JP3740389B2 - Electrophotographic photosensitive member, electrophotographic apparatus, and process cartridge - Google Patents

Description

【００３７】
式中、Ｒ_１１、Ｒ_１２およびＲ_１３はそれぞれ炭素数１〜８の枝分かれしてもよい２価の炭化水素基を表し、α、βおよびγはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表し、ａ１、ｂ１およびｃ１は１または０であり、ｍ１およびｎ１は０または１である。
【外１１】

【００３８】
式中、Ｒ_２１、Ｒ_２２およびＲ_２３はそれぞれ炭素数１〜８の枝分かれしてもよい２価の炭化水素基を表し、δおよびεはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表し、ａ２、ｂ２およびｃ２は１または０である。ｍ２、ｎ２およびｐ２は０または１であり、総てが同時に０になることはない。τおよびυはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表す。なお、τとυは置換基を介して共同で環をなしてもよい。
【外１２】

【００３９】
式中、Ｒ_３１、Ｒ_３２、Ｒ_３３およびＲ_３４はそれぞれ炭素数１〜８の枝分かれしてもよい２価の炭化水素基を表し、ζ、η、θおよびιはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表し、ａ３、ｂ３、ｃ３およびｄ３は１または０であり、ｍ３、ｎ３およびｐ３は０または１である。φおよびχはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表す。なお、φとχは置換基を介して共同で環をなしてもよい。
【００４０】
なお、上記式（１）中のａ１、ｂ１およびｃ１、上記式（２）中のａ２、ｂ２およびｃ２、上記式（３）中のａ３、ｂ３、ｃ３およびｄ３が０のとき、上記式（１）〜（３）で示される構造を有する電荷輸送物質は、それらはヒドロキシアルキル基を有する電荷輸送物質であり、１のとき、それらはヒドロキシアルコキシ基を有する電荷輸送物質である。
【００４１】
上記式（１）〜（３）における置換基などの構造について以下に詳しく説明する。
【００４２】
式中、Ｒ_１１〜Ｒ_１３、Ｒ_２１〜Ｒ_２３、Ｒ_３１〜Ｒ_３４はそれぞれ炭素数１〜８の枝分かれしてもよい、メチレン基、エチレン基、プロピレン基およびブチレンなどの２価の炭化水素基を表す。式中、α、β、γ、δ、ε、ζ、η、θおよびιが表すベンゼン環が有してもよい置換基としては、フッ素、塩素、臭素およびヨウ素などのハロゲン原子、置換基を有してもよいメチル基、エチル基、プロピル基およびブチル基などのアルキル基、置換基を有してもよいメトキシ基、エトキシ基、プロポキシ基およびブトキシ基などのアルコキシ基、置換基を有してもよいフェニル基、ナフチル基、アンスリル基およびピレニル基などのアリール基、置換基を有してもよいピリジル基、チエニル基、フリル基およびキノリル基などの複素環基を示す。
【００４３】
式中、τ、υ、φおよびχがあらわすベンゼン環が有してもよい置換基としては、フッ素、塩素、臭素およびヨウ素などのハロゲン原子、置換基を有してもよいメチル基、エチル基、プロピル基およびブチル基などのアルキル基、置換基を有してもよいメトキシ基、エトキシ基、プロポキシ基およびブトキシ基などのアルコキシ基、置換基を有してもよいフェニル基、ナフチル基、アンスリル基およびピレニル基などのアリール基、置換基を有してもよいピリジル基、チエニル基、フリル基およびキノリル基などの複素環基を示す。なお、τとυ、および、φとχは共同でそれぞれが結合しているビフェニル骨格を介して、フルオレン骨格やジヒドロフェナントレン骨格などの環状構造を形成してもよい。
【００４４】
式（１）〜（３）において有してもよい置換基としては、メチル基、エチル基、プロピル基およびブチル基などのアルキル基；ベンジル基、フェネチル基およびナフチルメチル基などのアラルキル基；フェニル基、ナフチル基、アンスリル基、ピレニル基、フルオレニル基、カルバゾリル基、ジベンゾフリル基およびジベンゾチオフェニル基などの芳香環基；メトキシ基、エトキシ基およびプロポキシ基などのアルコキシ基、フェノキシ基およびナフトキシ基などのアリールオキシ基；フッ素、塩素、臭素およびヨウ素などのハロゲン原子；ニトロ基、またはシアノ基などが挙げられる。
【００４５】
以下に、本発明で用いられるヒドロキシアルキル基を有する電荷輸送物質、および、ヒドロキシアルコキシ基を有する電荷輸送物質の具体例を示すが、本発明の電荷輸送物質は、これらに限定されるものではない。
【外１３】

【００４６】
【外１４】

【００４７】
【外１５】

【００４８】
【外１６】

【００４９】
【外１７】

【００５０】
【外１８】

【００５１】
【外１９】

【００５２】
【外２０】

【００５３】
【外２１】

【００５４】
【外２２】

【００５５】
【外２３】

【００５６】
【外２４】

【００５７】
【外２５】

【００５８】
【外２６】

【００５９】
【外２７】

【００６０】
【外２８】

【００６１】
【外２９】

【００６２】
【外３０】

【００６３】
【外３１】

【００６４】
【外３２】

【００６５】
【外３３】

【００６６】
【外３４】

【００６７】
【外３５】

【００６８】
これらの中でも、上記式（１）で示される構造を有する電荷輸送物質の中では、（１−３）、（１−５）、（１−２１）、（１−２２）、（１−２３）、（１−２８）、（１−４０）、（１−４１）、（１−４４）、（１−５３）、（１−５４）、（１−５５）、（１−５６）、（１−５７）、（１−５８）、（１−５９）、（１−６０）および（１−６１）が好ましく、特には（１−５）、（１−２２）、（１−２３）、（１−４１）、（１−５４）および（１−５９）がより好ましい。
【００６９】
上記式（２）で示される構造を有する電荷輸送物質の中では、（２−７）、（２−２０）、（２−２９）、（２−３０）および（２−３２）が好ましく、特には（２−２０）および（２−３０）がより好ましい。
【００７０】
上記式（３）で示される構造を有する電荷輸送物質の中では、（３−７）、（３−９）、（３−１０）、（３−１７）、（３−２２）および（３−２３）が好ましく、特には（３−１０）および（３−２３）がより好ましい。
【００７１】
また、本発明に用いられる電荷輸送物質のうち、置換基を有してもよいヒドロキシフェニル基を有する電荷輸送物質は、下記式（４）〜（６）のいずれかで表される特定の構造を有する化合物であることが好ましい。
【外３６】

【００７２】
式中、Ｒ_４１は炭素数１〜８の枝分かれしてもよい２価の炭化水素基を表し、Ｒ_４２は水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいフェニル基を表す。Ａｒ_４１およびＡｒ_４２は置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を表す。Ａｒ_４３は置換基を有してもよいアリーレン基、２価の置換基を有してもよい複素環基を表す。ｍ４およびｎ４はそれぞれ０または１である。ただし、ｎ４＝０のとき、ｍ４＝０である。κおよびλはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表す。
【外３７】

【００７３】
式中、Ｒ_５１は炭素数１〜８の枝分かれしてもよい２価の炭化水素基を表す。Ａｒ_５１およびＡｒ_５２は置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を表す。μおよびνはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表す。なお、μとνは置換基を介して共同で環をなしてもよい。ｍ５は０または１である。
【外３８】

【００７４】
式中、Ｒ_６１およびＲ_６２はそれぞれ炭素数１〜８の枝分かれしてもよい２価の炭化水素基を表す。Ａｒ_６１は置換基を有してもよいアルキル基、置換基を有してもよいアラルキル基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を表す。ξ、π、ρおよびσはそれぞれ置換基としてハロゲン原子、置換基を有してもよいアルキル基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリール基、置換基を有してもよい複素環基を１つ以上有してもよいベンゼン環を表す。なお、ξとπ、および、ρとσは置換基を介して共同で環をなしてもよい。ｍ６およびｎ６はそれぞれ０または１である。
【００７５】
上記一般式（４）〜（６）における置換基などの構造について以下に詳しく説明する。
【００７６】
式中、Ｒ_４１、Ｒ_５１、Ｒ_６１およびＲ_６２はそれぞれ炭素数１〜８の枝分かれしてもよい、メチレン基、エチレン基、プロピレン基およびブチレン基などの２価の炭化水素基を表す。Ｒ_４２は水素原子、置換基を有してもよいメチル基、エチル基、プロピル基およびブチル基などのアルキル基、置換基を有してもよいベンジル基、フェネチル基およびナフチルメチル基などのアラルキル基、またはフェニル基を示す。
【００７７】
式中、κ、λ、μ、ν、ξ、π、ρおよびσが表すベンゼン環が有してもよい置換基としては、フッ素、塩素、臭素およびヨウ素などのハロゲン原子、置換基を有してもよいメチル基、エチル基、プロピル基およびブチル基などのアルキル基、置換基を有してもよいメトキシ基、エトキシ基、プロポキシ基およびブトキシ基などのアルコキシ基、置換基を有してもよいフェニル基、ナフチル基、アンスリル基およびピレニル基などのアリール基、または置換基を有してもよいピリジル基、チエニル基、フリル基およびキノリル基などの複素環基を示す。
【００７８】
また、μとν、ξとπおよびρとσは共同でそれぞれが結合している置換基などを介して、フルオレン骨格やジヒドロフェナントレン骨格などの環状構造を形成してもよい。
【００７９】
Ａｒ_４１、Ａｒ_４２、Ａｒ_５１、Ａｒ_５２およびＡｒ_６１は置換基を有してもよいメチル基、エチル基、プロピル基およびブチル基などのアルキル基、置換基を有してもよいベンジル基、フェネチル基およびナフチルメチル基などのアラルキル基、置換基を有してもよいフェニル基、ナフチル基、アンスリル基およびピレニル基などのアリール基、または置換基を有してもよいピリジル基、チエニル基、フリル基およびキノリル基などの複素環基を示す。
【００８０】
Ａｒ_４３は置換基を有してもよいフェニレン基、ナフチレン基、アンスリレン基およびピレニレン基などのアリーレン基、ピリジレン基、またはチエニレン基などの２価の複素環基を示す。
【００８１】
式（４）〜（６）において有してもよい置換基としては、メチル基、エチル基、プロピル基およびブチル基などのアルキル基；ベンジル基、フェネチル基およびナフチルメチル基などのアラルキル基；フェニル基、ナフチル基、アンスリル基、ピレニル基、フルオレニル基、カルバゾリル基、ジベンゾフリル基およびジベンゾチオフェニル基などの芳香環基；メトキシ基、エトキシ基およびプロポキシ基などのアルコキシ基；フェノキシ基およびナフトキシ基などのアリールオキシ基；フッ素、塩素、臭素およびヨウ素などのハロゲン原子；ニトロ基およびシアノ基などが挙げられる。
【００８２】
以下に、本発明で用いられる置換基を有してもよいヒドロキシフェニル基を有する電荷輸送物質の具体例を示すが、本発明の電荷輸送物質は、これらに限定されるものではない。
【外３９】

【００８３】
【外４０】

【００８４】
【外４１】

【００８５】
【外４２】

【００８６】
【外４３】

【００８７】
【外４４】

【００８８】
【外４５】

【００８９】
【外４６】

【００９０】
【外４７】

【００９１】
【外４８】

【００９２】
【外４９】

【００９３】
【外５０】

【００９４】
【外５１】

【００９５】
【外５２】

【００９６】
【外５３】

【００９７】
【外５４】

【００９８】
【外５５】

【００９９】
【外５６】

【０１００】
【外５７】

【０１０１】
【外５８】

【０１０２】
【外５９】

【０１０３】
【外６０】

【０１０４】
これらの中でも、上記式（４）で示される構造を有する電荷輸送物質の中では、（４−６）、（４−８）、（４−１３）、（４−１４）および（４−５５）が好ましく、特には（４−１４）および（４−５５）がより好ましい。
【０１０５】
上記式（５）で示される構造を有する電荷輸送物質の中では、（５−１３）、（５−１４）、（５−１６）、（５−１８）、（５−１９）、（５−２８）および（５−２９）が好ましく、特には（５−２９）がより好ましい。
【０１０６】
上記式（６）で示される構造を有する電荷輸送物質の中では、（６−１０）、（６−１１）、（６−１２）、（６−１４）、（６−１５）、（６−１８）、（６−１９）および（６−２０）が好ましく、特には（６−１４）、（６−１８）、（６−１９）および（６−２０）がより好ましい。
【０１０７】
保護層の強度の観点からは、保護層の結着樹脂であるフェノール樹脂と共に硬化、３次元的に架橋する置換基を有してもよいヒドロキシフェニル基を有する電荷輸送物質がより好ましく、一方、感度低下や残留電位上昇の観点からは、ヒドロキシアルキル基を有する電荷輸送物質およびヒドロキシアルコキシ基を有する電荷輸送物質が湿度の影響を受けにくくより好ましい。
【０１０８】
さらに、電荷輸送物質と硬化性フェノール樹脂との相溶性をより一層良好にするためには、上記式（１）〜（６）中のＲ_１１、Ｒ_１２、Ｒ_１３、Ｒ_２１、Ｒ_２２、Ｒ_２３、Ｒ_３１、Ｒ_３２、Ｒ_３３、Ｒ_３４、Ｒ_４１、Ｒ_５１、Ｒ_６１およびＲ_６２で示される２価の炭化水素基は炭素数４以下であることがより好ましく、また、ヒドロキシアルキル基、ヒドロキシアルコキシ基および置換基を有してもよいヒドロキシフェニル基の数は２個以上であることがより好ましい。
【０１０９】
また、本発明に用いられる電荷輸送物質は、該保護層を作製するための塗料中に均一に溶解または分散させ、塗布して形成する。本発明の電荷輸送物質と硬化性フェノール樹脂の混合割合は、質量比で、電荷輸送物質／硬化性フェノール樹脂＝０．１／１０〜２０／１０が好ましく、特には０．５／１０〜１０／１０が好ましい。硬化性フェノール樹脂に対して電荷輸送物質が少なすぎると残留電位低下の効果が小さくなり、多すぎると保護層の強度を弱める可能性がある。
【０１１０】
上記の保護層を有する電子写真感光体において、さらに導電性微粒子を含有させることによって、電子写真感光体の残留電位低下をより高い次元で達成できる。
【０１１１】
導電性微粒子としては、金属、金属酸化物およびカーボンブラックなどが挙げられる。金属としては、アルミニウム、亜鉛、銅、クロム、ニッケル、銀およびステンレスなど、またはこれらの金属をプラスチックの粒子の表面に蒸着したものなどが挙げられる。金属酸化物としては、酸化亜鉛、酸化チタン、酸化スズ、酸化アンチモン、酸化インジウム、酸化ビスマス、スズをドープした酸化インジウム、アンチモンやタンタルをドープした酸化スズおよびアンチモンをドープした酸化ジルコニウムなどが挙げられる。これらは、単独で用いることも、２種以上を組み合わせて用いることもできる。２種以上を組み合わせて用いる場合は、単に混合しても、固溶体や融着の形にしてもよい。
【０１１２】
本発明においては、上述した各種導電性微粒子の中でも透明性の点から金属酸化物を用いることが特に好ましい。さらに、これら金属酸化物の中でも透明性、分散性、抵抗制御性などの点から酸化スズを用いることが特に好ましい。ここで用いられる酸化スズは、分散性、液安定性を改良する目的で表面処理などされていてもよく、抵抗制御性を良くする目的でアンチモンやタンタルをドープすることもできる。
【０１１３】
本発明において用いられる導電性微粒子の体積平均粒径は、保護層の透明性の点で０．３μｍ以下が好ましく、特に０．１μｍ以下が好ましい。
【０１１４】
本発明において用いられる保護層は、本質的に抵抗体として電荷の移動をさせるものではなく、保護層中に含有させた電荷輸送物質により電荷を移動させて、保護層を施した電子写真感光体の感度を維持し、残留電位を低下させるものである。したがって、抵抗体としての体積抵抗率は低く設定する必要はなく、その体積抵抗率として、１×１０^１２（Ω・ｃｍ）以上にすることにより、形成された静電潜像の流れなどを高い次元で抑制することができる。
【０１１５】
本発明における導電性微粒子は、保護層の体積抵抗率を調整する補助的な役割を担うものであり、必要なければ必ずしも用いなくてよい。
【０１１６】
膜強度的には、導電性微粒子の量が増えれば増えるほど弱くなるため、導電性微粒子の量は、保護層の体積抵抗および残留電位が許容できる範囲において、少なくする方が好ましい。
【０１１７】
上記の保護層を有する電子写真感光体において、さらにフッ素原子含有樹脂微粒子を含有させることによって、電子写真感光体表面の離型性の向上をより高い次元で達成できる。
【０１１８】
フッ素原子含有樹脂微粒子としては、四フッ化エチレン、三フッ化塩化エチレン樹脂、六フッ化エチレンプロピレン樹脂、フッ化ビニル樹脂、フッ化ビニリデン樹脂、二フッ化二塩化エチレン樹脂およびこれらの共重合体の中から１種あるいは２種以上を適宜選択するのが好ましいが、特に、四フッ化エチレン樹脂およびフッ化ビニリデン樹脂が好ましい。樹脂粒子の分子量分布や粒径は、適宜選択することができ、特に制限されるものではない。
【０１１９】
このフッ素原子含有樹脂微粒子を導電性微粒子と共に樹脂溶液中で相互の粒子を凝集させないようにするために、フッ素原子含有化合物を導電性微粒子の分散時に添加したり、また、導電性微粒子の表面をフッ素原子含有化合物で表面処理したりすることが好ましい。
【０１２０】
フッ素原子含有化合物を添加または導電性微粒子に表面処理を行うことにより、フッ素原子含有化合物のない場合に比べて、樹脂溶液中での導電性微粒子とフッ素原子含有樹脂微粒子の分散性および分散安定性が格段に向上した。また、フッ素原子含有化合物を添加し導電性微粒子を分散した液、または表面処理を施した導電性微粒子を分散した液に、フッ素原子含有樹脂微粒子を分散することによって分散粒子の二次粒子の形成もなく、経時的にも非常に安定した分散性のよい塗工液が得られる。
【０１２１】
フッ素原子含有化合物としては、含フッ素シランカップリング剤、フッ素変性シリコーンオイルおよびフッ素系界面活性剤などが挙げられる。表１〜表３に好ましい化合物例を挙げるが、本発明はこれらの化合物に限定されるものではない。
【０１２２】
【表１】

【０１２３】
【表２】

【０１２４】
【表３】

【０１２５】
導電性微粒子の表面処理方法としては、導電性微粒子と表面処理剤とを適当な溶剤中で混合、分散し、表面処理剤を導電性微粒子表面に付着させる。分散の方法としてはボールミルやサンドミルなどの通常の分散手段を用いることができる。次に、この分散溶液から溶剤を除去し、導電性微粒子表面に固着させればよい。また、必要に応じて、この後にさらに熱処理を行ってもよい。また、処理液中には反応促進のための触媒を添加することもできる。さらに、必要に応じて表面処理後の導電性微粒子にさらに粉砕処理を施すことができる。
【０１２６】
導電性微粒子に対するフッ素原子含有化合物の割合は、粒子の粒径、形状および表面積などに影響を受けるが、表面処理済みの導電性微粒子全質量に対し、１〜６５質量％が好ましく、特には１〜５０質量％である。
【０１２７】
さらに、本発明においては、より環境安定性のある保護層とするために、下記式で示されるシロキサン化合物を導電性微粒子分散時に添加したり、または下記式で示されるシロキサン化合物で表面処理を施した導電性微粒子を混合したりすることが好ましい。
【外６１】

【０１２８】
式中、Ｔは水素原子またはメチル基であり、かつ、Ｔの全部における水素原子の割合は０．１〜５０％の範囲、ｔは０以上の整数である。
【０１２９】
このシロキサン化合物を添加後分散した塗工液、またはこれを表面処理した導電性金属酸化物微粒子を溶剤に溶かした結着樹脂中に分散することによって、分散粒子の二次粒子の形成もなく、経時的にも安定した分散性の良い塗工液が得られ、さらにこの塗工液より形成した保護層は透明性が高く、耐環境性に特に優れた膜が得られる。
【０１３０】
上記式で示されるシロキサン化合物の分子量は、特に制限されるものではないが、表面処理をする場合は、その容易さからは粘度が高すぎない方がよく、重量平均分子量で数百〜数万程度が適当である。
【０１３１】
表面処理の方法としては、湿式・乾式の二通りがある。湿式処理では、導電性金属酸化物粒子を上記式で示されるシロキサン化合物とを溶剤中で分散し、該シロキサン化合物を微粒子表面に付着させる。分散の手段としては、ボールミルやサンドミルなどの一般の分散手段を使用することができる。次に、この分散溶液を導電性金属酸化物微粒子表面に固着させる。この熱処理においては、シロキサン中のＳｉ−Ｈ結合が熱処理過程において空気中の酸素によって水素原子の酸化が起こり、新たなシロキサン結合ができる。その結果、シロキサンが三次元構造にまで発達し、導電性金属酸化物微粒子表面がこの網状構造で包まれる。このように表面処理は、該シロキサン化合物を導電性金属酸化物微粒子表面に固着させることによって完了するが、必要に応じて処理後の微粒子に粉砕処理を施してもよい。
【０１３２】
乾式処理においては、溶剤を用いずにシロキサン化合物と導電性金属酸化物微粒子とを混合し混練を行うことによってシロキサン化合物を微粒子表面に付着させる。その後は、湿式処理と同様に熱処理、粉砕処理を施して表面処理を完了する。
【０１３３】
保護層の塗料を分散する溶剤としては、硬化性フェノール樹脂を良く溶解し、本発明の上記電荷輸送物質も良く溶解し、導電性微粒子を用いる場合は、その分散性が良く、さらに、フッ素原子含有樹脂微粒子、フッ素原子含有化合物およびシロキサン化合物を用いる場合は、それらとの相溶性や処理性が良好で、さらに、保護層の塗料と接触する電荷輸送層に悪影響を与えない溶剤が好ましい。
【０１３４】
したがって、溶剤としては、メタノール、エタノールおよび２−プロパノールなどのアルコール類、アセトンやメチルエチルケトンなどのケトン類、酢酸メチルや酢酸エチルなどのエステル類、テトラヒドロフランやジオキサンなどのエーテル類、トルエンやキシレンなどの芳香族炭化水素類、またはクロロベンゼンやジクロロメタンなどのハロゲン系炭化水素類などが使用可能であり、さらにこれらを混合して用いてもよい。これらの中でも、フェノール樹脂の形態に最も好適な溶剤はメタノール、エタノールおよび２−プロパノールなどのアルコール類である。
【０１３５】
従来の電荷輸送物質は、一般的にアルコール類の溶剤には不溶または難溶であり、一般のフェノール樹脂への均一な分散は困難であるが、本発明の電荷輸送物質の多くはアルコール類を主成分とする溶剤に可溶であるので、フェノール樹脂塗料への分散が可能となる。
【０１３６】
本発明の保護層の塗布方法としては、浸漬コーティング法、スプレーコーティング法、スピンナーコーティング法、ローラーコーティング法、マイヤーバーコーティング法およびブレードコーティング法などの一般的な塗工方法を用いることができる。
【０１３７】
本発明の保護層の膜厚は、薄すぎると電子写真感光体の耐久性を損ない、厚すぎると保護層を設けたことによる残留電位が上昇するため、適度な厚さにする必要がある。具体的には、０．１μｍ〜１０μｍの範囲が好ましく、０．５μｍ〜７μｍの範囲がより好ましい。
【０１３８】
本発明においては、前記保護層中に、帯電時に発生するオゾンやＮＯｘなどの活性物質の付着による表面層の劣化などを防止する目的で、酸化防止剤の添加材を加えてもよい。
【０１３９】
次に、感光層について以下に説明する。
【０１４０】
本発明の電子写真感光体は、主に積層構造を有することが好ましい。図１（ａ）の電子写真感光体は、支持体４の上に電荷発生層３、電荷輸送層２が順に設けており、さらに最表面に保護層１を設けている。また、図１の（ｂ）、（ｃ）の様に支持体と電荷発生層の間に、結着層５、さらには干渉縞防止などを目的とする下引き層６を設けてもよい。
【０１４１】
支持体４としては、支持体自身が導電性を持つもの、例えば、アルミニウム、アルミニウム合金またはステンレスなどを用いることができ、その他にアルミニウム、アルミニウム合金または酸化インジウム−酸化スズ合金などを真空蒸着によって被膜形成された層を有する前記支持体やプラスチック、導電性微粒子（例えば、カーボンブラック、酸化スズ、酸化チタンおよび銀粒子など）を適当な結着樹脂と共にプラスチックや紙に含浸した支持体、導電性結着樹脂を有するプラスチックなどを用いることができる。
【０１４２】
また、支持体と感光層の間には、バリアー機能と接着機能を持つ結着層（接着層）を設けることができる。結着層は、感光層の接着性改良、塗工性改良、支持体の保護、支持体の欠陥の被覆、支持体からの電荷注入性改良および感光層の電気的破壊に対する保護などのために形成される。結着層には、カゼイン、ポリビニルアルコール、エチルセルロース、エチレン−アクリル酸コポリマー、ポリアミド、変性ポリアミド、ポリウレタン、ゼラチンまたは酸化アルミニウムなどによって形成できる。結着層の膜厚は、５μｍ以下が好ましく、特には０．１〜３μｍが好ましい。
【０１４３】
本発明に用いられる電荷発生物質としては、（１）モノアゾ、ジスアゾおよびトリスアゾなどのアゾ系顔料、（２）金属フタロシアニンおよび非金属フタロシアニンなどのフタロシアニン系顔料、（３）インジゴおよびチオインジゴなどのインジゴ系顔料、（４）ペリレン酸無水物およびペリレン酸イミドなどのペリレン系顔料、（５）アンスラキノンおよびピレンキノンなどの多環キノン系顔料、（６）スクワリリウム色素、（７）ピリリウム塩およびチアピリリウム塩類、（８）トリフェニルメタン系色素、（９）セレン、セレン−テルルおよびアモルファスシリコンなどの無機物質、（１０）キナクリドン顔料、（１１）アズレニウム塩顔料、（１２）シアニン染料、（１３）キサンテン色素、（１４）キノンイミン色素、（１５）スチリル色素、（１６）硫化カドミウムおよび（１７）酸化亜鉛などが挙げられる。
【０１４４】
電荷発生層に用いる結着樹脂としては、例えば、ポリカーボネート樹脂、ポリエステル樹脂、ポリアリレート樹脂、ブチラール樹脂、ポリスチレン樹脂、ポリビニルアセタール樹脂、ジアリルフタレート樹脂、アクリル樹脂、メタクリル樹脂、酢酸ビニル樹脂、フェノール樹脂、シリコーン樹脂、ポリスルホン樹脂、スチレン−ブタジエン共重合体樹脂、アルキッド樹脂、エポキシ樹脂、尿素樹脂および塩過ビニル−酢酸ビニル共重合体樹脂などが挙げられるが、これらに限定されるものではない。これらは、単独・混合あるいは共重合体ポリマーとして１種または２種以上用いることができる。
【０１４５】
電荷発生層用塗料に用いる溶剤は、使用する樹脂や電荷発生物質の溶解性や分散安定性から選択されるが、有機溶剤としては、アルコール類、スルホキシド類、ケトン類、エーテル類、エステル類、脂肪族ハロゲン化炭化水素類または芳香族化合物などを用いることができる。
【０１４６】
電荷発生層３は、前記の電荷発生物質を質量基準で０．３〜４倍量の結着樹脂および溶剤と共に、ホモジナイザー、超音波、ボールミル、サンドミル、アトライターまたはロールミルなどの方法でよく分散し、塗布、乾燥されて形成される。その厚みは、５μｍ以下が好ましく、特には０．０１〜１μｍの範囲が好ましい。
【０１４７】
また、電荷発生層には、種々の増感剤、酸化防止剤、紫外線吸収剤、可塑剤および公知の電荷発生物質を必要に応じて添加することもできる。
【０１４８】
用いられる電荷輸送物質としては、各種トリアリールアミン系化合物、各種ヒドラゾン系化合物、各種スチリル系化合物、各種スチルベン系化合物、各種ピラゾリン系化合物、各種オキサゾール系化合物、各種チアゾール系化合物および各種トリアリールメタン系化合物などが挙げられる。
【０１４９】
電荷輸送層２を形成するのに用いられる結着樹脂としては、アクリル樹脂、スチレン系樹脂、ポリエステル、ポリカーボネート樹脂、ポリアリレート、ポリサルホン、ポリフェニレンオキシド、エポキシ樹脂、ポリウレタン樹脂、アルキド樹脂および不飽和樹脂などから選ばれる樹脂が好ましい。特に好ましい樹脂としては、ポリメチルメタクリレート、ポリスチレン、スチレン−アクリロニトリル共重合体、ポリカーボネート樹脂およびジアリルフタレート樹脂が挙げられる。
【０１５０】
電荷輸送層２は、一般的には前記の電荷輸送物質と結着樹脂を溶剤に溶解し、塗布して形成する。電荷輸送物質と結着樹脂との混合割合（質量比）は、２：１〜１：２程度である。溶剤としては、アセトンやメチルエチルケトンなどのケトン類、酢酸メチルや酢酸エチルなどのエステル類、トルエンやキシレンなどの芳香族炭化水素類、クロロベンゼン、クロロホルムおよび四塩化炭素などの塩素系炭化水素類、テトラヒドロフランやジオキサンなどのエーテル類などが用いられる。この溶液を塗布する際には、例えば、浸漬コーティング法、スプレーコーティング法およびスピンナーコーティング法などのコーティング法を用いることができ、乾燥は１０℃〜２００℃が好ましく、より好ましくは２０℃〜１５０℃の範囲の温度で、５分〜５時間が好ましく、より好ましくは１０分〜２時間の時間で送風乾燥または静止乾燥下で行うことができる。
【０１５１】
電荷輸送層は、上述の電荷発生層と電気的の接続されており、電界の存在下で電荷発生層から注入された電荷キャリアを受け取ると共に、これらの電荷キャリアを保護層との界面まで輸送する機能を有している。この電荷輸送層は、電荷キャリアを輸送する限界があるので必要以上に膜厚を厚くすることができないが、５〜４０μｍが好ましく、特には７〜３０μｍの範囲が好ましい。
【０１５２】
さらに、電荷輸送層中に酸化防止剤、紫外線吸収剤、可塑剤および公知の電荷輸送物質を必要に応じて添加することもできる。
【０１５３】
本発明ではさらに、この電荷輸送層の上に前記保護層を塗布、硬化させて成膜することで完成される。
【０１５４】
図２に本発明の電子写真感光体を有するプロセスカートリッジを用いた電子写真装置の概略構成を示す。
【０１５５】
図において、１１はドラム状の本発明の電子写真感光体であり、軸１２を中心に矢印方向に所定の周速度で回転駆動される。電子写真感光体１１は、回転過程において、一次帯電手段１３によりその周面に正または負の所定電位の均一帯電を受け、次いで、スリット露光やレーザービーム走査露光などの露光手段（不図示）から出力される目的の画像情報の時系列電気デジタル画像信号に対応して強調変調された露光光１４を受ける。こうして電子写真感光体１１の周面に対し、目的の画像情報に対応した静電潜像が順次形成されていく。
【０１５６】
形成された静電潜像は、次いで現像手段１５によりトナー現像され、不図示の給紙部から電子写真感光体１１と転写手段１６との間に電子写真感光体１１の回転と同期して取り出されて給紙された転写材１７に、電子写真感光体１１の表面に形成担持されているトナー画像が転写手段１６により順次転写されていく。
【０１５７】
トナー画像の転写を受けた転写材１７は、電子写真感光体面から分離されて像定着手段１８へ導入されて像定着を受けることにより画像形成物（プリント、コピー）として装置外へプリントアウトされる。
【０１５８】
像転写後の電子写真感光体１１の表面は、クリーニング手段１９によって転写残りトナーの除去を受けて清浄面化され、さらに前露光手段（不図示）からの前露光光２０により除電処理された後、繰り返し画像形成に使用される。なお、一次帯電手段１３が帯電ローラーなどを用いた接触帯電手段である場合は、前露光は必ずしも必要ではない。
【０１５９】
本発明においては、上述の電子写真感光体１１、一次帯電手段１３、現像手段１５およびクリーニング手段１９などの構成要素のうち、複数のものを容器２１に納めてプロセスカートリッジとして一体に結合して構成し、このプロセスカートリッジを複写機やレーザービームプリンターなどの電子写真装置本体に対して着脱自在に構成してもよい。例えば、一次帯電手段１３、現像手段１５およびクリーニング手段１９の少なくとも１つを電子写真感光体１１と共に一体に支持してカートリッジ化して、装置本体のレールなどの案内手段２２を用いて装置本体に着脱自在なプロセスカートリッジとすることができる。
【０１６０】
また、露光光１４は、電子写真装置が複写機やプリンターである場合には、原稿からの反射光や透過光、あるいは、センサーで原稿を読取り、信号化し、この信号にしたがって行われるレーザービームの走査、ＬＥＤアレイの駆動および液晶シャッターアレイの駆動などにより照射される光である。
【０１６１】
本発明の電子写真感光体は、電子写真複写機に利用するのみならず、レーザービームプリンター、ＣＲＴプリンター、ＬＥＤプリンター、ＦＡＸ、液晶プリンターおよびレーザー製版などの電子写真応用分野にも広く用いることができる。
【０１６２】
【実施例】
次に、本発明を実施例により説明する。ただし、本発明の実施の形態は、これらに限定されるものではない。なお、実施例中の「部」は質量部を示す。
【０１６３】
（実施例１）
長さ２６０．５ｍｍ、直径３０ｍｍのアルミニウムシリンダー（ＪＩＳ Ａ３００３アルミニウムの合金）を支持体として、この上にポリアミド樹脂（商品名：アミランＣＭ８０００、東レ製）の５質量％メタノール溶液を浸漬法で塗布し、膜厚が０．５μｍの下引き層を設けた。
【０１６４】
次に、電荷発生物質として下記式で示される構造を有し、ＣｕＫαの特性Ｘ線回折におけるブラッグ角２θ±０．２゜の９．６°および２７．３゜に強いピークを有する結晶型であるオキシチタニウムフタロシアニン顔料４部、
【外６２】

【０１６５】
ポリビニルブチラール樹脂ＢＸ−１（積水化学工業（株）製）２部、および、シクロヘキサノン１１０部を、直径１ｍｍガラスビーズを用いてサンドミルで、４．５時間分散した。その後、酢酸エチル１３０部で希釈し電荷発生層用塗料とした。この分散液を前記下引き層上に浸漬法で塗布し、膜厚が０．１８μｍの電荷発生層を形成した。
【０１６６】
次いで、下記式で示される構造を有する電荷輸送物質７．５部、
【外６３】

【０１６７】
およびビスフェノールＺ型ポリカーボネート（商品名：Ｚ−２００、三菱ガス化学（株）製）１０部を、モノクロロベンゼン６０部／ジクロロメタン２０部に溶解した。この溶液を、前記電荷発生層上に浸漬塗布し、１１０℃で１時間で熱風乾燥し、膜厚が２０μｍの電荷輸送層を形成した。
【０１６８】
次に、保護層として、アンチモンドープ酸化スズ微粒子１００部を下記式で示される構造を有するフッ素原子含有化合物（商品名：ＬＳ−１０９０、信越化学工業（株）製）７部で表面処理した（以下、処理量：７％と表す）処理済み酸化スズ微粒子３５部と
【外６４】

【０１６９】
エタノール１５０部を、サンドミルにて、６６時間かけて分散を行い、さらに、ポリテトラフルオロエチレン微粒子（体積平均粒径０．１８μｍ）１８部を加えて、さらに１２時間サンドミルで分散を行った。
【０１７０】
その後、樹脂成分として、住友デュレズ（株）製レゾール型硬化性フェノール樹脂（商品名：ＰＲ−５３１２３）５４部（不揮発分：４５％）、さらにヒドロキシアルキル基を有する電荷輸送物質として前記化合物Ｎｏ．１−２３を１５部溶解し、エタノール３５部で希釈して保護層用塗料とした。
【０１７１】
この塗料を用いて、先の電荷輸送層上に浸漬塗布法により、膜を形成した後、１４５℃で１時間熱風乾燥し、膜厚が３μｍの保護層を形成した。保護層塗料の分散性は良好で、作製された保護層はムラのない均一な膜であった。
【０１７２】
電子写真特性の評価は、常温常湿（２３℃６０％ＲＨ）環境下および常温低湿（２３℃１０％ＲＨ）環境下でレーザービームプリンター（商品名：ＬＢＰ−ＮＸ：キヤノン（株）製）の改造機に取り付けて行った。電子写真感度として、暗部電位が−７００Ｖになるように帯電設定をし、これに波長７８０ｎｍのレーザー光を照射して−７００Ｖの電位を−２００Ｖまで下げるのに必要な光量を測定し、感度とした。また、２０μＪ／ｃｍ^２の光量を照射した場合の電位を残留電位Ｖｒとして測定した。さらに、同様のレーザービームプリンターを用いて初期転写効率、またさらに５０００枚の耐久による削れ量の測定を行った。
【０１７３】
電子写真感光体上での評価とは別に、膜硬度と体積抵抗率の測定を別途サンプルを作製して行った。
【０１７４】
保護層の硬度はドイツ、ＦＩＳＣＨＥＲ社製硬度計（Ｈ１００ＶＰ−ＨＣＵ）を用いて測定した。この測定による硬度は、次のようにして定められる。
【０１７５】
すなわち、四角錐で先端の対面角１３６°のダイヤモンド圧子で荷重をかけて保護層の膜に１μｍまで押し込み、圧子の幾何学的形状から計算された圧痕の表面積とその時の荷重から次の式（Ｉ）のように求まる。
ユニバーサル硬さ値ＨＵ(Ｎ／ｍｍ^２)＝荷重(Ｎ)／荷重下での圧痕の表面積(ｍｍ^２)・・・(Ｉ)
本実施例の保護層の硬度測定は、ガラスプレート上に保護層塗料を塗布し、硬化条件は上記電子写真感光体の作製時と同様に行い、この保護層膜を３〜４回塗工して膜厚を約１０μｍにして硬度測定サンプルとした。
【０１７６】
体積抵抗率の測定用サンプルは、ポリエチレンテレフタレートフィルム上に１８０μｍのギャップを持つ櫛形電極をアルミニウム蒸着により作製し、その上に上記電子写真感光体上に塗布したと同様の保護層用塗料をマイヤーバーを用いて同様の膜厚で塗布し、上記と同様の硬化条件で熱風乾燥して保護層膜を作製した。
【０１７７】
体積抵抗率の測定は、米国ヒューレットパッカード社製ｐＡメーター （４１４０Ｂ型）を用いて、印加電圧１００Ｖの条件で、温度：２３℃、湿度：５０％の環境下で測定した。結果を表４に示す。
【０１７８】
（実施例２〜９）
実施例１において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．１−２３）の代わりに、表４に示される電荷輸送物質に代えた以外は、実施例１と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０１７９】
（実施例１０〜１３）
実施例１、５、６および９において、前記フッ素原子含有化合物で示される化合物で表面処理した（処理量：７％）アンチモンドープ酸化スズ微粒子を２０部に代え、メチルハイドロジェンシリコーンオイル（商品名：ＫＦ９９、信越化学工業（株）製）で処理した（処理量：２０％）アンチモンドープ酸化スズ微粒子１５部をさらに添加分散して塗料を作製した以外は、実施例１、５、６および９と同様にして行った。結果を同様に表４に示す。
【０１８０】
（実施例１４〜１７）
実施例１、５、６および９において、前記フッ素原子含有化合物で表面処理したアンチモンドープ酸化スズ微粒子に代えて、表面処理を施していないアンチモンドープ酸化スズ微粒子（商品名：Ｔ−１、三菱マテリアル（株）製）を３５部、前記フッ素原子含有化合物（商品名：ＬＳ−１０９０、信越化学工業（株）製）を３．５部を添加し分散した以外は、実施例１と同様にして行った。結果を同様に表４に示す。
【０１８１】
（実施例１８〜２１）
実施例１４〜１７において用いた保護層塗工用塗料に対し、さらにメチルハイドロジェンシリコーンオイル（商品名：ＫＦ９９、信越化学工業（株）製）を１．５部を添加し、４時間攪拌して塗料とした以外は、実施例１４〜１７と同様にして行った。結果を同様に表４に示す。
【０１８２】
（実施例２２〜２５）
実施例１と同様の処理済み酸化スズ微粒子３５部とエタノール１５０部を、サンドミルにて、６６時間かけて分散を行い、その後、樹脂成分として、同様のフェノール樹脂を６７部（不揮発分：４５％）、さらに表４に示される本発明の電荷輸送物質１５部を溶解し４時間攪拌して保護層用塗料とした。
【０１８３】
この塗料を実施例１と同様にして感光層上に塗工し保護層を施し、実施例１と同様にして評価した。結果を同様に表４に示す。
【０１８４】
（実施例２６〜３０）
実施例１と同様のフェノール樹脂を６７部（不揮発分：４５％）、さらに表４に示される本発明の電荷輸送物質２１部とエタノール８２部を溶解し４時間攪拌して保護層用塗料とした。
【０１８５】
この塗料を実施例１と同様にして感光層上に塗工し保護層を施し、実施例１と同様にして評価した。結果を同様に表４に示す。
【０１８６】
（実施例３１）
電荷輸送層までを実施例１と同様にして作製した。
【０１８７】
次に、保護層として、実施例１で使用したフェノール樹脂に代えて、群栄化学工業（株）製レゾール型硬化性フェノール樹脂（商品名：ＰＬ−２２１１）４２部（不揮発分：５８％）を使用し、さらにヒドロキシアルキル基を有する電荷輸送物質として前記化合物Ｎｏ．１−２３を１５部溶解し保護層用塗料とした。
【０１８８】
この塗料を用いて、先の電荷輸送層上に浸漬塗布法により膜を形成した後、１４５℃で１時間熱風乾燥し膜厚が３μｍの保護層を形成した。保護層塗料の分散性は良好で、作製された保護層はムラのない均一な膜であった。得られた電子写真感光体を実施例１と同様にして評価を行った。結果を同様に表４に示す。
【０１８９】
（実施例３２〜３５）
実施例３１において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．１−２３）の代わりに、表４に示される本発明の電荷輸送物質に代えた以外は、実施例３１と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０１９０】
（実施例３６〜３９）
実施例３１と同様のフェノール樹脂を５２部（不揮発分：５８％）、さらに表４に示される本発明の電荷輸送物質２１部とエタノール８２部を溶解し４時間攪拌して保護層用塗料とした。
【０１９１】
この塗料を実施例１と同様にして感光層上に塗工し保護層を施し、実施例１と同様にして評価した。結果を同様に表４に示す。
【０１９２】
（実施例４０）
アンチモンドープ酸化スズ超微粒子１００部を前記フッ素原子含有化合物（商品名：ＬＳ−１０９０、信越化学工業（株）製）７部で表面処理した（以下、処理量：７％と表す）処理済み酸化スズ微粒子３５部とエタノール１５０部を、サンドミルにて、６６時間かけて分散を行い、さらに、ポリテトラフルオロエチレン微粒子（平均粒径０．１８μｍ）１８部を加えて、さらに１２時間サンドミルで分散を行った。その後、樹脂成分として、住友デュレズ（株）製硬化性レゾール型フェノール樹脂（商品名：ＰＲ−５３１２３）５４部（不揮発分：４５％）、さらに、本発明の置換基を有してもよいヒドロキシフェニル基を有する電荷輸送物質として前記化合物Ｎｏ．４−１４を１５部溶解し、アセトン３５部で希釈して保護層用塗料とした。
【０１９３】
この塗料を実施例１と同様にして感光層上に塗工し保護層を施し、実施例１と同様にして評価した。結果を同様に表４に示す。
【０１９４】
（実施例４１〜４５）
実施例４０において用いた本発明の電荷輸送物質（化合物Ｎｏ．４−１４）を表４に示される電荷輸送物質に代えた以外は、実施例４０と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０１９５】
（実施例４６〜４８）
実施例４０、４２および４４において、前記フッ素原子含有化合物で表面処理した（処理量：７％）アンチモンドープ酸化スズ微粒子を２０部に減らし、代わりにメチルハイドロジェンシリコーン（商品名：ＫＦ９９、信越化学工業（株）製）で処理した（処理量：２０％）アンチモンドープ酸化スズ微粒子１５部を添加、分散して塗料を作製した以外は、実施例４０、４２および４４と同様にして行った。結果を同様に表４に示す。
【０１９６】
（実施例４９〜５１）
実施例４０、４２および４４において、前記フッ素原子含有化合物で表面処理したアンチモンドープ酸化スズ微粒子に代えて、表面処理を施していないアンチモンドープ酸化スズ微粒子（商品名：Ｔ−１、三菱マテリアル（株）製）を３５部、前記フッ素原子含有化合物（商品名：ＬＳ−１０９０、信越化学工業（株）製）３．５部を添加し分散した以外は、実施例４０、４２および４４と同様にして行った。結果を同様に表４に示す。
【０１９７】
（実施例５２〜５４）
実施例４９〜５１において用いた保護層塗工用塗料に対し、さらにメチルハイドロジェンシリコーン（商品名：ＫＦ９９、信越化学工業（株）製）１．５部を添加し、４時間攪拌して塗料とした以外は、実施例４９〜５１と同様にして行った。結果を同様に表４に示す。
【０１９８】
（実施例５５〜５７）
実施例４０と同様の処理済み酸化スズ微粒子３５部とエタノール１５０部を、サンドミルにて、６６時間かけて分散を行い、その後、樹脂成分として、同様のフェノール樹脂を６７部（不揮発分：４５％）、さらに表４に示される本発明の電荷輸送物質１５部を溶解し、アセトン３５部で希釈して４時間攪拌して保護層用塗料とした。
【０１９９】
この塗料を実施例４０と同様に感光層上に塗工し保護層を施し、実施例４０と同様にして評価した。結果を同様に表４に示す。
【０２００】
（実施例５８〜６４）
電荷輸送層までを実施例４０と同様にして作製した。
【０２０１】
実施例４０と同様のフェノール樹脂を６７部（不揮発分：４５％）に、表４に示される本発明の電荷輸送物質２１部とエタノール５８部とアセトン２４部加え溶解し、４時間攪拌して保護層用塗料とした。
【０２０２】
この塗料を実施例４０と同様に電荷輸送層上に浸漬塗布法により、膜を形成した後、１４５℃で１時間熱風乾燥し、膜厚が３μｍの保護層を形成した。実施例４０と同様にして評価した。結果を同様に表４に示す。
【０２０３】
（実施例６５）
電荷輸送層までを実施例４０と同様にして作製した。
【０２０４】
次に、保護層として、実施例４０で使用したフェノール樹脂に代えて、群栄化学工業（株）製硬化性レゾール型フェノール樹脂（商品名：ＰＬ−２２１１）４２部（不揮発分：５８％）を使用し、さらに、本発明の電荷輸送物質として前記化合物Ｎｏ．４−４４を１５部溶解し保護層用塗料とした。
【０２０５】
この塗料を用いて、先の電荷輸送層上に浸漬塗布法により、膜を形成した後、１４５℃で１時間熱風乾燥して、膜厚が３μｍの保護層を形成した。保護層塗料の分散性は良好で、作製された保護層はムラのない均一な膜であった。得られた電子写真感光体を実施例４０と同様にして評価を行った。結果を同様に表４に示す。
【０２０６】
（実施例６６〜６８）
実施例６５において用いた本発明の電荷輸送物質（化合物Ｎｏ．４−４４）を表４に示される本発明の電荷輸送物質に代えた以外は、実施例６５と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０２０７】
（実施例６９〜７４）
実施例６５と同様のフェノール樹脂を５２部（不揮発分：５８％）、さらに表４に示される本発明の電荷輸送物質２１部とエタノール５８部とアセトン２４部加え溶解し、４時間攪拌して保護層用塗料とした。
【０２０８】
この塗料を実施例４０と同様に電荷輸送層上に浸漬塗布法により、膜を形成した後、１４５℃で１時間熱風乾燥し、膜厚が３μｍの保護層を形成し、実施例１と同様にして評価した。結果を同様に表４に示す。
【０２０９】
（実施例７５〜８１）
実施例１において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．１−２３）の代わりに、表４に示される電荷輸送物質に代えた以外は、実施例１と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０２１０】
（実施例８２〜８８）
実施例２６において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．１−２３）の代わりに、表４に示される電荷輸送物質に代えた以外は、実施例２６と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０２１１】
（実施例８９〜９２）
実施例４０において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．４−１４）の代わりに、表４に示される電荷輸送物質に代えた以外は、実施例４０と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０２１２】
（実施例９３〜９６）
実施例５８において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．４−６）の代わりに、表４に示される電荷輸送物質に代えた以外は、実施例５８と同様にして電子写真感光体などを作製し、評価した。結果を同様に表４に示す。
【０２１３】
【表４】

【０２１４】
【表５】

【０２１５】
【表６】

【０２１６】
【表７】

【０２１７】
（比較例１）
電荷輸送層まで実施例１と同様にして作製した。
【０２１８】
次に、保護層として、実施例１で使用したのと同様の住友デュレズ（株）製レゾール型硬化性フェノール樹脂（商品名：ＰＲ−５３１２３）を希釈して塗料とし、浸漬塗布法により、膜を形成した。その後、１４５℃で１時間熱風乾燥し、膜厚が３μｍの保護層を形成し、電子写真感光体などを作製し、評価した。結果を同様に表５に示す。
【０２１９】
（比較例２）
電荷輸送層まで実施例１と同様にして作製した。
【０２２０】
次に、保護層として、実施例３１で使用したのと同様の群栄化学工業（株）製レゾール型硬化性フェノール樹脂（商品名：ＰＬ−２２１１）を希釈して塗料とし、浸漬塗布法により、膜を形成した。その後、１４５℃で１時間熱風乾燥し、膜厚が３μｍの保護層を形成し、電子写真感光体などを作製し、評価した。結果を同様に表５に示す。
【０２２１】
（比較例３〜１０）
電荷輸送層まで実施例１と同様にして作製した。
【０２２２】
樹脂成分として、実施例１と同様の住友デュレズ（株）製レゾール型硬化性フェノール樹脂（商品名：ＰＲ−５３１２３）６７部（不揮発分：４５％）を用い、さらに実施例１において用いたヒドロキシアルキル基を有する電荷輸送物質（化合物Ｎｏ．１−２３）の代わりに、下記式で示される比較化合物１〜８に代えた２１部を１，４−ジオキサン４００部とＴＨＦ１８０部に溶解し、４時間攪拌して保護層用塗料とした。
【外６５】

【０２２３】
この塗料を用いて、先の電荷輸送層上にスプレー塗布法により、膜を形成した後、１４５℃で１時間熱風乾燥し、膜厚が３μｍの保護層を形成し、同様に評価した。結果を同様に表５に示す。
【０２２４】
（比較例１１、１２）
実施例１における保護層の代わりに、実施例１で用いた処理済み酸化スズ微粒子３５部と１，４−ジオキサン１５０部を、サンドミルにて６６時間かけて分散を行い、さらにポリテトラフルオロエチレン微粒子（平均粒径０．１８μｍ）１８部を加えて、さらに１２時間サンドミルで分散を行った。その後、樹脂成分として硬化性フェノール樹脂の代わりにポリメタクリル酸メチル（商品名：Ｊ−８９９、星光化学工業社製）２４部を溶解し、さらに表５に示される本発明の電荷輸送物質を１５部溶解し、さらに１時間サンドミルで分散を行い、１，４−ジオキサン７００部とＴＨＦ３７０部で希釈して保護層用塗料とした。
【０２２５】
この塗料を用いて、電荷輸送層上にスプレー塗布法により、膜を形成した後、１００℃で３０分間熱風乾燥し、膜厚が３μｍの保護層を形成した。実施例１と同様にして評価した。結果を同様に表５に示す。
【０２２６】
（比較例１３）
実施例１において、保護層を塗布しなかった以外は、実施例１と同様にして行った。結果を同様に表５に示す。
【０２２７】
【表８】

【０２２８】
表４および表５に示すように、本発明の保護層を有する電子写真感光体を用いることにより、保護層を施したことに伴う感度の低下や、残留電位の上昇が小さく、高転写効率であり、さらに膜強度を保ち、耐削れ性を維持し、高耐久、高安定である。
【０２２９】
また、本発明による保護層は体積抵抗率が十分高抵抗であるため、形成された静電潜像の流れが生じることなく、鮮明で良好な画像を得ることができた。一方、比較例３〜１２に示される保護層は、体積抵抗率が低いため静電潜像の流れによる画質低下が見られた。
【０２３０】
【発明の効果】
以上説明してきたように、本発明により、保護層を施した電子写真感光体の感度低下と残留電位の上昇が小さく、さらに高転写効率、高耐久、高安定で、良好な画像を得ることができる電子写真感光体を提供することが可能となった。
【０２３１】
また、該電子写真感光体を有するプロセスカートリッジおよび電子写真装置において同様に顕著な効果を奏することができた。
【図面の簡単な説明】
【図１】本発明の電子写真感光体の層構成を示す図である。
【図２】本発明の電子写真感光体を有するプロセスカートリッジを用いる電子写真装置の概略構成の例を示す図である。
【符号の説明】
１ 保護層
２ 電荷輸送層
３ 電荷発生層
４ 導電性支持体
５ 結着層
６ 下引き層
１１ 電子写真感光体
１２ 軸
１３ 帯電手段
１４ 露光光
１５ 現像手段
１６ 転写手段
１７ 転写材
１８ 定着手段
１９ クリーニング手段
２０ 前露光光
２１ プロセスカートリッジ容器
２２ 案内手段[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an electrophotographic photosensitive member, a process cartridge, and an electrophotographic apparatus, and more specifically, an electrophotographic photosensitive member containing a specific resin and a specific charge transport material in a protective layer, a process cartridge having the electrophotographic photosensitive member, and The present invention relates to an electrophotographic apparatus.
[0002]
[Prior art]
In recent years, research and development of electrophotographic photoreceptors using organic photoconductive materials have been actively conducted due to advantages such as high safety, excellent productivity, and low cost, and many proposals have been made so far. It has been put into practical use.
[0003]
However, an electrophotographic photoreceptor mainly composed of a photoconductive polymer typified by poly-N-vinylcarbazole and a charge transfer complex formed from 2,4,7-trinitrofluorene or the like is sensitive and durable. It was not always satisfactory in terms of characteristics and residual potential.
[0004]
On the other hand, the function-separated type electrophotographic photosensitive member in which the charge generation function and the charge transporting function are assigned to different substances significantly improves the sensitivity and durability that have been regarded as the disadvantages of conventional organic electrophotographic photosensitive members. Brought. In addition, the function-separated type electrophotographic photosensitive member has an advantage that a material selection range of each of the charge generation material and the charge transport material is wide and an electrophotographic photosensitive member having arbitrary characteristics can be relatively easily manufactured. Yes.
[0005]
Known charge generating materials include various azo pigments, polycyclic quinone pigments, phthalocyanine pigments, cyanine dyes, squaric acid dyes, pyrylium salt dyes, and the like.
[0006]
Known charge transport materials include pyrazoline compounds, hydrazone compounds, and triphenylamine compounds.
[0007]
By the way, with the recent improvement in image quality, high speed and high durability, organic electrophotographic photoreceptors are also required to have further improved mechanical durability.
[0008]
In recent years, printers, copiers, facsimiles, and the like using electrophotographic photoreceptors have been used in a wide variety of fields, and it has been more strictly required to always provide stable images even in more various environments. Therefore, there is a high possibility of being exposed to chemical, electrical, and mechanical impacts on the surface characteristics of the photosensitive layer, and the requirements for the surface layer are becoming strict.
[0009]
The electrophotographic photosensitive member is required to have durability against the above-described electrical and mechanical external forces that are directly applied. Specifically, durability against surface abrasion and scratches due to rubbing and deterioration of the surface layer due to adhesion of active substances such as ozone and NOx generated during charging is required.
[0010]
Furthermore, the electrophotographic photosensitive member is repeatedly applied with means such as charging, exposure, development, transfer, cleaning, and charge removal. The electrostatic latent image formed by charging and exposure becomes a toner image by a fine particle developer called toner. Further, the toner image is transferred onto a transfer material such as paper by a transfer unit, but not all the toner is transferred, and a part of the toner image remains on the electrophotographic photosensitive member.
[0011]
If the amount of the residual toner is large, the image on the transfer material becomes a so-called bulging shape in which further transfer failure occurs, and the uniformity of the image is not only lost, but also the toner is fused or filmed to the electrophotographic photosensitive member. The problem of occurrence occurs. For these problems, it is required to improve the releasability of the surface layer of the electrophotographic photosensitive member.
[0012]
In order to satisfy the above-described requirements for the electrophotographic photoreceptor, attempts have been made to provide various protective layers. Among them, many protective layers mainly composed of a resin have been proposed. For example, Japanese Patent Application Laid-Open No. 57-30846 discloses a protective layer in which volume resistance can be controlled by adding a metal oxide as a conductive powder to a resin.
[0013]
Japanese Patent Application Laid-Open No. 5-181299 discloses the use of a curable phenol resin as a protective layer resin.
[0014]
Dispersing the metal oxide in the protective layer of the electrophotographic photosensitive member is to control the volume resistance of the protective layer itself and to prevent an increase in the residual potential in the electrophotographic photosensitive member due to repetition of the electrophotographic process. On the other hand, an appropriate volume resistance value of a protective layer for an electrophotographic photoreceptor is 10 ¹⁰ -10 ¹⁵ It is known to be Ω · cm. However, in the volume resistance value in the above range, the volume resistance of the protective layer is easily affected by ion conduction, and therefore the volume resistance tends to change greatly due to environmental changes. In particular, when the metal oxide is dispersed in the film, the water resistance of the surface of the metal oxide is high, so that the volume resistance of the protective layer is reduced in all environments and when the electrophotographic process is repeated. It has been very difficult to keep the above in the above range.
[0015]
In particular, in a high-humidity environment, the volume resistance of the electrophotographic photosensitive member surface is decreased by allowing the volume resistance to gradually decrease when left standing or active substances such as ozone and NOx generated by charging repeatedly adhere to the surface. And the toner releasability from the surface layer is reduced, so that defects such as so-called image flow and image blur occur, and image uniformity is insufficient.
[0016]
In general, when the particles are dispersed in the protective layer, the particle diameter of the particles is preferably smaller than the wavelength of the incident light, that is, 0.3 μm or less in order to prevent scattering of incident light by the dispersed particles. . However, the metal oxide particles usually tend to aggregate in the resin solution, and are difficult to uniformly disperse. Even if dispersed once, secondary aggregation and precipitation are likely to occur, so fine particles having a particle size of 0.3 μm or less are good. It was very difficult to produce a dispersion film stably. Further, it is preferable to disperse fine particles having a small particle size (primary particle size of 0.1 μm or less) from the viewpoint of improving transparency and conductivity uniformity, but the dispersibility and dispersion stability of such fine particles are further deteriorated. There was a trend.
[0017]
In order to compensate for the above drawbacks, for example, JP-A-1-306857 discloses a fluorine-containing silane coupling agent, a titanate coupling agent or C ₇ F ₁₅ A protective layer to which a compound such as NCO is added is disclosed in Japanese Patent Application Laid-Open No. 62-295066 as a metal fine powder or metal oxide fine powder whose dispersibility and moisture resistance are improved by water-repellent treatment in a binder resin. JP-A-2-50167 discloses a metal oxide fine powder surface-treated with a titanate coupling agent, a fluorine-containing silane coupling agent and acetoalkoxyaluminum diisopropylate in a binder resin. A dispersed protective layer is disclosed.
[0018]
Examples of the charge transport material having a hydroxy group such as the charge transport material used in the present invention in the protective layer are disclosed in JP-A-10-228126 and JP-A-10-228127. Yes.
[0019]
However, these protective layers are still satisfying as protective layers for various impacts on the surface, durability against the occurrence of wear and scratches, releasability, etc. in order to meet the recent demand for high durability and high image quality. At present, no electrophotographic characteristics that can be obtained have been obtained.
[0020]
[Problems to be solved by the invention]
The object of the present invention is to effectively prevent a decrease in sensitivity and an increase in residual potential, which are problems by applying a protective layer to the electrophotographic photosensitive member, and has excellent releasability and generation of wear and scratches. It is an object of the present invention to provide an electrophotographic photosensitive member having a surface property with excellent durability and maintaining high image quality, a process cartridge and an electrophotographic apparatus having the electrophotographic photosensitive member.
[0021]
[Means for Solving the Problems]
That is, the present invention provides an electrophotographic photosensitive member having a photosensitive layer and a protective layer on a support, wherein the protective layer contains a curable phenol resin, and has a hydroxyalkyl group, a hydroxyalkoxy group, and a substituent. An electrophotographic photoreceptor comprising a charge transport material having at least one group selected from the group consisting of hydroxyphenyl groups.
[0022]
Further, the present invention is characterized in that the electrophotographic photosensitive member and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and are detachable from the main body of the electrophotographic apparatus. Process cartridge.
[0023]
Furthermore, the present invention is an electrophotographic apparatus comprising the electrophotographic photosensitive member, a charging unit, an exposure unit, a developing unit, and a transfer unit.
[0024]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, embodiments of the present invention will be described in detail.
[0025]
As a result of intensive studies, the present inventors have found that the above problems can be solved by using an electrophotographic photosensitive member having a protective layer formed by combining a specific binder resin and a specific compound. It was.
[0026]
That is, the present invention has the effect of quickly dissipating charges accumulated at the interface between the charge transport layer and the protective layer, etc., with respect to the curable phenol resin layer obtained mainly by the condensation reaction of phenols and aldehydes. And an electrophotographic photosensitive member capable of maintaining the sensitivity of the electrophotographic photosensitive member having the protective layer and reducing the residual potential without impairing the strength of the protective layer by containing the charge transporting substance together. Is.
[0027]
First, the curable phenol resin which is a binder resin used for the protective layer in the present invention is a resin generally obtained by a reaction between phenols and formaldehyde. There are two types of phenolic resins: a resole type obtained by reacting with phenol with an excess of formaldehyde and reacting with an alkali catalyst, and a novolak obtained by reacting with phenol and an excess of phenol with formaldehyde. Divided into molds.
[0028]
The resol type is also soluble in alcohol and ketone solvents, and is three-dimensionally crosslinked and polymerized by heating to form a cured product. On the other hand, the novolak type generally does not cure even when heated as it is, but forms a cured product by adding a formaldehyde source such as paraformaldehyde or hexamethylenetetramine and heating.
[0029]
In general, the resol type is used as a varnish for paints, adhesives, cast products and laminates, and the novolak type is mainly used as a molding material or a binder.
[0030]
The phenolic resin used as the binder resin in the present invention can be used in either the above-mentioned resol type or novolak type, but it is a resol type from the viewpoint of curing without adding a curing agent and operability as a paint. Is preferably used.
[0031]
In the present invention, these phenol resins can be used singly or in combination of two or more, and a resol type and a novolac type can also be mixed and used.
[0032]
As the phenol resin used in the present invention, any known phenol resin may be used.
[0033]
The protective layer of the present invention is formed by applying a coating obtained by dissolving or diluting a curable phenolic resin with a solvent or the like onto a photosensitive layer, and a polymerization reaction occurs after coating to form a cured layer. As a form of polymerization, it proceeds by addition and condensation reaction with heat, and after coating the protective layer, it is heated to cause a polymerization reaction to produce a polymer hardened layer.
[0034]
Further, the charge transport material having a hydroxyalkyl group, a hydroxyalkoxy group or a hydroxyphenyl group which may have a substituent according to the present invention has a good compatibility with the curable phenol resin and is a uniformly dispersed protective layer Although a film can be easily produced, a triphenylamine derivative is preferable in order to further improve the compatibility.
[0035]
Examples of the substituent that the hydroxyphenyl group may have include halogen atoms such as fluorine, chlorine, bromine and iodine, and optionally substituted methyl, ethyl, propyl and butyl groups. Alkyl groups, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group which may have a substituent, aryl groups such as phenyl group, naphthyl group, anthryl group and pyrenyl group which may have a substituent Or heterocyclic groups such as pyridyl group, thienyl group, furyl group and quinolyl group which may have a substituent.
[0036]
First, among the charge transport materials used in the present invention, a charge transport material having a hydroxyalkyl group or a hydroxyalkoxy group is a compound having a specific structure represented by any one of the following formulas (1) to (3). Preferably there is.
[Outside 10]

[0037]
Where R ₁₁ , R ₁₂ And R ₁₃ Represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and α, β and γ each have a halogen atom as a substituent, an alkyl group which may have a substituent, or a substituent. Represents an alkoxy group that may be substituted, an aryl group that may have a substituent, a benzene ring that may have one or more heterocyclic groups that may have a substituent, and a1, b1, and c1 are 1 Or 0, and m1 and n1 are 0 or 1.
[Outside 11]

[0038]
Where R ₂₁ , R ₂₂ And R ₂₃ Each represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and δ and ε each have a halogen atom as a substituent, an alkyl group which may have a substituent, or a substituent. Represents an alkoxy group which may have a substituent, an aryl group which may have a substituent, a benzene ring which may have one or more heterocyclic groups which may have a substituent, and a2, b2 and c2 are 1 or 0 It is. m2, n2 and p2 are 0 or 1, and all do not become 0 at the same time. τ and υ each have a halogen atom as a substituent, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, and a substituent. Represents a benzene ring which may have one or more heterocyclic groups. In addition, τ and υ may form a ring jointly via a substituent.
[Outside 12]

[0039]
Where R ₃₁ , R ₃₂ , R ₃₃ And R ₃₄ Each represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and ζ, η, θ and ι are each a halogen atom as a substituent, an alkyl group which may have a substituent, or a substituent. Represents a benzene ring which may have one or more heterocyclic groups which may have an alkoxy group, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, a3, b3, c3 And d3 is 1 or 0, and m3, n3, and p3 are 0 or 1. φ and χ each have a halogen atom as a substituent, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, and a substituent. Represents a benzene ring which may have one or more heterocyclic groups. Φ and χ may form a ring jointly via a substituent.
[0040]
When a1, b1 and c1 in the above formula (1), a2, b2 and c2 in the above formula (2), and a3, b3, c3 and d3 in the above formula (3) are 0, the above formula ( The charge transport materials having the structures represented by 1) to (3) are charge transport materials having a hydroxyalkyl group, and when 1, they are charge transport materials having a hydroxyalkoxy group.
[0041]
The structures of the substituents in the above formulas (1) to (3) will be described in detail below.
[0042]
Where R ₁₁ ~ R ₁₃ , R ₂₁ ~ R ₂₃ , R ₃₁ ~ R ₃₄ Represents a divalent hydrocarbon group such as a methylene group, an ethylene group, a propylene group and a butylene, each of which may be branched from 1 to 8 carbon atoms. In the formula, the benzene ring represented by α, β, γ, δ, ε, ζ, η, θ and ι may have a halogen atom such as fluorine, chlorine, bromine and iodine, and a substituent. Alkyl groups such as methyl group, ethyl group, propyl group and butyl group which may have, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group which may have substituents, and substituents An aryl group such as a phenyl group, a naphthyl group, an anthryl group and a pyrenyl group which may be substituted, and a heterocyclic group such as a pyridyl group, a thienyl group, a furyl group and a quinolyl group which may have a substituent are shown.
[0043]
In the formula, a benzene ring represented by τ, υ, φ and χ may have a halogen atom such as fluorine, chlorine, bromine and iodine, a methyl group which may have a substituent, or an ethyl group Alkyl groups such as propyl group and butyl group, methoxy group which may have a substituent, alkoxy group such as ethoxy group, propoxy group and butoxy group, phenyl group which may have a substituent, naphthyl group, anthryl And aryl groups such as a pyrenyl group, and optionally substituted heterocyclic groups such as a pyridyl group, a thienyl group, a furyl group, and a quinolyl group. Note that τ and υ, and φ and χ may form a cyclic structure such as a fluorene skeleton or a dihydrophenanthrene skeleton via a biphenyl skeleton in which they are bonded together.
[0044]
Examples of the substituent that may be present in the formulas (1) to (3) include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aralkyl group such as a benzyl group, a phenethyl group, and a naphthylmethyl group; Groups, naphthyl groups, anthryl groups, pyrenyl groups, fluorenyl groups, carbazolyl groups, dibenzofuryl groups, dibenzothiophenyl groups and other aromatic ring groups; methoxy groups, ethoxy groups, propoxy groups, etc. alkoxy groups, phenoxy groups, naphthoxy groups, etc. A halogen atom such as fluorine, chlorine, bromine and iodine; a nitro group or a cyano group.
[0045]
Specific examples of the charge transport material having a hydroxyalkyl group and the charge transport material having a hydroxyalkoxy group used in the present invention are shown below, but the charge transport material of the present invention is not limited thereto. .
[Outside 13]

[0046]
[Outside 14]

[0047]
[Outside 15]

[0048]
[Outside 16]

[0049]
[Outside 17]

[0050]
[Outside 18]

[0051]
[Outside 19]

[0052]
[Outside 20]

[0053]
[Outside 21]

[0054]
[Outside 22]

[0055]
[Outside 23]

[0056]
[Outside 24]

[0057]
[Outside 25]

[0058]
[Outside 26]

[0059]
[Outside 27]

[0060]
[Outside 28]

[0061]
[Outside 29]

[0062]
[Outside 30]

[0063]
[Outside 31]

[0064]
[Outside 32]

[0065]
[Outside 33]

[0066]
[Outside 34]

[0067]
[Outside 35]

[0068]
Among these, among the charge transport materials having the structure represented by the above formula (1), (1-3), (1-5), (1-21), (1-22), (1-23) ), (1-28), (1-40), (1-41), (1-44), (1-53), (1-54), (1-55), (1-56), (1-57), (1-58), (1-59), (1-60) and (1-61) are preferred, and in particular, (1-5), (1-22), (1-23) ), (1-41), (1-54) and (1-59) are more preferred.
[0069]
Among the charge transport materials having the structure represented by the above formula (2), (2-7), (2-20), (2-29), (2-30) and (2-32) are preferable, In particular, (2-20) and (2-30) are more preferable.
[0070]
Among the charge transport materials having the structure represented by the above formula (3), (3-7), (3-9), (3-10), (3-17), (3-22) and (3 −23) is preferable, and (3-10) and (3-23) are particularly preferable.
[0071]
Among the charge transport materials used in the present invention, the charge transport material having a hydroxyphenyl group which may have a substituent is a specific structure represented by any of the following formulas (4) to (6). It is preferable that it is a compound which has this.
[Outside 36]

[0072]
Where R ₄₁ Represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and R ₄₂ Represents a hydrogen atom, an alkyl group which may have a substituent, an aralkyl group which may have a substituent, or a phenyl group which may have a substituent. Ar ₄₁ And Ar ₄₂ Represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. Ar ₄₃ Represents an arylene group which may have a substituent and a heterocyclic group which may have a divalent substituent. m4 and n4 are each 0 or 1. However, when n4 = 0, m4 = 0. κ and λ each have a halogen atom as a substituent, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, and a substituent. Represents a benzene ring which may have one or more heterocyclic groups.
[Outside 37]

[0073]
Where R ₅₁ Represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ₅₁ And Ar ₅₂ Represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. μ and ν each have a halogen atom as a substituent, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, and a substituent. Represents a benzene ring which may have one or more heterocyclic groups. Μ and ν may form a ring jointly via a substituent. m5 is 0 or 1.
[Outside 38]

[0074]
Where R ₆₁ And R ₆₂ Each represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ₆₁ Represents an alkyl group which may have a substituent, an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent. ξ, π, ρ and σ are each a halogen atom as a substituent, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, or a substituent Represents a benzene ring which may have one or more heterocyclic groups which may have In addition, ξ and π, and ρ and σ may form a ring jointly through a substituent. m6 and n6 are 0 or 1, respectively.
[0075]
The structures of the substituents in the general formulas (4) to (6) will be described in detail below.
[0076]
Where R ₄₁ , R ₅₁ , R ₆₁ And R ₆₂ Each represents a divalent hydrocarbon group such as a methylene group, an ethylene group, a propylene group and a butylene group, which may be branched from 1 to 8 carbon atoms. R ₄₂ Is a hydrogen atom, an alkyl group such as an optionally substituted methyl group, an ethyl group, a propyl group and a butyl group, an optionally substituted benzyl group, an aralkyl group such as a phenethyl group and a naphthylmethyl group, Or a phenyl group is shown.
[0077]
In the formula, the benzene ring represented by κ, λ, μ, ν, ξ, π, ρ and σ may have a halogen atom such as fluorine, chlorine, bromine and iodine, or a substituent. Alkyl groups such as methyl group, ethyl group, propyl group and butyl group, alkoxy groups such as methoxy group, ethoxy group, propoxy group and butoxy group which may have a substituent, and substituents A preferable aryl group such as phenyl group, naphthyl group, anthryl group and pyrenyl group, or a heterocyclic group such as pyridyl group, thienyl group, furyl group and quinolyl group which may have a substituent.
[0078]
Further, μ and ν, ξ and π, and ρ and σ may form a cyclic structure such as a fluorene skeleton or a dihydrophenanthrene skeleton through a substituent or the like to which they are bonded together.
[0079]
Ar ₄₁ , Ar ₄₂ , Ar ₅₁ , Ar ₅₂ And Ar ₆₁ Represents an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group which may have a substituent, an aralkyl group such as a benzyl group, a phenethyl group and a naphthylmethyl group which may have a substituent, and a substituent. An aryl group such as an optionally substituted phenyl group, naphthyl group, anthryl group and pyrenyl group, or a heterocyclic group such as a pyridyl group, thienyl group, furyl group and quinolyl group which may have a substituent is shown.
[0080]
Ar ₄₃ Represents a divalent heterocyclic group such as an arylene group such as a phenylene group, a naphthylene group, an anthrylene group, and a pyrenylene group, a pyridylene group, or a thienylene group that may have a substituent.
[0081]
Examples of the substituent that may be present in the formulas (4) to (6) include an alkyl group such as a methyl group, an ethyl group, a propyl group, and a butyl group; an aralkyl group such as a benzyl group, a phenethyl group, and a naphthylmethyl group; Groups, naphthyl groups, anthryl groups, pyrenyl groups, fluorenyl groups, carbazolyl groups, dibenzofuryl groups, dibenzothiophenyl groups, and other aromatic ring groups; methoxy groups, ethoxy groups, propoxy groups, and other alkoxy groups; phenoxy groups, naphthoxy groups, etc. Aryloxy groups; halogen atoms such as fluorine, chlorine, bromine and iodine; nitro groups and cyano groups.
[0082]
Specific examples of the charge transport material having a hydroxyphenyl group which may have a substituent used in the present invention are shown below, but the charge transport material of the present invention is not limited thereto.
[Outside 39]

[0083]
[Outside 40]

[0084]
[Outside 41]

[0085]
[Outside 42]

[0086]
[Outside 43]

[0087]
[Outside 44]

[0088]
[Outside 45]

[0089]
[Outside 46]

[0090]
[Outside 47]

[0091]
[Outside 48]

[0092]
[Outside 49]

[0093]
[Outside 50]

[0094]
[Outside 51]

[0095]
[Outside 52]

[0096]
[Outside 53]

[0097]
[Outside 54]

[0098]
[Outside 55]

[0099]
[Outside 56]

[0100]
[Outside 57]

[0101]
[Outside 58]

[0102]
[Outside 59]

[0103]
[Outside 60]

[0104]
Among these, among the charge transport materials having the structure represented by the above formula (4), (4-6), (4-8), (4-13), (4-14) and (4-55) ) Is preferred, and (4-14) and (4-55) are more preferred.
[0105]
Among the charge transport materials having the structure represented by the above formula (5), (5-13), (5-14), (5-16), (5-18), (5-19), (5 -28) and (5-29) are preferred, with (5-29) being more preferred.
[0106]
Among the charge transport materials having the structure represented by the above formula (6), (6-10), (6-11), (6-12), (6-14), (6-15), (6 −18), (6-19) and (6-20) are preferable, and (6-14), (6-18), (6-19) and (6-20) are more preferable.
[0107]
From the viewpoint of the strength of the protective layer, a charge transporting substance having a hydroxyphenyl group that may be cured together with a phenol resin that is a binder resin of the protective layer and may have a substituent that crosslinks three-dimensionally is more preferable, From the viewpoint of lowering the sensitivity and increasing the residual potential, a charge transport material having a hydroxyalkyl group and a charge transport material having a hydroxyalkoxy group are more preferred because they are less susceptible to humidity.
[0108]
Furthermore, in order to further improve the compatibility between the charge transport material and the curable phenol resin, R in the above formulas (1) to (6) is used. ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ , R ₂₃ , R ₃₁ , R ₃₂ , R ₃₃ , R ₃₄ , R ₄₁ , R ₅₁ , R ₆₁ And R ₆₂ The divalent hydrocarbon group represented by is more preferably 4 or less carbon atoms, and the number of hydroxyalkyl groups, hydroxyalkoxy groups, and optionally substituted hydroxyphenyl groups is 2 or more. It is more preferable.
[0109]
In addition, the charge transport material used in the present invention is formed by uniformly dissolving or dispersing in a coating material for producing the protective layer and applying it. The mixing ratio of the charge transporting material and the curable phenolic resin of the present invention is preferably a mass ratio of charge transporting material / curable phenolic resin = 0.1 / 10-20 / 10, particularly 0.5 / 10-10. / 10 is preferred. If the amount of the charge transport material is too small relative to the curable phenol resin, the effect of lowering the residual potential is reduced, and if it is too much, the strength of the protective layer may be weakened.
[0110]
In the electrophotographic photosensitive member having the protective layer described above, by further containing conductive fine particles, the residual potential of the electrophotographic photosensitive member can be lowered at a higher level.
[0111]
Examples of the conductive fine particles include metals, metal oxides, and carbon black. Examples of the metal include aluminum, zinc, copper, chromium, nickel, silver, and stainless steel, or those obtained by depositing these metals on the surface of plastic particles. Examples of the metal oxide include zinc oxide, titanium oxide, tin oxide, antimony oxide, indium oxide, bismuth oxide, tin-doped indium oxide, antimony and tantalum-doped tin oxide, and antimony-doped zirconium oxide. . These can be used alone or in combination of two or more. When two or more types are used in combination, they may be simply mixed, or may be in the form of a solid solution or fusion.
[0112]
In the present invention, among the various conductive fine particles described above, it is particularly preferable to use a metal oxide from the viewpoint of transparency. Further, among these metal oxides, it is particularly preferable to use tin oxide from the viewpoints of transparency, dispersibility, resistance controllability, and the like. The tin oxide used here may be surface-treated for the purpose of improving dispersibility and liquid stability, and may be doped with antimony or tantalum for the purpose of improving resistance controllability.
[0113]
The volume average particle size of the conductive fine particles used in the present invention is preferably 0.3 μm or less, particularly preferably 0.1 μm or less, from the viewpoint of the transparency of the protective layer.
[0114]
The protective layer used in the present invention does not essentially transfer charges as a resistor, but an electrophotographic photosensitive member provided with a protective layer by transferring charges using a charge transport material contained in the protective layer. The sensitivity is maintained and the residual potential is lowered. Therefore, it is not necessary to set the volume resistivity as a resistor low, and the volume resistivity is 1 × 10 ¹² By setting it to (Ω · cm) or more, the flow of the formed electrostatic latent image can be suppressed at a high level.
[0115]
The conductive fine particles in the present invention play an auxiliary role in adjusting the volume resistivity of the protective layer and are not necessarily used if not necessary.
[0116]
Since the film strength becomes weaker as the amount of the conductive fine particles increases, it is preferable to reduce the amount of the conductive fine particles within a range in which the volume resistance and the residual potential of the protective layer are acceptable.
[0117]
In the electrophotographic photosensitive member having the protective layer described above, by further containing fluorine atom-containing resin fine particles, the releasability on the surface of the electrophotographic photosensitive member can be improved at a higher level.
[0118]
Examples of the fluorine atom-containing resin fine particles include ethylene tetrafluoride, ethylene trifluoride chloride resin, hexafluoroethylene propylene resin, vinyl fluoride resin, vinylidene fluoride resin, ethylene difluoride dichloride resin, and copolymers thereof. Of these, it is preferable to select one or more types as appropriate, and particularly preferred are tetrafluoroethylene resin and vinylidene fluoride resin. The molecular weight distribution and particle size of the resin particles can be appropriately selected and are not particularly limited.
[0119]
To prevent the fluorine atom-containing resin fine particles from coagulating with the conductive fine particles in the resin solution, a fluorine atom-containing compound is added when the conductive fine particles are dispersed, or the surface of the conductive fine particles is coated. Surface treatment with a fluorine atom-containing compound is preferred.
[0120]
Dispersibility and dispersion stability of conductive fine particles and fluorine atom-containing resin fine particles in resin solution compared to the case without fluorine atom-containing compounds by adding fluorine atom-containing compounds or surface treatment of conductive fine particles Has improved dramatically. Also, secondary particles of dispersed particles are formed by dispersing fluorine atom-containing resin fine particles in a liquid in which conductive fine particles are dispersed by adding a fluorine atom-containing compound or in a liquid in which conductive fine particles are subjected to surface treatment. In addition, a coating liquid having a very stable dispersibility can be obtained over time.
[0121]
Examples of fluorine atom-containing compounds include fluorine-containing silane coupling agents, fluorine-modified silicone oils, and fluorine-based surfactants. Although the example of a preferable compound is given to Table 1-Table 3, this invention is not limited to these compounds.
[0122]
[Table 1]

[0123]
[Table 2]

[0124]
[Table 3]

[0125]
As a surface treatment method for the conductive fine particles, the conductive fine particles and the surface treatment agent are mixed and dispersed in an appropriate solvent, and the surface treatment agent is adhered to the surface of the conductive fine particles. As a dispersion method, a normal dispersion means such as a ball mill or a sand mill can be used. Next, the solvent may be removed from the dispersion and fixed to the surface of the conductive fine particles. Moreover, you may heat-process further after this as needed. Further, a catalyst for promoting the reaction can be added to the treatment liquid. Furthermore, if necessary, the conductive fine particles after the surface treatment can be further pulverized.
[0126]
The ratio of the fluorine atom-containing compound to the conductive fine particles is influenced by the particle diameter, shape, surface area, and the like of the particles, but is preferably 1 to 65% by mass, particularly 1 based on the total mass of the surface-treated conductive fine particles. -50 mass%.
[0127]
Further, in the present invention, in order to obtain a more environmentally stable protective layer, a siloxane compound represented by the following formula is added at the time of dispersing the conductive fine particles, or surface treatment is performed with the siloxane compound represented by the following formula. It is preferable to mix the conductive fine particles.
[Outside 61]

[0128]
In the formula, T is a hydrogen atom or a methyl group, the proportion of hydrogen atoms in all of T is in the range of 0.1 to 50%, and t is an integer of 0 or more.
[0129]
By dispersing the coating solution in which the siloxane compound is dispersed after being dispersed in the binder resin in which the conductive metal oxide fine particles whose surface has been treated is dissolved in a solvent, there is no formation of secondary particles of the dispersed particles, A coating solution that is stable over time and has good dispersibility can be obtained. Further, a protective layer formed from this coating solution has high transparency, and a film having particularly excellent environmental resistance can be obtained.
[0130]
The molecular weight of the siloxane compound represented by the above formula is not particularly limited. However, in the case of surface treatment, it is better that the viscosity is not too high for ease of treatment, and the weight average molecular weight is several hundred to several tens of thousands. The degree is appropriate.
[0131]
There are two surface treatment methods, wet and dry. In the wet treatment, the conductive metal oxide particles are dispersed in a solvent with the siloxane compound represented by the above formula, and the siloxane compound is adhered to the surface of the fine particles. As a dispersion means, a general dispersion means such as a ball mill or a sand mill can be used. Next, this dispersion solution is fixed to the surface of the conductive metal oxide fine particles. In this heat treatment, Si—H bonds in the siloxane are oxidized by hydrogen atoms by oxygen in the air during the heat treatment process, and new siloxane bonds are formed. As a result, siloxane develops to a three-dimensional structure, and the surface of the conductive metal oxide fine particles is covered with this network structure. Thus, the surface treatment is completed by fixing the siloxane compound to the surface of the conductive metal oxide fine particles, but the treated fine particles may be pulverized as necessary.
[0132]
In the dry process, the siloxane compound and the conductive metal oxide fine particles are mixed and kneaded without using a solvent to adhere the siloxane compound to the surface of the fine particles. Thereafter, heat treatment and pulverization are performed in the same manner as the wet treatment to complete the surface treatment.
[0133]
As the solvent for dispersing the coating material of the protective layer, the curable phenol resin is well dissolved, and the charge transporting material of the present invention is also well dissolved. When the fine resin-containing fine particles, the fluorine atom-containing compound, and the siloxane compound are used, a solvent that has good compatibility and processability with them and that does not adversely affect the charge transporting layer in contact with the protective layer coating is preferable.
[0134]
Therefore, solvents include alcohols such as methanol, ethanol and 2-propanol, ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, ethers such as tetrahydrofuran and dioxane, and aromatics such as toluene and xylene. Group hydrocarbons or halogen hydrocarbons such as chlorobenzene and dichloromethane can be used, and these may be used in combination. Among these, the most suitable solvent for the form of the phenol resin is alcohols such as methanol, ethanol and 2-propanol.
[0135]
Conventional charge transport materials are generally insoluble or hardly soluble in alcohol solvents, and it is difficult to uniformly disperse them in general phenol resins, but many of the charge transport materials of the present invention contain alcohols. Since it is soluble in the solvent as a main component, it can be dispersed in a phenol resin paint.
[0136]
As a method for applying the protective layer of the present invention, general coating methods such as a dip coating method, a spray coating method, a spinner coating method, a roller coating method, a Meyer bar coating method and a blade coating method can be used.
[0137]
If the thickness of the protective layer of the present invention is too thin, the durability of the electrophotographic photosensitive member is impaired, and if it is too thick, the residual potential due to the provision of the protective layer increases. Specifically, the range of 0.1 μm to 10 μm is preferable, and the range of 0.5 μm to 7 μm is more preferable.
[0138]
In the present invention, an antioxidant additive may be added to the protective layer for the purpose of preventing deterioration of the surface layer due to adhesion of active substances such as ozone and NOx generated during charging.
[0139]
Next, the photosensitive layer will be described below.
[0140]
The electrophotographic photoreceptor of the present invention preferably has mainly a laminated structure. In the electrophotographic photoreceptor of FIG. 1A, a charge generation layer 3 and a charge transport layer 2 are provided in this order on a support 4, and a protective layer 1 is further provided on the outermost surface. Further, as shown in FIGS. 1B and 1C, a binder layer 5 and an undercoat layer 6 for the purpose of preventing interference fringes may be provided between the support and the charge generation layer.
[0141]
As the support 4, the support itself can be conductive, for example, aluminum, aluminum alloy, stainless steel, etc. In addition, aluminum, aluminum alloy, indium oxide-tin oxide alloy, or the like is coated by vacuum deposition. The support having the formed layer, the plastic, the conductive fine particles (for example, carbon black, tin oxide, titanium oxide and silver particles) impregnated in plastic or paper together with an appropriate binder resin, the conductive binder. Plastic having a resin can be used.
[0142]
Further, a binder layer (adhesive layer) having a barrier function and an adhesive function can be provided between the support and the photosensitive layer. The binder layer is used to improve the adhesion of the photosensitive layer, improve the coatability, protect the support, cover defects on the support, improve the charge injection from the support, and protect against electrical breakdown of the photosensitive layer. It is formed. The binder layer can be formed of casein, polyvinyl alcohol, ethyl cellulose, ethylene-acrylic acid copolymer, polyamide, modified polyamide, polyurethane, gelatin, aluminum oxide, or the like. The film thickness of the binder layer is preferably 5 μm or less, and particularly preferably 0.1 to 3 μm.
[0143]
Examples of the charge generating substance used in the present invention include (1) azo pigments such as monoazo, disazo and trisazo, (2) phthalocyanine pigments such as metal phthalocyanine and nonmetal phthalocyanine, and (3) indigo compounds such as indigo and thioindigo. Pigments, (4) perylene pigments such as perylene anhydride and perylene imide, (5) polycyclic quinone pigments such as anthraquinone and pyrenequinone, (6) squarylium dyes, (7) pyrylium salts and thiapyrylium salts ( 8) Triphenylmethane dyes, (9) inorganic substances such as selenium, selenium-tellurium and amorphous silicon, (10) quinacridone pigments, (11) azulenium salt pigments, (12) cyanine dyes, (13) xanthene dyes, 14) Quinone imine dye, (15) Su Lil dyes, and (16) cadmium sulfide and (17) zinc oxide.
[0144]
Examples of the binder resin used for the charge generation layer include polycarbonate resin, polyester resin, polyarylate resin, butyral resin, polystyrene resin, polyvinyl acetal resin, diallyl phthalate resin, acrylic resin, methacrylic resin, vinyl acetate resin, phenol resin, Examples thereof include, but are not limited to, silicone resins, polysulfone resins, styrene-butadiene copolymer resins, alkyd resins, epoxy resins, urea resins, and vinyl chloride-vinyl acetate copolymer resins. These can be used alone or as a mixture or as a copolymer polymer.
[0145]
The solvent used for the charge generation layer coating is selected from the solubility and dispersion stability of the resin used and the charge generation material, but examples of the organic solvent include alcohols, sulfoxides, ketones, ethers, esters, Aliphatic halogenated hydrocarbons or aromatic compounds can be used.
[0146]
The charge generation layer 3 is well dispersed by a method such as a homogenizer, ultrasonic wave, ball mill, sand mill, attritor or roll mill together with the above-mentioned charge generation material in an amount of 0.3 to 4 times the binder resin and solvent. It is formed by coating and drying. The thickness is preferably 5 μm or less, and particularly preferably in the range of 0.01 to 1 μm.
[0147]
In addition, various sensitizers, antioxidants, ultraviolet absorbers, plasticizers, and known charge generating substances can be added to the charge generation layer as necessary.
[0148]
The charge transport materials used include various triarylamine compounds, various hydrazone compounds, various styryl compounds, various stilbene compounds, various pyrazoline compounds, various oxazole compounds, various thiazole compounds, and various triarylmethane compounds. Compound etc. are mentioned.
[0149]
Examples of the binder resin used to form the charge transport layer 2 include acrylic resin, styrene resin, polyester, polycarbonate resin, polyarylate, polysulfone, polyphenylene oxide, epoxy resin, polyurethane resin, alkyd resin, and unsaturated resin. A resin selected from is preferred. Particularly preferred resins include polymethyl methacrylate, polystyrene, styrene-acrylonitrile copolymer, polycarbonate resin and diallyl phthalate resin.
[0150]
The charge transport layer 2 is generally formed by dissolving the charge transport material and the binder resin in a solvent and applying them. The mixing ratio (mass ratio) of the charge transport material and the binder resin is about 2: 1 to 1: 2. Solvents include ketones such as acetone and methyl ethyl ketone, esters such as methyl acetate and ethyl acetate, aromatic hydrocarbons such as toluene and xylene, chlorinated hydrocarbons such as chlorobenzene, chloroform and carbon tetrachloride, tetrahydrofuran, Ethers such as dioxane are used. When this solution is applied, for example, a coating method such as a dip coating method, a spray coating method and a spinner coating method can be used, and drying is preferably 10 ° C to 200 ° C, more preferably 20 ° C to 150 ° C. The temperature is in the range of 5 minutes to 5 hours, and more preferably 10 minutes to 2 hours.
[0151]
The charge transport layer is electrically connected to the above-described charge generation layer, receives charge carriers injected from the charge generation layer in the presence of an electric field, and transports these charge carriers to the interface with the protective layer. It has a function. Since this charge transport layer has a limit to transport charge carriers, the film thickness cannot be increased more than necessary, but it is preferably 5 to 40 μm, and particularly preferably 7 to 30 μm.
[0152]
Furthermore, an antioxidant, an ultraviolet absorber, a plasticizer, and a known charge transport material can be added to the charge transport layer as necessary.
[0153]
In the present invention, the protective layer is applied on the charge transport layer and cured to form a film.
[0154]
FIG. 2 shows a schematic configuration of an electrophotographic apparatus using a process cartridge having the electrophotographic photosensitive member of the present invention.
[0155]
In the figure, reference numeral 11 denotes a drum-shaped electrophotographic photosensitive member of the present invention, which is rotationally driven in a direction of an arrow about a shaft 12 at a predetermined peripheral speed. In the rotation process, the electrophotographic photosensitive member 11 is uniformly charged at a predetermined positive or negative potential on the peripheral surface thereof by the primary charging unit 13, and then from an exposure unit (not shown) such as slit exposure or laser beam scanning exposure. The exposure light 14 that is enhanced and modulated corresponding to the time-series electric digital image signal of the target image information to be output is received. In this way, electrostatic latent images corresponding to target image information are sequentially formed on the peripheral surface of the electrophotographic photosensitive member 11.
[0156]
The formed electrostatic latent image is then developed with toner by the developing means 15 and taken out from a paper feeding unit (not shown) between the electrophotographic photosensitive member 11 and the transfer means 16 in synchronization with the rotation of the electrophotographic photosensitive member 11. The toner image formed and supported on the surface of the electrophotographic photosensitive member 11 is sequentially transferred by the transfer means 16 to the transfer material 17 thus fed.
[0157]
The transfer material 17 that has received the transfer of the toner image is separated from the surface of the electrophotographic photosensitive member, introduced into the image fixing means 18, and subjected to image fixing to be printed out as an image formed product (print, copy). .
[0158]
After the image is transferred, the surface of the electrophotographic photosensitive member 11 is cleaned by the transfer unit 19 after the transfer residual toner is removed, and is further subjected to charge removal by pre-exposure light 20 from a pre-exposure unit (not shown). Used repeatedly for image formation. When the primary charging unit 13 is a contact charging unit using a charging roller or the like, pre-exposure is not always necessary.
[0159]
In the present invention, among the above-described components such as the electrophotographic photosensitive member 11, the primary charging unit 13, the developing unit 15, and the cleaning unit 19, a plurality of components are housed in a container 21 and integrally combined as a process cartridge. The process cartridge may be configured to be detachable from an electrophotographic apparatus main body such as a copying machine or a laser beam printer. For example, at least one of the primary charging unit 13, the developing unit 15, and the cleaning unit 19 is integrally supported together with the electrophotographic photosensitive member 11 to form a cartridge, and is attached to and detached from the apparatus body using the guide unit 22 such as a rail of the apparatus body A flexible process cartridge can be obtained.
[0160]
Further, when the electrophotographic apparatus is a copying machine or a printer, the exposure light 14 is a reflected light or transmitted light from a document, or a signal read by a document by a sensor, and a laser beam performed according to this signal. The light is emitted by scanning, driving the LED array, driving the liquid crystal shutter array, and the like.
[0161]
The electrophotographic photosensitive member of the present invention can be used not only in electrophotographic copying machines but also widely in electrophotographic application fields such as laser beam printers, CRT printers, LED printers, FAX, liquid crystal printers, and laser plate making. .
[0162]
【Example】
Next, an example explains the present invention. However, embodiments of the present invention are not limited to these. In addition, "part" in an Example shows a mass part.
[0163]
Example 1
An aluminum cylinder (JIS A3003 aluminum alloy) with a length of 260.5 mm and a diameter of 30 mm was used as a support, and a 5 mass% methanol solution of polyamide resin (trade name: Amilan CM8000, manufactured by Toray) was applied thereon by a dipping method. An undercoat layer having a thickness of 0.5 μm was provided.
[0164]
Next, it has a structure represented by the following formula as a charge generating substance, and has a crystal type having strong peaks at 9.6 ° and 27.3 ° with a Bragg angle 2θ ± 0.2 ° in the characteristic X-ray diffraction of CuKα. 4 parts of an oxytitanium phthalocyanine pigment,
[Outside 62]

[0165]
2 parts of polyvinyl butyral resin BX-1 (manufactured by Sekisui Chemical Co., Ltd.) and 110 parts of cyclohexanone were dispersed in a sand mill for 4.5 hours using glass beads having a diameter of 1 mm. Thereafter, it was diluted with 130 parts of ethyl acetate to obtain a charge generation layer coating material. This dispersion was applied onto the undercoat layer by a dipping method to form a charge generation layer having a thickness of 0.18 μm.
[0166]
Next, 7.5 parts of a charge transport material having a structure represented by the following formula:
[Outside 63]

[0167]
And 10 parts of bisphenol Z-type polycarbonate (trade name: Z-200, manufactured by Mitsubishi Gas Chemical Co., Ltd.) was dissolved in 60 parts of monochlorobenzene / 20 parts of dichloromethane. This solution was dip-coated on the charge generation layer and dried with hot air at 110 ° C. for 1 hour to form a charge transport layer having a thickness of 20 μm.
[0168]
Next, as a protective layer, 100 parts of antimony-doped tin oxide fine particles were surface-treated with 7 parts of a fluorine atom-containing compound (trade name: LS-1090, manufactured by Shin-Etsu Chemical Co., Ltd.) having a structure represented by the following formula ( (Treatment amount: expressed as 7%) 35 parts of treated tin oxide fine particles
[Outside 64]

[0169]
150 parts of ethanol was dispersed in a sand mill over 66 hours, 18 parts of polytetrafluoroethylene fine particles (volume average particle size 0.18 μm) were further added, and dispersion was further performed in a sand mill for 12 hours.
[0170]
Thereafter, as a resin component, 54 parts (nonvolatile content: 45%) of a resol-type curable phenol resin (trade name: PR-53123) manufactured by Sumitomo Durez Co., Ltd., and the compound No. 1 as a charge transport material having a hydroxyalkyl group. 15 parts of 1-23 was dissolved and diluted with 35 parts of ethanol to obtain a coating material for a protective layer.
[0171]
Using this paint, a film was formed on the previous charge transport layer by dip coating, followed by hot air drying at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. The dispersibility of the protective layer paint was good, and the produced protective layer was a uniform film without unevenness.
[0172]
The evaluation of the electrophotographic characteristics is that of a laser beam printer (trade name: LBP-NX: manufactured by Canon Inc.) in a normal temperature and normal humidity (23 ° C., 60% RH) environment and a normal temperature, low humidity (23 ° C., 10% RH) environment. Attached to a modified machine. The electrophotographic sensitivity is set so that the dark part potential becomes −700 V, and the amount of light necessary to lower the −700 V potential to −200 V by irradiating the laser beam with a wavelength of 780 nm is measured. did. 20 μJ / cm ² The potential when the amount of light was irradiated was measured as the residual potential Vr. Further, using the same laser beam printer, the initial transfer efficiency and the scraping amount due to the durability of 5000 sheets were measured.
[0173]
Separately from the evaluation on the electrophotographic photosensitive member, film hardness and volume resistivity were measured by separately preparing samples.
[0174]
The hardness of the protective layer was measured using a hardness meter (H100VP-HCU) manufactured by FISCHER, Germany. The hardness by this measurement is determined as follows.
[0175]
That is, a diamond pyramid with a tip angle of 136 ° is pressed with a square pyramid and pushed into the protective layer film to 1 μm. From the surface area of the indentation calculated from the geometric shape of the indenter and the load at that time, the following formula ( I) is obtained.
Universal hardness value HU (N / mm ² ) = Load (N) / Surface area of indentation under load (mm ² ) ... (I)
The hardness of the protective layer in this example was measured by applying a protective layer paint on a glass plate, and curing conditions were the same as in the preparation of the electrophotographic photosensitive member, and this protective layer film was applied 3 to 4 times. The film thickness was about 10 μm to obtain a hardness measurement sample.
[0176]
A sample for measuring volume resistivity was prepared by forming a comb-shaped electrode having a gap of 180 μm on a polyethylene terephthalate film by aluminum vapor deposition, and applying a protective layer coating similar to that applied on the electrophotographic photosensitive member onto the Meyer bar. Was applied with the same film thickness and dried with hot air under the same curing conditions as above to prepare a protective layer film.
[0177]
The volume resistivity was measured using a pA meter (4140B type) manufactured by Hewlett-Packard USA under the condition of an applied voltage of 100 V and an environment of temperature: 23 ° C. and humidity: 50%. The results are shown in Table 4.
[0178]
(Examples 2-9)
In the same manner as in Example 1, except that the charge transporting material shown in Table 4 was used instead of the charge transporting material having a hydroxyalkyl group (Compound No. 1-23) used in Example 1, the electrophotographic photosensitive material was used. A body and the like were prepared and evaluated. The results are also shown in Table 4.
[0179]
(Examples 10 to 13)
In Examples 1, 5, 6 and 9, the amount of antimony-doped tin oxide fine particles surface-treated with the compound represented by the fluorine atom-containing compound (treatment amount: 7%) was changed to 20 parts, methyl hydrogen silicone oil (trade name) : KF99, manufactured by Shin-Etsu Chemical Co., Ltd. (treatment amount: 20%) Examples 1, 5, 6 and 9 except that 15 parts of antimony-doped tin oxide fine particles were further added and dispersed to prepare a paint. And performed in the same manner. The results are also shown in Table 4.
[0180]
(Examples 14 to 17)
In Examples 1, 5, 6 and 9, in place of the antimony-doped tin oxide fine particles surface-treated with the fluorine atom-containing compound, antimony-doped tin oxide fine particles not subjected to surface treatment (trade name: T-1, Mitsubishi Materials Ex. 35) and 35 parts of the fluorine atom-containing compound (trade name: LS-1090, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and dispersed in the same manner as in Example 1. went. The results are also shown in Table 4.
[0181]
(Examples 18 to 21)
1.5 parts of methyl hydrogen silicone oil (trade name: KF99, manufactured by Shin-Etsu Chemical Co., Ltd.) was further added to the protective layer coating paint used in Examples 14 to 17, and the mixture was stirred for 4 hours. The procedure was the same as in Examples 14 to 17 except that the paint was used. The results are also shown in Table 4.
[0182]
(Examples 22 to 25)
35 parts of treated tin oxide fine particles and 150 parts of ethanol as in Example 1 were dispersed in a sand mill over 66 hours, and then 67 parts of the same phenol resin (nonvolatile content: 45% as a resin component) Further, 15 parts of the charge transport material of the present invention shown in Table 4 was dissolved and stirred for 4 hours to obtain a coating material for a protective layer.
[0183]
This paint was applied onto the photosensitive layer in the same manner as in Example 1 to provide a protective layer, and evaluated in the same manner as in Example 1. The results are also shown in Table 4.
[0184]
(Examples 26 to 30)
67 parts (nonvolatile content: 45%) of the same phenol resin as in Example 1, 21 parts of the charge transport material of the present invention and 82 parts of ethanol shown in Table 4 were dissolved and stirred for 4 hours to obtain a coating material for protective layer did.
[0185]
This paint was applied onto the photosensitive layer in the same manner as in Example 1 to provide a protective layer, and evaluated in the same manner as in Example 1. The results are also shown in Table 4.
[0186]
(Example 31)
Up to the charge transport layer was produced in the same manner as in Example 1.
[0187]
Next, instead of the phenol resin used in Example 1, as a protective layer, 42 parts (nonvolatile content: 58%) of a resol type curable phenol resin (trade name: PL-2211) manufactured by Gunei Chemical Industry Co., Ltd. As a charge transport material having a hydroxyalkyl group. 15 parts of 1-23 was dissolved to prepare a coating material for a protective layer.
[0188]
Using this paint, a film was formed on the above charge transport layer by dip coating, and then dried with hot air at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. The dispersibility of the protective layer paint was good, and the produced protective layer was a uniform film without unevenness. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 1. The results are also shown in Table 4.
[0189]
(Examples 32-35)
Instead of the charge transport material having a hydroxyalkyl group (Compound No. 1-23) used in Example 31, the charge transport material of the present invention shown in Table 4 was used. An electrophotographic photoreceptor was prepared and evaluated. The results are also shown in Table 4.
[0190]
(Examples 36 to 39)
52 parts (nonvolatile content: 58%) of the same phenol resin as in Example 31, 21 parts of the charge transport material of the present invention shown in Table 4 and 82 parts of ethanol were dissolved and stirred for 4 hours to obtain a coating material for protective layer did.
[0191]
This paint was applied onto the photosensitive layer in the same manner as in Example 1 to provide a protective layer, and evaluated in the same manner as in Example 1. The results are also shown in Table 4.
[0192]
(Example 40)
100 parts of antimony-doped tin oxide ultrafine particles were surface-treated with 7 parts of the above fluorine atom-containing compound (trade name: LS-1090, manufactured by Shin-Etsu Chemical Co., Ltd.) (hereinafter treated as 7%) and oxidized. Disperse 35 parts of tin fine particles and 150 parts of ethanol in a sand mill over 66 hours, add 18 parts of polytetrafluoroethylene fine particles (average particle size 0.18 μm), and further disperse in a sand mill for 12 hours. went. Thereafter, as a resin component, 54 parts (nonvolatile content: 45%) of a curable resol type phenol resin (trade name: PR-53123) manufactured by Sumitomo Durez Co., Ltd., and a hydroxy group which may have a substituent of the present invention As the charge transport material having a phenyl group, the above-mentioned compound No. 1 is used. 15 parts of 4-14 was dissolved and diluted with 35 parts of acetone to obtain a coating material for a protective layer.
[0193]
This paint was applied onto the photosensitive layer in the same manner as in Example 1 to provide a protective layer, and evaluated in the same manner as in Example 1. The results are also shown in Table 4.
[0194]
(Examples 41 to 45)
An electrophotographic photosensitive member was prepared in the same manner as in Example 40 except that the charge transport material (Compound No. 4-14) of the present invention used in Example 40 was replaced with the charge transport material shown in Table 4. ,evaluated. The results are also shown in Table 4.
[0195]
(Examples 46 to 48)
In Examples 40, 42 and 44, the amount of antimony-doped tin oxide fine particles surface-treated with the fluorine atom-containing compound was reduced to 20 parts, instead of methyl hydrogen silicone (trade name: KF99, Shin-Etsu Chemical) This was carried out in the same manner as in Examples 40, 42 and 44, except that 15 parts of antimony-doped tin oxide fine particles treated by Kogyo Co., Ltd. (treatment amount: 20%) were added and dispersed. The results are also shown in Table 4.
[0196]
(Examples 49 to 51)
In Examples 40, 42 and 44, instead of the antimony-doped tin oxide fine particles surface-treated with the fluorine atom-containing compound, antimony-doped tin oxide fine particles not subjected to surface treatment (trade name: T-1, Mitsubishi Materials Corporation) )) And 35 parts of the fluorine atom-containing compound (trade name: LS-1090, manufactured by Shin-Etsu Chemical Co., Ltd.) were added and dispersed in the same manner as in Examples 40, 42 and 44. I went. The results are also shown in Table 4.
[0197]
(Examples 52 to 54)
1.5 parts of methyl hydrogen silicone (trade name: KF99, manufactured by Shin-Etsu Chemical Co., Ltd.) was further added to the protective layer coating paint used in Examples 49 to 51, and the resulting mixture was stirred for 4 hours. The procedure was the same as in Examples 49 to 51 except that. The results are also shown in Table 4.
[0198]
(Examples 55-57)
35 parts of treated tin oxide fine particles and 150 parts of ethanol similar to Example 40 were dispersed in a sand mill over 66 hours, and then 67 parts of the same phenol resin (nonvolatile content: 45% as a resin component) Further, 15 parts of the charge transport material of the present invention shown in Table 4 was dissolved, diluted with 35 parts of acetone, and stirred for 4 hours to obtain a coating material for a protective layer.
[0199]
This paint was applied onto the photosensitive layer in the same manner as in Example 40 to provide a protective layer, and evaluated in the same manner as in Example 40. The results are also shown in Table 4.
[0200]
(Examples 58 to 64)
Up to the charge transport layer was prepared in the same manner as in Example 40.
[0201]
In 67 parts (nonvolatile content: 45%) of the same phenol resin as in Example 40, 21 parts of the charge transport material of the present invention shown in Table 4, 58 parts of ethanol, and 24 parts of acetone are dissolved and stirred for 4 hours. A protective layer coating was obtained.
[0202]
In the same manner as in Example 40, a film was formed on the charge transport layer by dip coating as in Example 40, followed by hot-air drying at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. Evaluation was performed in the same manner as in Example 40. The results are also shown in Table 4.
[0203]
(Example 65)
Up to the charge transport layer was prepared in the same manner as in Example 40.
[0204]
Next, as a protective layer, instead of the phenol resin used in Example 40, 42 parts (nonvolatile content: 58%) of a curable resol type phenol resin (trade name: PL-2211) manufactured by Gunei Chemical Industry Co., Ltd. Further, the compound No. 1 is used as the charge transport material of the present invention. 15 parts of 4-44 was dissolved to form a protective layer coating.
[0205]
Using this paint, a film was formed on the previous charge transport layer by dip coating, and then dried with hot air at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm. The dispersibility of the protective layer paint was good, and the produced protective layer was a uniform film without unevenness. The obtained electrophotographic photoreceptor was evaluated in the same manner as in Example 40. The results are also shown in Table 4.
[0206]
(Examples 66 to 68)
An electrophotographic photoreceptor and the like in the same manner as in Example 65 except that the charge transport material of the present invention (Compound No. 4-44) used in Example 65 is replaced with the charge transport material of the present invention shown in Table 4. Were made and evaluated. The results are also shown in Table 4.
[0207]
(Examples 69 to 74)
52 parts (nonvolatile content: 58%) of the same phenol resin as in Example 65, 21 parts of the charge transport material of the present invention shown in Table 4, 58 parts of ethanol and 24 parts of acetone were dissolved and stirred for 4 hours. A protective layer coating was obtained.
[0208]
A film was formed on the charge transport layer by dip coating as in Example 40, and then dried with hot air at 145 ° C. for 1 hour to form a protective layer with a thickness of 3 μm. And evaluated. The results are also shown in Table 4.
[0209]
(Examples 75 to 81)
In the same manner as in Example 1, except that the charge transporting material shown in Table 4 was used instead of the charge transporting material having a hydroxyalkyl group (Compound No. 1-23) used in Example 1, the electrophotographic photosensitive material was used. A body and the like were prepared and evaluated. The results are also shown in Table 4.
[0210]
(Examples 82 to 88)
In the same manner as in Example 26 except that the charge transport material shown in Table 4 was used instead of the charge transport material having a hydroxyalkyl group (Compound No. 1-23) used in Example 26, electrophotographic photosensitive A body and the like were prepared and evaluated. The results are also shown in Table 4.
[0211]
(Examples 89 to 92)
In the same manner as in Example 40, except that the charge transport material shown in Table 4 was used instead of the charge transport material (Compound No. 4-14) having a hydroxyalkyl group used in Example 40, electrophotographic photosensitive A body and the like were prepared and evaluated. The results are also shown in Table 4.
[0212]
(Examples 93 to 96)
In the same manner as in Example 58, except that the charge transport material shown in Table 4 was used instead of the charge transport material having a hydroxyalkyl group (Compound No. 4-6) used in Example 58, electrophotographic photosensitive A body and the like were prepared and evaluated. The results are also shown in Table 4.
[0213]
[Table 4]

[0214]
[Table 5]

[0215]
[Table 6]

[0216]
[Table 7]

[0217]
(Comparative Example 1)
The charge transport layer was prepared in the same manner as in Example 1.
[0218]
Next, as a protective layer, the same resol type curable phenolic resin (trade name: PR-53123) manufactured by Sumitomo Durez Co., Ltd. as used in Example 1 was diluted to form a paint, and the film was formed by dip coating. Formed. Then, it dried with hot air at 145 degreeC for 1 hour, formed the protective layer with a film thickness of 3 micrometers, produced and evaluated the electrophotographic photoreceptor. The results are also shown in Table 5.
[0219]
(Comparative Example 2)
The charge transport layer was prepared in the same manner as in Example 1.
[0220]
Next, as a protective layer, the same resol type curable phenolic resin (trade name: PL-2211) manufactured by Gunei Chemical Industry Co., Ltd. used in Example 31 was diluted to form a paint, A film was formed. Then, it dried with hot air at 145 degreeC for 1 hour, formed the protective layer with a film thickness of 3 micrometers, produced and evaluated the electrophotographic photoreceptor. The results are also shown in Table 5.
[0221]
(Comparative Examples 3 to 10)
The charge transport layer was prepared in the same manner as in Example 1.
[0222]
As the resin component, 67 parts (non-volatile content: 45%) of a resole type curable phenol resin (trade name: PR-53123) manufactured by Sumitomo Durez Co., Ltd. as in Example 1 was used, and the hydroxy used in Example 1 was further used. Instead of the charge transport material having an alkyl group (Compound No. 1-23), 21 parts instead of Comparative Compounds 1 to 8 represented by the following formula were dissolved in 400 parts of 1,4-dioxane and 180 parts of THF. It stirred for time and was set as the protective layer coating material.
[Outside 65]

[0223]
Using this paint, a film was formed on the previous charge transport layer by spray coating, followed by hot air drying at 145 ° C. for 1 hour to form a protective layer having a thickness of 3 μm, and evaluated in the same manner. The results are also shown in Table 5.
[0224]
(Comparative Examples 11 and 12)
Instead of the protective layer in Example 1, 35 parts of the treated tin oxide fine particles and 150 parts of 1,4-dioxane used in Example 1 were dispersed in a sand mill over 66 hours, and further polytetrafluoroethylene fine particles 18 parts (average particle size 0.18 μm) was added, and the mixture was further dispersed in a sand mill for 12 hours. Thereafter, 24 parts of polymethyl methacrylate (trade name: J-899, manufactured by Hoshi Kogaku Kogyo Co., Ltd.) is dissolved in place of the curable phenol resin as a resin component, and 15 charge transport materials of the present invention shown in Table 5 are further added. Partly dissolved, further dispersed with a sand mill for 1 hour, diluted with 700 parts of 1,4-dioxane and 370 parts of THF to obtain a coating material for a protective layer.
[0225]
Using this paint, a film was formed on the charge transport layer by spray coating, and then dried with hot air at 100 ° C. for 30 minutes to form a protective layer having a thickness of 3 μm. Evaluation was performed in the same manner as in Example 1. The results are also shown in Table 5.
[0226]
(Comparative Example 13)
In Example 1, it carried out like Example 1 except not having applied a protective layer. The results are also shown in Table 5.
[0227]
[Table 8]

[0228]
As shown in Tables 4 and 5, by using the electrophotographic photosensitive member having the protective layer of the present invention, the decrease in sensitivity due to the protective layer and the increase in the residual potential are small, and the transfer efficiency is high. Furthermore, the film strength is maintained, the abrasion resistance is maintained, and it is highly durable and highly stable.
[0229]
Further, since the volume resistivity of the protective layer according to the present invention is sufficiently high, a clear and good image can be obtained without causing the flow of the formed electrostatic latent image. On the other hand, since the protective layers shown in Comparative Examples 3 to 12 have a low volume resistivity, image quality deterioration due to the flow of the electrostatic latent image was observed.
[0230]
【The invention's effect】
As described above, according to the present invention, it is possible to obtain a good image with high transfer efficiency, high durability, high stability, and a small decrease in sensitivity and increase in residual potential of an electrophotographic photoreceptor provided with a protective layer. It has become possible to provide an electrophotographic photoreceptor that can be used.
[0231]
In addition, in the process cartridge and the electrophotographic apparatus having the electrophotographic photosensitive member, a remarkable effect can be similarly obtained.
[Brief description of the drawings]
FIG. 1 is a diagram showing a layer structure of an electrophotographic photosensitive member of the present invention.
FIG. 2 is a diagram showing an example of a schematic configuration of an electrophotographic apparatus using a process cartridge having the electrophotographic photosensitive member of the present invention.
[Explanation of symbols]
1 Protective layer
2 Charge transport layer
3 Charge generation layer
4 Conductive support
5 binding layers
6 Underlayer
11 Electrophotographic photoreceptor
12 axes
13 Charging means
14 Exposure light
15 Development means
16 Transfer means
17 Transfer material
18 Fixing means
19 Cleaning means
20 Pre-exposure light
21 Process cartridge container
22 Guide means

Claims (14)

In an electrophotographic photosensitive member having a photosensitive layer and a protective layer on a support, the protective layer contains a curable phenol resin and may have a hydroxyalkyl group, a hydroxyalkoxy group and a substituent. An electrophotographic photoreceptor comprising a charge transport material having at least one group selected from the group consisting of: The electrophotographic photosensitive member according to claim 1, wherein the charge transport material has a hydroxyalkyl group. The electrophotographic photosensitive member according to claim 2, wherein the charge transport material has a structure represented by a formula selected from the group consisting of the following formulas (1) to (3).
[Outside 1]

(Wherein R ₁₁ , R ₁₂ and R ₁₃ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched; α, β and γ are each a halogen atom or a substituent as a substituent; It may have one or more alkyl groups that may have, alkoxy groups that may have substituents, aryl groups that may have substituents, and heterocyclic groups that may have substituents. Represents a benzene ring, a1, b1 and c1 are 0, and m1 and n1 are 0 or 1.)
[Outside 2]

(Wherein R ₂₁ , R ₂₂ and R ₂₃ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and δ and ε each have a halogen atom or a substituent as a substituent. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and a benzene ring optionally having one or more optionally substituted heterocyclic groups A2, b2 and c2 are 0. m2, n2 and p2 are 0 or 1, and all are not simultaneously 0. τ and υ are each a halogen atom or a substituent as a substituent. It may have one or more alkyl groups that may have, alkoxy groups that may have substituents, aryl groups that may have substituents, and heterocyclic groups that may have substituents. Represents a benzene ring, where τ and υ form a ring together through a substituent. You may do it.)
[Outside 3]

(Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and ζ, η, θ and ι are each a halogen as a substituent. One or more atoms, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent Represents a benzene ring which may have, a3, b3, c3 and d3 are 0, m3, n3 and p3 are 0 or 1. φ and χ each have a halogen atom and a substituent as a substituent. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and a benzene ring optionally having one or more optionally substituted heterocyclic groups In addition, φ and χ may form a ring jointly through a substituent. .) The electrophotographic photosensitive member according to claim 1, wherein the charge transport material has a hydroxyalkoxy group. The electrophotographic photosensitive member according to claim 4, wherein the charge transport material has a structure represented by a formula selected from the group consisting of the following formulas (1) to (3).
[Outside 4]

(Wherein R ₁₁ , R ₁₂ and R ₁₃ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched; α, β and γ are each a halogen atom or a substituent as a substituent; It may have one or more alkyl groups that may have, alkoxy groups that may have substituents, aryl groups that may have substituents, and heterocyclic groups that may have substituents. Represents a benzene ring, and a1, b1 and c1 are 0 or 1, and all are not simultaneously 0. m1 and n1 are 0 or 1.)
[Outside 5]

(Wherein R ₂₁ , R ₂₂ and R ₂₃ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and δ and ε each have a halogen atom or a substituent as a substituent. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and a benzene ring optionally having one or more optionally substituted heterocyclic groups A2, b2 and c2 are 0 or 1, and all are not simultaneously 0. m2, n2 and p2 are 0 or 1 and are not all 0 at the same time. And υ each have a halogen atom as a substituent, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, or a substituent. Represents a benzene ring which may have one or more good heterocyclic groups Incidentally, tau and υ may form a ring jointly through a substituent.)
[Outside 6]

(Wherein R ₃₁ , R ₃₂ , R ₃₃ and R ₃₄ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and ζ, η, θ and ι are each a halogen as a substituent. One or more atoms, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent A3, b3, c3 and d3 are 0 or 1, and all are not simultaneously 0. m3, n3 and p3 are 0 or 1. φ and χ Are each a halogen atom as a substituent, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, an aryl group that may have a substituent, or a complex that may have a substituent. A benzene ring that may have one or more ring groups. χ may form a ring jointly through a substituent.) The electrophotographic photosensitive member according to claim 1, wherein the charge transport material has a hydroxyphenyl group which may have a substituent. The electrophotographic photosensitive member according to claim 6, wherein the charge transport material has a structure represented by a formula selected from the group consisting of the following formulas (4) to (6).
[Outside 7]

(In the formula, R ₄₁ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched, and R ₄₂ has a hydrogen atom, an alkyl group which may have a substituent, or a substituent. Represents an aralkyl group which may have a substituent and a phenyl group which may have a substituent, Ar ₄₁ and Ar ₄₂ each have an alkyl group which may have a substituent, an aralkyl group which may have a substituent, and a substituent; An aryl group that may be substituted, or a heterocyclic group that may have a substituent, Ar ₄₃ represents an arylene group that may have a substituent, or a heterocyclic group that may have a divalent substituent. M4 and n4 are each 0 or 1. However, when n4 = 0, m4 = 0, κ and λ are each a halogen atom as a substituent, an alkyl group which may have a substituent, a substituent An alkoxy group which may have a group, an aryl group which may have a substituent, Have one or more heterocyclic group which may have a substituent represents a benzene ring.)
[Outside 8]

(In the formula, R ₅₁ represents a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ₅₁ and Ar ₅₂ have an alkyl group which may have a substituent, and a substituent. Represents an aralkyl group which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group which may have a substituent, and μ and ν represent a halogen atom as a substituent and an alkyl which may have a substituent, respectively. A group, an alkoxy group that may have a substituent, an aryl group that may have a substituent, and a benzene ring that may have one or more heterocyclic groups that may have a substituent. , Μ and ν may form a ring together through a substituent, and m5 is 0 or 1.)
[Outside 9]

(In the formula, R ₆₁ and R ₆₂ each represent a divalent hydrocarbon group having 1 to 8 carbon atoms which may be branched. Ar ₆₁ has an alkyl group which may have a substituent, or a substituent. Represents an aralkyl group that may be substituted, an aryl group that may have a substituent, or a heterocyclic group that may have a substituent, where ξ, π, ρ, and σ each have a halogen atom or a substituent as a substituent. An optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryl group, and an optionally substituted heterocyclic group (Note that ξ and π, and ρ and σ may form a ring together through a substituent, and m6 and n6 are 0 or 1, respectively.) The electrophotographic photosensitive member according to claim 1, wherein the curable phenolic resin is a resol type phenolic resin. The electrophotographic photosensitive member according to claim 1, wherein the protective layer contains conductive fine particles. The electrophotographic photosensitive member according to claim 9, wherein the conductive fine particles are tin oxide that may be surface-treated or doped. The electrophotographic photosensitive member according to claim 1, wherein the protective layer contains a fluorine atom-containing compound and fluorine atom-containing resin fine particles. The electrophotographic photosensitive member according to claim 1, wherein the protective layer contains a fluorine atom-containing compound, fluorine atom-containing resin fine particles, and a siloxane compound. The electrophotographic photosensitive member according to any one of claims 1 to 12 and at least one means selected from the group consisting of a charging means, a developing means and a cleaning means are integrally supported and detachably attached to the main body of the electrophotographic apparatus. Process cartridge characterized by being. An electrophotographic apparatus comprising the electrophotographic photosensitive member according to claim 1, a charging unit, an exposure unit, a developing unit, and a transfer unit.

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