Among these, polycarbonate, polyester, methacrylic resin, and acrylic resin are particularly preferable because they tend to improve the compatibility with the charge transport material, the solubility in a solvent, and the mechanical strength. In addition, these binder resin may be used individually by 1 type, and may be used as a 2 or more types of mixture.
[0051]
Furthermore, in the present invention, additives such as a plasticizer, a surface modifier, an antioxidant and a photodegradation inhibitor can be blended in the charge transport layer 5. Specific examples of the plasticizer used in the present invention include biphenyl, biphenyl chloride, terphenyl, dibutyl phthalate, diethylene glycol phthalate, dioctyl phthalate, triphenyl phosphate, methyl naphthalene, benzophenone, chlorinated paraffin, polypropylene, polystyrene, Various fluoro hydrocarbons;
Specific examples of the antioxidant include a phenol compound, a sulfur compound, a phosphorus compound, and an amine compound;
Specific examples of the photodegradation inhibitor include benzotriazole compounds, benzophenone compounds, hindered amine compounds,
Is mentioned.
[0052]
As a method for forming the charge transport layer 5, a conventionally known method can be used. When the charge transport material is a low-molecular compound, a charge transport material, a coating liquid containing a binder resin and an organic solvent, and in the case of a charge transport polymer, a coating liquid containing a charge transport polymer and an organic solvent, respectively. The prepared coating solution is applied onto the support by the blade coating method, Meyer bar coating method, spray coating method, dip coating method, bead coating method, air knife coating method, curtain coating method, etc. And a drying method. Here, specific examples of the organic solvent used in the film forming process of the charge transport layer 5 include the organic solvents exemplified in the description of the film forming method of the undercoat layer 7. The film thickness of the charge transport layer thus obtained is preferably 5 to 50 μm, more preferably 10 to 40 μm. If the film thickness of the charge transport layer is less than 5 μm, the chargeability tends to be insufficient. On the other hand, if the film thickness exceeds 50 μm, the electrophotographic characteristics tend to be remarkably deteriorated.
[0053]
In the electrophotographic photoreceptor of the present invention, it is preferable to provide a surface protective layer 6 containing the organosilicon compound represented by the general formula (1) on the photosensitive layer 2 as shown in FIG. Thus, when the surface protective layer containing the organosilicon compound (1) is provided, there is a tendency that sufficiently high durability is imparted to the photoreceptor surface while maintaining the photoelectric characteristics at a high level. Further, when the surface protective layer 6 further contains a lubricant, inorganic fine particles or the like in addition to the organosilicon compound (1), the lubricity, the antifouling property and the mechanical strength of the surface protective layer 6 are improved. There is a tendency that an electrophotographic photosensitive member having a longer life is obtained. Here, examples of the lubricant used in the present invention include silicone oil and fluorine-based silane coupling agents. Examples of inorganic fine particles include silicon-containing fine particles such as silica fine particles and silicone fine particles; ethylene tetrafluoride fine particles, three. Fluorine-containing fine particles such as fluorinated ethylene fine particles, hexafluoropropylene fine particles, and vinyl fluoride fine particles; ZnO-Al₂O_Three, SnO₂-S₂O_Three, In₂O_Three-SnO₂ZnO-TiO₂MgO-Al₂O_Three, FeO-TiO₂TiO₂, SnO₂, In₂O_ThreeFine particles made of semiconductive metal oxides such as ZnO and MgO, or fine particles obtained by copolymerization of a polymerizable monomer having a hydroxyl group and a fluororesin (Proceedings of the 8th Polymer Materials Forum Lecture, p. 89) Among these, it is preferable to use colloidal silica or silicone fine particles.
[0054]
Here, when the silica fine particles according to the present invention are blended in the surface protective layer 6, commercially available colloidal silica can be used, among which silica fine particles having an average particle diameter of 1 to 100 nm, preferably 10 to 30 nm are used. An aqueous dispersion dispersed in an acidic or alkaline aqueous solution, or a dispersion in an organic solvent such as alcohol, ketone, or ester is preferably used. Further, the content of the silica fine particles in the surface protective layer 6 is preferably 1 to 50% by weight, more preferably 5 to 30% by weight, based on the total solid content in the surface protective layer 6. If the solid content of the silica fine particles in the surface protective layer 6 is within the above-mentioned preferred range, the film formability, electrical characteristics and mechanical strength tend to be improved.
[0055]
Moreover, the silicone fine particles according to the present invention are preferably one kind selected from the group consisting of silicone resin particles, silicone rubber particles, and silicone surface-treated silica particles, and the shape thereof is spherical and the average particle diameter is 1 to 500 nm. The thickness is preferably 10 to 100 nm. Such silicone fine particles are small particles that are chemically inert and excellent in dispersibility in the resin, and since the content required for obtaining sufficient properties is low, the crosslinking reaction is not hindered. The surface properties of the electrophotographic photosensitive member can be improved. In other words, it is possible to improve the lubricity and water repellency of the surface of the electrophotographic photosensitive member while being uniformly dispersed in a strong cross-linked structure, and to maintain good wear resistance and adherence to contaminants over a long period of time. it can. The content of the silicone fine particles in the outermost surface layer in the electrophotographic photosensitive member of the present invention is preferably 0.1 to 20% by weight based on the total amount of the total solid content of the surface protective layer, and preferably 0.5 to 10% by weight. It is more preferable that
[0056]
As a method for forming the surface protective layer 6, a conventionally known method can be used. Specifically, a coating liquid containing an organosilicon compound represented by the general formula (1) is prepared. The obtained coating liquid is applied onto a support by a blade coating method, a Meyer bar coating method, a spray coating method, a dip coating method, a bead coating method, an air knife coating method, a curtain coating method, etc., and dried. The method of letting it be mentioned. Here, as the organic solvent used in the film forming step of the surface protective layer 6, the raw material compound constituting the surface protective layer can be sufficiently dissolved, and the charge transport layer 5 which is the lower layer is not adversely affected. Those are preferred. Specific examples of such organic solvents include alcohols such as methanol, ethanol, propanol, isopropanol, butanol, t-butanol, and cyclohexanol; ethers such as diethyl ether, dibutyl ether, dimethoxyethane, and diethoxyethane. Preferred are aromatic solvents such as xylene and p-cymene, and cellsolves such as methylcellosolve and ethylcellosolve. Among these, alcohols having a boiling point of 60 to 150 ° C. are suitable for film formation and storage stability of coating solutions. It is particularly preferable in terms of sex. Moreover, the film thickness of the surface protective layer thus obtained is preferably 0.1 to 10 μm, more preferably 0.5 to 7 μm. If the thickness of the surface protective layer is less than 0.1 μm, the durability tends to be insufficient. On the other hand, if the thickness exceeds 10 μm, the electrophotographic characteristics tend to deteriorate.
[0057]
The charge transport layer 5 contains an organosilicon compound represented by the general formula (1) as a charge transport material, and²⁹When the peak area ratio of the Si-NMR spectrum satisfies the condition expressed by the relational expression (2), the charge transport layer 5 may be the outermost surface layer instead of providing the surface protective layer 6. FIG. 1 shows an example of a multilayer electrophotographic photosensitive member. However, instead of the multilayer photosensitive layer 3 in FIG. 1, a single layer type containing a charge generation material and a charge transport material in the same layer. A photosensitive layer may be laminated.
[0058]
Thus, by using the electrophotographic photosensitive member of the present invention having sufficiently high photoelectric characteristics (electrophotographic characteristics) and sufficiently high durability, charging, image input (exposure), development, transfer, fixing, cleaning In an electrophotographic image forming process including such processes as described above, it is possible to obtain a high level of image quality over a long period of time.
[0059]
A preferred embodiment of the electrophotographic image forming apparatus of the present invention is shown in FIG. In the electrophotographic image forming apparatus shown in FIG. 2, a drum-shaped electrophotographic photosensitive member 1 having the laminated structure shown in FIG. 1 is held by a support 2, and the photosensitive member 1 is centered on the support 8 in the direction of the arrow. Are rotated at a predetermined rotational speed. During this rotation process, the photosensitive member 1 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the contact charging member 10 supplied with voltage from the power source 9. Here, as the contact charging member 10, a rubber-like roll imparted with conductivity such as BCR is preferably used. Further, other methods for charging the photoreceptor 1 include a corona discharge method, and it is preferable to perform charging by a contact charging method because ozone is hardly generated.
[0060]
Next, the photoreceptor 1 is subjected to optical image exposure by the image input device (exposure device) 11, whereby an electrostatic latent image corresponding to the exposure image is formed on the peripheral surface. Thereafter, the developing device 12 attaches toner to the electrostatic latent image to form a toner image, and the transfer device 13 transfers the toner image onto the transfer material P. The transfer material P after the toner image is transferred is subjected to image fixing by the image fixing device 14 and printed out as a copy. After the transfer process, the photosensitive member 1 is cleaned by the toner remaining on the peripheral surface thereof by the cleaning device 15, and then is neutralized by the static eliminator 16 and repeatedly used for image formation.
[0061]
Here, the electrophotographic photosensitive member 1 has a sufficiently high photoelectric property and sufficiently high durability as described above in a well-balanced manner. By using such an electrophotographic photosensitive member in an electrophotographic image forming apparatus, It is possible to maintain a high level of print quality over a long period of time.
[0062]
In the present invention, the use of a process cartridge comprising an electrophotographic photosensitive member and one selected from the group consisting of a charging device, a developing device and a cleaning device means that the electrophotographic photosensitive member in the electrophotographic image forming apparatus is used. It is preferable in that the body can be easily detached and the efficiency of exchanging these components is improved.
[0063]
As a preferred embodiment of the organic electronic device of the present invention, an organic electroluminescence element (organic EL element) shown in FIGS. 3 and 4 can be exemplified.
[0064]
In FIG. 3, a transparent electrode 18, a hole transport layer 19 containing an organosilicon compound represented by the general formula (1), a light emitting layer 20, and a back electrode 21 are formed on a transparent insulating substrate 17. They are sequentially stacked.
[0065]
In FIG. 4, on the transparent insulating substrate 17, a transparent electrode 18, a light emitting layer 22 having a carrier transport function including an organosilicon compound represented by the general formula (1), a back electrode 21, Are sequentially stacked.
[0066]
Here, the transparent insulating substrate according to the present invention is preferably transparent in order to extract emitted light, and glass, plastic film or the like is used as the material thereof.
[0067]
Further, the transparent electrode according to the present invention is preferably transparent in order to extract emitted light in the same manner as the transparent insulating substrate, and preferably has a large work function for injecting holes. As the transparent electrode according to the present invention, oxide films such as indium tin oxide (ITO), tin oxide (NESA), indium oxide, and zinc oxide, and gold, platinum, palladium, or the like deposited or sputtered can be used.
[0068]
The layer containing the organosilicon compound represented by the above general formula (1) according to the present invention acts as the hole transport layer 19 in the organic EL device of FIG. 3, while the carrier transport in the organic EL device of FIG. It functions as the light emitting layer 22 having a function.
[0069]
When the organic EL element has the layer configuration shown in FIG. 3, the hole transport layer 19 may be composed of the organosilicon compound represented by the general formula (1) alone, but in order to adjust the hole mobility. It may be formed by dispersing a tetraphenylenediamine derivative in the range of 1 to 50% by weight. Moreover, you may mix other general purpose resin.
[0070]
In FIG. 3, as the light emitting material of the light emitting layer 20, a compound showing a high fluorescence quantum yield in a solid state is used. Here, when the light-emitting material is a low-molecular organic compound, a favorable thin film can be formed by applying a vacuum deposition method or applying and drying a solution or dispersion containing the light-emitting material and a binder resin. Is a condition. As such a low molecular weight organic compound, a chelate-type organometallic complex, a polynuclear or condensed aromatic ring compound, a perylene derivative, a coumarin derivative, a styrylarylene derivative, a silole derivative, an oxazole derivative, an oxathiazole derivative or an oxadiazole derivative is used. It is preferable that the following formulas (IV-1) to (IV-12):
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It is more preferable to use the compound represented by these.
[0071]
Moreover, when the light emitting material of the light emitting layer 20 concerning this invention is a high molecular compound, it is the conditions that a favorable thin film formation is possible by apply | coating and drying the solution or dispersion liquid containing a light emitting material. As such a polymer compound, a polyparaphenylene derivative, a polyparaphenylene vinylene derivative, a polythiophene derivative or a polyacetylene derivative is preferably used, and the following formulas (IV-13) to (IV-15):
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[In the above formulas (IV-13) to (IV-15), n represents an integer of 1 or more (preferably 1 to 20, more preferably 1 to 10), and x is an integer of 1 or more (preferably 5 to 5). 10,000, more preferably 10 to 1000)]
It is more preferable to use the compound represented by these.
[0072]
Further, for the purpose of improving the durability and light emission efficiency of the organic EL element, the above light emitting material may be doped with a dye compound different from the light emitting material as a guest material. As a method for doping a dye compound, a method in which a dye compound is co-evaporated in the process of forming a light emitting layer by vacuum deposition, a solution or a dispersion is applied, and a dye compound is mixed in the solution or dispersion in a process of forming a light emitting layer by drying. And the like. Here, the proportion of the dye compound doped in the light emitting layer is usually 0.001 to 40% by weight, preferably 0.001 to 10% by weight. The dye compound used in the present invention is preferably an organic compound that has good compatibility with the light-emitting material and does not hinder good film formation of the light-emitting layer. Specific examples include DMC derivatives, quinacdrine derivatives, and rubrene. It is preferable to use a derivative or porphyrin, and the following formulas (V-1) to (V-4):
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It is more preferable to use the compound represented by these.
[0073]
Furthermore, a light emitting material that can form a thin film of the light emitting layer by vacuum deposition, application of a solution or dispersion, or drying, but cannot provide a good thin film, or one that does not exhibit clear electron transport properties is used. In this case, an electron transport layer may be inserted between the light emitting layer 20 and the back electrode 21 for the purpose of improving the durability and light emission efficiency of the organic EL element. As an electron transport material used for such an electron transport layer, it is preferable to use an organic compound capable of forming a good thin film by a vacuum deposition method, and specifically, an oxadiazole derivative, a nitro-substituted fluorenone derivative, diphenoquinone. It is preferable to use a derivative, an oxide derivative at the time of thiopyran, and a fluorenylidenemethane derivative, and the following formulas (VI-1) to (VI-3):
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It is more preferable to use the compound represented by these.
[0074]
When the organic EL device has the layer structure shown in FIG. 4, the light emitting layer 22 is an organic compound in which a light emitting material is dispersed at a blending ratio of 50% by weight or less in at least the organosilicon compound represented by the general formula (1). As the light emitting material, compounds represented by the above formulas (IV-1) to (IV-15) are preferably used. Here, in order to adjust the balance between holes and electrons injected into the organic EL element, an electron transport material may be further dispersed by 10 to 50% by weight, or electrons between the light emitting layer 22 and the back electrode 21 may be dispersed. An electron transport layer made of a transport material may be inserted. As the electron transport material used for the electron transport layer according to the present invention, it is preferable to use an organic compound that does not exhibit strong electron interaction with the organosilicon compound represented by the general formula (1), specifically, The following formula (VII):
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It is preferable to use the compound represented by these. In the present invention, similarly, an appropriate amount of tetraphenylenediamine derivative may be simultaneously dispersed in order to adjust the hole mobility. Furthermore, in the present invention, the light emitting layer 22 may be doped with a dye compound different from the light emitting material.
[0075]
As the back electrode 21, it is preferable to use a metal that can be vacuum-deposited and has a small work function for performing electron injection. Specifically, magnesium, aluminum, silver, indium, or an alloy thereof is used. preferable.
[0076]
In the organic EL device according to the present invention, the hole transport layer 19 or the light emitting layer 22 emits light with the organic silicon compound represented by the general formula (1) alone or the organic silicon compound represented by the general formula (1). A material, and if necessary, an electron transport material and a hole (hole) transport material are dissolved or dispersed in an organic solvent, and a spin coating method, a dip method, or the like is applied on the transparent electrode using the obtained coating solution. Can be obtained by forming a film. Here, the film thicknesses of the hole transport layer and the light emitting layer according to the present invention are preferably 0.03 to 0.2 μm, respectively. The dispersion state of the light emitting material in these layers may be either a molecular dispersion state or a fine particle dispersion state. When the dispersed state of the light emitting material is changed to the molecular dispersed state, it is necessary to use a common solvent of the organosilicon compound represented by the general formula (1), the light emitting material, the electron transporting material and the hole transporting material as the dispersing solvent. On the other hand, when the dispersed state of the luminescent material is changed to the fine particle dispersed state, the dispersibility of the luminescent material and the solubility of the organosilicon compound represented by the general formula (1), the electron transport material, and the hole transport material, It is necessary to select a dispersion solvent in consideration of the above. Further, when the dispersed state of the light emitting material is changed to the fine particle dispersed state, a ball mill, a sand mill, a paint shaker, an attritor, a homogenizer, an ultrasonic wave, or the like can be used.
[0077]
A light emitting material, an electron transport material, or a back electrode is formed on the layer containing the organosilicon compound represented by the above general formula (1), depending on the layer structure of each organic EL element. The organic EL device according to the present invention can be obtained by vacuum deposition. Here, in this invention, it is preferable that the film thickness of the light emitting layer and electron transport layer which have an electron transport ability is respectively 0.1 micrometer or less, and it is especially preferable that it is 0.03-0.08 micrometer. The organic EL device according to the present invention has a current density of 1 to 200 mA / cm between a pair of electrodes, for example, at 4 to 20 V.²It is possible to emit light by applying a direct current voltage.
[0078]
【Example】
EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example. In the following examples, among the organosilicon compounds represented by the above general formula (4), those having a combination of functional groups shown in the above Tables 1 to 3 are given corresponding compound numbers. Example compound [No. 28] ”and the like. Similarly, among the organic compounds represented by the general formula (3), those having the structures shown in Table 4 are given corresponding compound numbers, and are referred to as “Exemplary Compound [III-6]” and the like. And
[0079]
(Preparation of electrophotographic photoreceptor)
Example 1
In accordance with the following procedure, 16 electrophotographic photoreceptors were produced at the same time.
[0080]
First, on a cylindrical aluminum substrate having an outer diameter of 30 mm subjected to a honing treatment, 100 parts by weight of a zirconium compound (trade name: Olga Chicks ZC540, manufactured by Matsumoto Pharmaceutical Co., Ltd.), a silane compound (trade name: A1100, manufactured by Nihon Unicar) A solution consisting of 10 parts by weight, 400 parts by weight of isopropanol and 200 parts by weight of butanol was applied by dip coating and dried by heating at 150 ° C. for 10 minutes to form an undercoat layer of 0.1 μm.
[0081]
Next, as a charge generation material, Bragg angles (2θ ± 0.2 °) in X-ray diffraction spectrum have strong diffraction peaks at 7.4 °, 16.6 °, 25.5 ° and 28.3 °. 10 parts by weight of chlorogallium phthalocyanine crystal is mixed with 10 parts by weight of polyvinyl butyral resin (trade name: ESREC BM-S, manufactured by Sekisui Chemical Co., Ltd.) and 1000 parts by weight of butyl acetate, and dispersed with glass beads for 1 hour using a paint shaker. went. The coating solution thus obtained was dip-coated on the undercoat layer and dried by heating at 100 ° C. for 10 minutes to form a charge generation layer having a thickness of about 0.15 μm.
[0082]
Furthermore, the following structural formula (32):
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And a bisphenol (Z) polycarbonate resin (viscosity average molecular weight: 4.4 × 10^Four) A coating solution obtained by dissolving 30 parts by weight in a mixed solvent of 150 parts by weight of monochlorobenzene and 150 parts by weight of tetrahydrofuran was dip coated on the charge generation layer and dried by heating at 115 ° C. for 1 hour. A 20 μm charge transport layer was formed.
[0083]
  Furthermore, the exemplified compound [No. 28] 20 parts by weight, Exemplified Compound [III-6] 30 parts by weight, Isopropyl alcohol (IPA) 20 parts by weight, Methanol 20 parts by weight were sampled and mixed well. Further, 2 parts by weight of ion exchange resin (Amberlyst 15E) and 24 parts by weight of distilled water were added and stirred at room temperature for 10 hours, and then thin layer chromatography (TLC, developing solvent: hexane / ethyl acetate = 3/1, Adsorbent: Silica gel) and the exemplified compound [No. 28] was confirmed. Thereafter, the ion exchange resin and a small amount of precipitate in the reaction solution are removed by filtration, and aluminum trisacease is removed.HA coating solution is prepared by adding 0.5 parts by weight of acetonate and 1 part by weight of acetylacetone and dissolving. The obtained coating solution is dip-coated on the charge transport layer and heated at 120 ° C. for 1 hour. It was dried to form a surface protective layer having a thickness of 5 μm to obtain a desired electrophotographic photosensitive member.
[0084]
The 16 electrophotographic photoreceptors thus prepared all had good surface conditions, and no film formation defects such as cracks and uneven drying were observed.
[0085]
Further, from the electrophotographic photoreceptor thus obtained, the surface protective layer was peeled off using an adhesive tape not containing silicon, and about 150 mg of the peeled material was finely ground in a mortar, and a zirconia sample tube (7 mmφ) To fill²⁹Si-NMR spectrum was measured. In addition,²⁹The Si-NMR spectrum was measured using a Varian UNITY-300 under the following conditions:
Frequency: 59.59MHz
Delay time: 10.00 seconds
Contact time: 2.5 milliseconds
Integration count: 10,000 times
Measurement temperature: 25 ° C
Sample rotation speed: 4000 ± 500 rpm
Measured with Obtained²⁹The Si-NMR spectrum was obtained in FIG.²⁹Peak area ratio S calculated based on Si-NMR spectrum₁/ (S₁+ S₂) Are shown in Table 5, respectively.
[0086]
Example 2
Exemplified compounds in Example 1 [No. 28] Exemplified compound [No. 29] 16 electrophotographic photoreceptors were simultaneously prepared in the same manner as in Example 1 except that 25 parts by weight and the amount of the exemplified compound [III-6] was 25 parts by weight.²⁹The Si-NMR spectrum was measured.
[0087]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0088]
Example 3
Exemplified compounds in Example 1 [No. 28] Exemplified compound [No. 37] In the same manner as in Example 1 except that 20 parts by weight were used, 16 electrophotographic photosensitive members were simultaneously prepared, and surface state observation and²⁹The Si-NMR spectrum was measured.
[0089]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0090]
Example 4
Exemplified compounds in Example 1 [No. 28] Exemplified compound [No. 29] Example except that 25 parts by weight, 5 parts by weight of the exemplified compound [III-4] and 20 parts by weight of the exemplified compound [III-6] were used in place of 30 parts by weight of the exemplified compound [III-6]. In the same manner as in No. 1, 16 electrophotographic photoreceptors were prepared at the same time, and surface state observation and²⁹The Si-NMR spectrum was measured.
[0091]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0092]
Example 5
Exemplified compounds in Example 1 [No. 28] Exemplified compound [No. 29] Example, except that 25 parts by weight, 15 parts by weight of exemplified compound [III-4] and 10 parts by weight of exemplified compound [III-6] were used in place of 30 parts by weight of exemplified compound [III-6]. In the same manner as in No. 1, 16 electrophotographic photoreceptors were prepared at the same time, and surface state observation and²⁹The Si-NMR spectrum was measured.
[0093]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0094]
Example 6
Exemplified compounds in Example 1 [No. 28] Exemplified compound [No. 29] Example, except that 25 parts by weight, 10 parts by weight of the exemplified compound [III-4] and 15 parts by weight of the exemplified compound [III-6] were used instead of 30 parts by weight of the exemplified compound [III-6]. In the same manner as in No. 1, 16 electrophotographic photoreceptors were prepared at the same time, and surface state observation and²⁹The Si-NMR spectrum was measured.
[0095]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0096]
Example 7
Exemplified compounds in Example 1 [No. 28] Exemplified compound [No. 29] Example, except that 25 parts by weight, 15 parts by weight of exemplified compound [III-6] and 10 parts by weight of silicone fine particles (AEROSIL R812) were used instead of 30 parts by weight of exemplified compound [III-6] In the same manner as in No. 1, 16 electrophotographic photoreceptors were prepared at the same time, and surface state observation and²⁹The Si-NMR spectrum was measured.
[0097]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0098]
Comparative Example 1
Except that the surface protective layer in Example 1 was not provided, 16 electrophotographic photoreceptors were simultaneously prepared in the same manner as in Example 1 to observe the surface state and²⁹The Si-NMR spectrum was measured.
[0099]
The surface state of the obtained electrophotographic photoreceptor and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0100]
Comparative Example 2
The process up to the preparation of the charge transport layer is carried out in the same manner as in Example 1. In the formation of the surface protective layer, the exemplified compound [No. 28] Exemplified compound [No. 29] Example, except that 25 parts by weight, Example compound [III-6] 20 parts by weight and Example compound [III-6] 5 parts by weight were used in place of 30 parts by weight of Example compound [III-6]. In the same manner as in No. 1, 16 electrophotographic photoreceptors were produced at the same time. In particular, wrinkle-like film formation defects were observed on the two photoreceptors arranged near the hot air outlet used during drying.
[0101]
The surface state of the electrophotographic photoreceptor thus obtained and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0102]
Comparative Example 3
The process up to the preparation of the charge transport layer is carried out in the same manner as in Example 1. In the formation of the surface protective layer, the exemplified compound [No. 28] Exemplified compound [No. 29] 25 parts by weight, and in the same manner as in Example 1 except that 25 parts by weight of the exemplified compound [III-4] was used instead of 30 parts by weight of the exemplified compound [III-6], the electrophotographic photoreceptor 16 When the book was produced at the same time, in particular, wrinkle-like film formation defects were observed on the four photoconductors arranged near the hot air outlet used during drying.
[0103]
The surface state of the electrophotographic photoreceptor thus obtained and²⁹Peak area ratio S in Si-NMR spectrum₁/ (S₁+ S₂) Is shown in Table 5.
[0104]
(Print test)
Using the electrophotographic photoreceptors of Examples 1 to 7 and Comparative Examples 1 to 3 thus obtained, an electrophotographic image forming apparatus (remodeled from Laser press 4161II) having the configuration shown in FIG. Then, 50,000 print tests (printing paper: acid paper) were performed on each device under two conditions of normal temperature and normal humidity (about 20 ° C., 40% RH) and high temperature and high humidity (about 29 ° C., 85% RH). The image quality of the copy and the surface condition of the photoreceptor were evaluated. The results are shown in Table 5. In the evaluation of the image quality, the first and 50,000th copies were observed for the presence of image quality defects, and in the evaluation of the surface state of the photoreceptor, the presence or absence of scratches or deposits was observed.
[0105]
[Table 5]

[0106]
As shown in Table 5, in Examples 1 to 7, all of the 16 electrophotographic photoreceptors produced simultaneously had a good surface state without wrinkles and the like. In any of the print tests using these electrophotographic photoreceptors, good image quality can be obtained even on the 50,000th copy, and the surface of the photoreceptor after the test has scratches and deposits. I was not able to admit.
[0107]
In contrast, when the electrophotographic photoreceptor of Comparative Example 1 was used, image quality defects in the 50,000th copy and scratches on the photoreceptor surface after the test were observed. Further, in Comparative Examples 2 and 3, wrinkles occurred in some of the 16 electrophotographic photoreceptors produced simultaneously, and when these electrophotographic photoreceptors were used, a copy was produced from the beginning of the print test. Image quality defects were observed, and deposits were observed on the surface of the photoreceptor after the test.
[0108]
【The invention's effect】
As described above, according to the present invention, an organic electronic device having sufficiently high photoelectric characteristics and sufficiently high durability and capable of being manufactured reliably and easily can be obtained. By applying the organic electronic device of the present invention to an electrophotographic photosensitive member and using it in an electrophotographic image forming apparatus, it is possible to obtain sufficiently good image quality over a long period of time.
[Brief description of the drawings]
FIG. 1 is a cross-sectional view showing a preferred embodiment of an electrophotographic photosensitive member of the present invention.
FIG. 2 is a schematic configuration diagram showing a preferred embodiment of the electrophotographic image forming apparatus of the present invention.
FIG. 3 is a schematic configuration diagram showing a preferred embodiment of an organic electroluminescence element according to the present invention.
FIG. 4 is a schematic configuration diagram showing a preferred embodiment of an organic electroluminescence element according to the present invention.
5 shows the surface protective layer of the electrophotographic photosensitive member obtained in Example 1. FIG.²⁹It is a graph showing a Si-NMR spectrum.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 1 ... Electrophotographic photosensitive member, 2 ... Conductive support body, 3 ... Photosensitive layer, 4 ... Charge generation layer, 5 ... Charge transport layer, 6 ... Surface protective layer, 7 ... Undercoat layer, 8 ... Support body, 9 ... Power supply, 10 ... charging member, 11 ... image input device, 12 ... developing device, 13 ... transfer device, 14 ... image fixing device, 15 ... cleaning device, 16 ... static eliminator, 17 ... transparent insulating substrate, 18 ... transparent electrode , 19 ... hole transport layer, 20 ... light emitting layer, 21 ... back electrode, 22 ... light emitting layer having carrier transport ability.

Claims (6)

A support and laminated on the support, the following general formula (1):
W- [D-SiR _3-a Q _a ] _b (1)
Wherein W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4).
An organic electronic device comprising: a layer formed by blending an organosilicon compound represented by:
The peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the ²⁹ Si-NMR spectrum of the layer are represented by the following relational expression (2):
0.5 ≦ S ₁ / (S ₁ + S ₂ ) (2)
(Wherein S ₁ represents a peak area of −35 to 0 ppm, and S ₂ represents a peak area of −100 to −40 ppm)
An organic electronic device characterized by satisfying the condition represented by A layer formed by blending the organosilicon compound represented by the general formula (1) further includes the following general formula (3):
A- [D′-SiR ′ _3-c Q ′ _c ] _n (3)
(In the formula, A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group or a siloxane group, and D ′ represents a divalent functional group. R ′ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q ′ represents a hydrolyzable group, c represents an integer of 1 to 3, and n represents an integer of 2 or more. To express)
The organic silicon compound represented by the formula (1) is contained in an amount of 0.1 to 10 parts by weight with respect to 1 part by weight of the organosilicon compound represented by the general formula (1). Organic electronic devices. A support, and the following general formula (1) laminated on the support:
W- [D-SiR _3-a Q _a ] _b (1)
(Wherein, W represents a photofunctional organic group, D represents a divalent functional group, R represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, and Q represents a hydrolyzable group. A represents an integer of 1 to 3, and b represents an integer of 1 to 4).
A layer formed by blending an organosilicon compound represented by:
The peak area of −35 to 0 ppm and the peak area of −100 to −40 ppm in the ²⁹ Si-NMR spectrum of the layer are represented by the following relational expression (2):
0.5 ≦ S ₁ / (S ₁ + S ₂ ) (2)
(Wherein S ₁ represents a peak area of −35 to 0 ppm, and S ₂ represents a peak area of −100 to −40 ppm)
An electrophotographic photoreceptor characterized by satisfying the condition represented by: A layer formed by blending the organosilicon compound represented by the general formula (1) further includes the following general formula (3):
A- [D′-SiR ′ _3-c Q ′ _c ] _n (3)
(In the formula, A represents a linear or branched n-valent aliphatic hydrocarbon group, a substituted or unsubstituted n-valent aromatic hydrocarbon group, an imino group or a siloxane group, and D ′ represents a divalent functional group. R ′ represents a hydrogen atom, an alkyl group or a substituted or unsubstituted aryl group, Q ′ represents a hydrolyzable group, c represents an integer of 1 to 3, and n represents an integer of 2 or more. To express)
The organic silicon compound represented by formula (1) is contained in an amount of 0.1 to 10 parts by weight based on 1 part by weight of the organosilicon compound represented by the general formula (1). Electrophotographic photoreceptor. An electrophotographic photosensitive member according to claim 3 or 4,
A charging device for charging the electrophotographic photoreceptor;
An exposure apparatus for forming an electrostatic latent image on the electrophotographic photosensitive member;
A developing device for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image;
A transfer device for transferring the toner image to a transfer material;
A cleaning device for removing toner remaining on the surface of the electrophotographic photosensitive member;
An electrophotographic image forming apparatus comprising: A charging device for charging the electrophotographic photosensitive member,
From the developing device for developing the electrostatic latent image formed on the electrophotographic photosensitive member with toner to form a toner image, and the cleaning device for removing the toner remaining on the surface of the electrophotographic photosensitive member At least one selected from the group consisting of:
An electrophotographic photosensitive member according to claim 3 or 4,
A process cartridge comprising:

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